Greenhouse Gases - Ed. by Bernardo Llamas Moya and Juan Pous

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Greenhouse Gases
Edited by Bernardo Llamas Moya and Juan Pous

Greenhouse Gases
Edited by Bernardo Llamas Moya and Juan Pous
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Contents
Preface
Chapter 1 The Changing Landscape of Energy Management in

Manufacturing
by Elliot Woolley, Yingying Seow, Jorge Arinez and Shahin
Rahimifard
Chapter 2 The Choice between Economic Policies to Face Greenhouse

Consequences
by Donatella Porrini
Chapter 3 Energy for Sustainable Development: The Energy–Poverty–

Climate Nexus
by Melanie L. Sattler
Chapter 4 Native Forest and Climate Change — The Role of the

Subtropical Forest, Potentials, and Threats
by Silvina M. Manrique and Judith Franco
Chapter 5 Greenhouse Gas Emissions – Carbon Capture, Storage and

Utilisation
by Bernardo Llamas, Benito Navarrete, Fernando Vega, Elías
Rodriguez, Luis F. Mazadiego, Ángel Cámara and Pedro Otero
Chapter 6 Review of Recent Developments in CO2 Capture Using Solid

Materials: Metal Organic Frameworks (MOFs)
by Mohanned Mohamedali, Devjyoti Nath, Hussameldin Ibrahim
and Amr Henni
Chapter 7 Carbon Dioxide Geological Storage (CGS) – Current Status

and Opportunities
by Kakouei Aliakbar, Vatani Ali, Rasaei Mohammadreza and Azin
Reza
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VI Contents
Chapter 8 Methane Emissions from Rice Production in the United States

— A Review of Controlling Factors and Summary of Research
by Kristofor R. Brye, Alden D. Smartt and Richard J. Norman
Chapter 9 Greenhouse Gases Production from Some Crops Growing

Under Greenhouse Conditions
by Fernando López-Valdez , Fabián Fernández-Luqueño ,
Carolina Pérez-Morales and Mariana Miranda-Arámbula
Chapter 10 Mitigating Greenhouse Gas Emissions from Winter

Production of Agricultural Greenhouses
by Lilong Chai, Chengwei Ma, Baoju Wang, Mingchi Liu and
Zhanhui Wu
Chapter 11 Livestock as Sources of Greenhouse Gases and Its

Significance to Climate Change
by Veerasamy Sejian, Raghavendra Bhatta, Pradeep Kumar
Malik, Bagath Madiajagan, Yaqoub Ali Saif Al-Hosni, Megan Sullivan and
John B. Gaughan
Chapter 12 Life Cycle Assessment Method – Tool for Evaluation of

Greenhouse Gases Emissions from Agriculture and Food Processing
by Zuzana Jelínková, Jan Moudrý Jr, Jan Moudrý, Marek Kopecký
and Jaroslav Bernas
Chapter 13 Carbon Footprint as a Tool to Limit Greenhouse Gas

Emissions
by Francesco Fantozzi and Pietro Bartocci
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Preface
Sustainability should be a key component of every process,

safeguarding resources and reserves for future generations.
This book shows how a responsible use of resources is possible,
offering valid technological alternatives to fight climate change.
We offer current technologies and valid methods for a wide range of

activities: teaching, investigation, work, business and even daily life.
We encourage all our readers to join us and become part of the
solution to climate change, rather than the problem.
After reading this book, we are certain that you will find justified
reasons to start your own personal and social awareness campaign
in favour of these effective technologies against climate change.
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Chapter 1
The Changing Landscape of Energy Management in

Manufacturing
Elliot Woolley, Yingying Seow, Jorge Arinez and Shahin Rahimifard
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/62227
Abstract
The production and use of energy accounts for around 60% of global greenhouse
gas (GHG) emissions, providing an intrinsic link between cause and effect. Consid‐
ering that the manufacturing industry is responsible for roughly one-third of the
global energy demand enforces the need to ensure that the manufacturing sector
continually strives to reduce its reliance on energy and thus minimise GHG re‐
leased into the atmosphere. Consequently, efficient management of energy con‐
sumption is of paramount importance for modern manufacturing businesses due to
well-documented negative impacts regarding energy generation from fossil fuels
and rapidly rising worldwide energy costs. This has resulted in a proliferation of re‐
search in this area which has considered improvements in energy consuming activi‐
ties at the enterprise, facility, cell, machine and turret levels. However, there is now
a need to go beyond incremental energy efficiency improvements and take more
radical approaches to reduce energy consumption. It is argued that the largest ener‐
gy reduction improvements can be achieved through better design of production
systems or by adopting new business strategies that reduce the reliance of manufac‐
turing businesses on resource consumption. This chapter initially provides a review
of research in energy management (EM) at various manufacturing focus levels. The
inappropriateness of current methods to cater for transformative and radical energy
reduction approaches is discussed. In particular, limitations are found at the busi‐
ness strategy level since no technique exists to consider the input of these high level
decisions on energy consumption. The main part of the chapter identifies areas of
further opportunity in energy management research, and describes a method to fa‐
cilitate further reductions in energy use and GHG production in manufacturing at
the business strategy level.
Keywords: Energy management, Greenhouse gases, business strategy, manufacturing,

sustainability
2 Greenhouse Gases
1. Introduction
There are two facts about the future of energy that we know: we will not be able to gener‐
ate the same quantities from easily accessible fossil-based sources as we currently do, and in
the short term this shortfall in energy supply will not be met by ‘renewable’ sources based
on current projections of investment and development [1]. In addition, energy consump‐
tion is currently increasing (see Figure 1) and is expected to increase by 22% by 2020 compared
to 2011 [2], due partly to increases in demand from China and India [3]. These factors will
create what has been termed the ‘energy gap’ [4]: the difference between demand for energy
and the ability to supply this demand, although it should be noted that demand is influ‐
enced by supply. The precise magnitude of this energy gap is difficult to predict but it will
have a severe influence on the way energy is consumed in the foreseeable future.
Figure 1. Total primary energy supply of resource by 1993, 2011 and 2020 (data from [2])
The management of energy consumption within the manufacturing sector is particularly

important since it is one of the largest energy consuming sectors, directly and indirectly
responsible for one-third of global energy use and carbon emissions [5]. This high level of
manufacturing related energy consumption is particularly true in developed and developing
countries [6]. Energy security is therefore vital for the future of the manufacturing industry
and provides a significant incentive to reduce consumption levels. Other incentives also exist
in the form of rising energy costs, national and international legislation and consumer demand
for greener products. This need has not gone unnoticed and a wide range of approaches have
been implemented by companies to reduce reliance on non-renewable (fossil-based) energy
sources by improving management practices of energy consuming activities.
These EM techniques have been, in general, quite successful for specific applications but are
limited in their scope and so can only ever have a predetermined impact on an enterprise’s
energy performance. Historically research and the resulting EM techniques have focused on
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The Changing Landscape of Energy Management in Manufacturing 3
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current manufacturing operations and management practices and have therefore tackled
problems that can be solved by existing industrial companies. However, modern manufac‐
turing businesses are under ever-increasing pressures to deliver innovative solutions for
highly complex tasks for adaptability, economic performance, maintainability, reliability, and
scalability. The “Factory of the Future” [7] has to be adaptable not only to the needs of the
market but also to the growing requirements for economic and ecological efficiency. Further‐
more, such factories will have to take into consideration increased levels of social responsibility
and, in particular, environmental sustainability. Based on these challenges, the need for
development and validation of new industrial models and strategies is relevant for industrial
transformation. These competitive sustainable manufacturing models and strategies will have
to aim at achieving long-term economic sustainability through an increase in added value and
improved production capability, responsiveness and quality as well as environmental
sustainability through the decrease in the consumption of raw materials, water and energy.
The shape of manufacturing is therefore changing as life cycle approaches become more
important for impact assessment and the use of ecological data to influence process planning
becomes necessary to meet the environmental performance characteristics demanded by
government, industry and consumers. In addition new business-strategies1 are being explored
[8–9], with a wide spectrum of product service systems, remanufacturing and product
upgradeability, all likely standard models for the future of sustainable manufacturing
industries.
This chapter, which identifies the existing trends in EM research for the manufacturing sector
and develops new EM regimes that are important for continued advances in energy rational‐
isation, is divided into three main sections:
• A brief review and analysis of existing EM techniques for manufacturing with a short
discussion on developing new EM techniques for evolving manufacturing approaches;
• A more detailed discussion regarding the need for the consideration of business strategies
within EM for manufacturing, with the development of a procedure to facilitate this
consideration; and finally,
• A case study to demonstrate the applicability of the developed EM procedure for the
business strategy manufacturing level.
2. Review of Existing EM Techniques
Manufacturing enterprises and facilities can be highly complex, where monitoring energy
consumption and associated GHG production can be cumbersome and expensive. Using a
1 In this work, business strategy defines the approach in which a manufacturer takes to fulfil the need or want of the
customer. The manufacturer will supply a solution through either the provision of a product or service (which uses a
product) and can, therefore, be a short-term or long-term interaction with the customer. Similarly, the business strategy
also defines where and when and how often manufacturing processes are undertaken. In short, business strategy defines
the model by which a company seeks to generate profit from its customers, but which is also linked to its suppliers and
external governing bodies.
4 Greenhouse Gases
well-structured framework can help industrialists identify where to focus their efforts to
achieve maximum energy savings. One structured approach to analysing a manufacturing
system is to decompose the system hierarchically. A variation of the ‘shop floor production
model’ as developed by the International Organisation for Standardization (ISO) can be used
to categorise research conducted on various levels. The adapted model has five levels, ranging
from a high level to a specific scope. The levels and the energy considerations for each are
summarised as follows:
1. Enterprise level – supply chain of materials or components, network of production sites,

inventory hubs, sales and distribution centres, R&D and the integration of various plants.
2. Facility level – building envelope, heating, ventilation and air-conditioning (HVAC),

infrastructure of the facility and site energy generation.
3. Production/machine cell level – planning, production engineering and management,

supply of material resources and maintenance.
4. Machine level – operation and control of equipment, lighting, cooling, work done on
material and communication systems.
5. Turret or tool-chip level – actual transformation of material.
Further, Vijayaraghavan and Dornfeld [10] also suggested that at each level of analysis, there
is a corresponding temporal scale of decision making that ranges from several days at the
enterprise level to micro-seconds at the tool-chip level. The range of variation in the analysis
and temporal scales along with the types of decisions that are made at each level is shown
in Figure 2. It is considered by the authors that although the temporal timescales suggested
by Vijayaraghavan and Dornfeld [10] are suitable for rapid, high-volume manufacturing
processes (e.g., low-tech electronics), for products that are highly complex (e.g., jet engines)
or for products that have very long product runs (e.g., cars), these decision timescales need
to be extended. This is particularly the case when a decision is based on the use of suffi‐
cient historical data (which needs to be collected and interpreted). The current research
considers temporal timescales between minutes (real-time) and years (strategic).
The following sections use the structure described above to briefly review some of the
techniques for EM and minimisation published in recent academic literature. The review is
not intended to be comprehensive (see [11] for a review with a wider scope) but is intended
to show the shape of research in this field with respect to decision time scales for each
manufacturing level. As will be shown, existing research (in EM) falls into the manufacturing
level-timescale relationship described by Vijayaraghavan and Dornfeld [10]. This research is
concerned with identifying the opportunities and needs for EM techniques that lie outside of
this existing envelope. These new areas of energy consideration in manufacturing are shown
in Figure 3.
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Figure 2. Energy considerations at different manufacturing levels. Adapted from [10].
Figure 3. Energy considerations in manufacturing. Existing research predominantly in dark grey areas. New areas de‐
scribed in this research shown in light grey.
6 Greenhouse Gases
2.1. Energy Research on an Enterprise Level

Manufacturing enterprises extend beyond the walls of a factory that just produces goods; they
encompass a range of activities from supply chain of materials or components to manufactur‐
ing processes and the logistics of the finished product. This involves a network of production
sites, suppliers, inventory hubs as well as sales and distribution centres.
Various studies have reported techniques for EM at the enterprise level. Concentrating on
logistics Kara and Manmek [12] found that the embodied energy of products could be reduced
by selecting local suppliers and avoiding road transport for high quantities of raw materials
over long distances. Their model focused on energy, materials and emissions, and waste with
considerations for how each of these are used or produced within lengthy supply chains.
Supplier location was shown to be a significant factor that can increase or reduce the embodied
energy of the raw materials. A similar study [13] used Google Maps to carefully plan and
optimise the embodied energy of transportation at the enterprise level. Both approaches
require detailed data regarding transport modes and routes and, in the event of instigating
changes, may require extensive replanning of multiple cross-linked supply chains. In addition,
Kara et al. [14] detail a methodology for assessing the impact of global manufacturing on the
embodied energy of products. They studied six different products manufactured from various
raw materials in a global manufacturing network and found that product, material and key
supply chain parameters played a crucial role.
Other research on the enterprise level has identified that energy improvements can be obtained
by changing manufacturing models (e.g., Seliger et al. [15] showed that a phone that is
remanufactured consumes less energy than a phone that has been sent to a land fill, over the
production, use and end-of-life phases). This is because the remanufacturing pathway, despite
requiring energy input into the reverse logistics, avoids repeating manufacturing steps with
characteristically high energy consumption and environmental emissions.
The globalisation of businesses has led to long and multi-tiered supply chains, making the
introduction of improvements across the entire enterprises complex and difficult. This has
been reflected in the number of studies that have been carried out at the enterprise level with
most publications focussing on case studies and observed trends rather than on new method‐
ologies [11]. In general, the higher costs, coordination effort and complexity and communica‐
tion difficulties of implementing sustainable supply chains has led companies to focus on
internal activities that present far more achievable environmental (and financial) gains over
shorter time periods.
2.2. Energy Research on a Facility Level

Research on the facility level primarily focuses on modelling and reducing the energy
consumed by infrastructure and other high level services such as ventilation, lighting, heating
and cooling. On-site energy generation is also taken into account.
A review of potential energy savings of a typical manufacturing facility has been performed
[16] and focused on high-level redesign strategies. It was concerned with the potential energy
saving that can be achieved through optimised building shape and form, improved building
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envelopes, improved efficiencies of individual energy using devices, alternative energy using
systems in buildings, and through enlightened occupant behaviour and operation of building
systems. In addition, a method for measuring plant-wide industrial energy savings that takes
into account changing weather and production between the pre- and post-retrofit periods has
been presented [17].
As a barrier to EM at the facility level, it has been highlighted there is a distinct lack of
manufacturing energy performance indicators (EPIs), and this has led to difficulties of
modelling ‘plant level’ energy consumption [18]. Benchmarking energy is essential for EM
program development, yet it has been noted that most industries have not, or at least have not
been able to, benchmark energy use across their plants. Combining the American Energy Star
performance rating system with EPIs, it has been possible to quantify the average energy
consumed for the manufacture of best practice vehicles [18]. On a more generic level, the
development of energy performance benchmarks and building energy ratings for non-
domestic buildings have been reported [19]. They outlined a methodology to develop energy
benchmarks and rating systems starting from the very first step of data collection from the
building stock.
Finally, on the facility level an economic comparison of three cogeneration steam systems for
a wood pulping mill was carried out [20], finding that economic and environmental optimi‐
sation could not be achieved simultaneously.
2.3. Energy Research at the Machine Cell Level

At this level, research focuses on planning, production engineering and management, supply
of material resources, transport waste material processing and maintenance. Energy flows are
closely related to the running of these activities that may be affected by production plans,
scheduling times and parameters.
Much of the research reported on the production level involves process planning and process
routing for improved energy performance, although most research focuses on costs and cycle
times. There is a lack of tools for optimising process flows based on sustainable development
objectives (environmental), and those that have been proposed have few practical results [21].
In an attempt to bridge this gap, Tan et al. [21] combined manufacturing process planning and
environmental impact assessments using a checklist analysis. They proposed an optimal
decision making method for new components that include energy consumption as part of the
sustainable development evaluation.
In addition, He et al. [22] have developed green manufacturing process planning and support
systems where the raw materials, secondary materials and energy consumption, and other
environmental impacts of process planning were optimised. This was supported with
databases and model repositories. Integration of the optimisation of energy consumption of
processes as part of the process selection algorithm in a process planning program is also
possible as and has been demonstrated [23].
Information is critical on a production level: Chiotellis et al. [24], Müller and Löffler [25] and
Herrmann et al. [26] have all proposed various information formats to aggregate energy values
8 Greenhouse Gases
for decision making on a production level. These groups specifically noted a current lack of
monitoring of energy flows within factories. In addition to the lack of monitoring systems, the
amount of information required can be very complex and requires a robust framework to deal
with information on all levels. They suggest that having online monitoring of the energy
consumption within a factory not only provides greater energy transparency, but also provides
a stream of useful information to be used for maintenance repair and overhaul. To facilitate
this, they have introduced the concept of EnergyBlocks, which can help planners to evaluate
the energy consumption profile of various alternatives and to deduce optimal system config‐
uration. However, data volumes increase (almost exponentially) as you move down the
manufacturing levels, and it is therefore important to set the correct resolution through
appropriate hardware and software systems.
Muller and Loffler’s [25] approach to the same problem provides guidance on energy-related
decision making during the planning procedure, from the product definition to energy
monitoring of the implemented plant. The availability of energy-related data in industry
during the planning process is still very rare, and so the main challenge is the development of
energy data standards for life cycle engineering (LCE) tools. They have suggested the devel‐
opment of energy performance ratios to influence more detailed standards and instruments
such as the dynamic simulation of energy demands.
The correlation of energy usage with operations being performed in the manufacturing system
through event stream processing techniques has been successfully implemented [10]. The
framework temporally analyses the energy consumption and operational data of machine tools
and other manufacturing equipment to enable decision making to improve the environmental
performance of the machine tools.
2.4. Energy Research Associated with Production Machines and Equipment
Research associated with the machine level has been concentrated in two subcategories: the
energy consumption of the machine for the ‘work done’ processes and the energy requirement
of the machine for auxiliary processes (e.g., cooling and control).
Cooperative Effort on Modelling Process Emissions in Manufacturing (CO2PE!) is an interna‐

tional initiative [27] to cluster forces in different continents, involving machine builders as well
as academics, to analyse existing and emerging manufacturing processes for their ecological
impact in terms of direct and indirect emissions. Substantial research has been targeted to
document, analyse and reduce process emissions for a wide range of available and emerging
manufacturing processes [24, 28–31].
In the life cycle phases of product manufacturing, the focus of resource efficiency moves from
the material applied per unit to resources used in the various production phases, for example,
cooling lubricants, compressed air or hydraulic oil and on the energy requirements of the
production processes [24]. Process relevant information is based on equipment energy
consumption curves. Each curve is specific to a production equipment item and enables an
accurate determination of the energy consumption of the item over the production time.
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Similarly, Overcash et al. [32] produced an engineering rule-of-practice-based analysis of

separate unit processes used in manufacturing. The information is collated in the form of a
unit process life cycle inventory, which then helps to evaluate the manufactured products
through the quantification of various parameters, including input materials, energy require‐
ments, material losses and machine variables.
In the context of an integrated consideration of economic and ecological impact, energy profiles
are an important basis for deriving optimisations to improve sustainability in manufacturing
[33]. On the process level, these profiles permit the identification of substantial energy drivers
in machines. In addition, the process-specific energy assessment has taken a step further to
develop generalised ‘equipment-level’ energy models, using average energy intensities of
different manufacturing processes to evaluate the efficiency of processing lines [34]. They
concluded that modern processes enable smaller dimensions and scales to be produced with
larger specific electrical energy requirements. They indicated that energy requirements
depend on the production rate and are consequently not constant as assumed by Life Cycle
Assessment software packages like Simapro or Umberto.
Dahmus and Gutowski [35] tracked energy flows when characterising the environmental
impact of machining, making a distinction between the energy required for chip formation
and operating the manufacturing equipment (Figure 4). In their studies, they showed that
machine tools with increasing levels of automation reveal higher basic energy consumptions
that result from the amount of additional integrated machine components.
Figure 4. Machining energy use breakdown for a 1988 Cincinnati Milacron automated milling machine with a 6.0 kW
spindle motor [35].
10 Greenhouse Gases
More specifically, a study on the energy consumption of cutting found that high speed cutting
required less energy per unit manufactured compared to the conventional cutting speed [36].
They also found that the installation of kinetic energy recovery systems (KERS) can reduce
average power consumption by up to 25% depending on workpiece geometry and machining
time. As the energy efficiency of the system is highly part specific, a KERS should be custom
defined. A framework has also been developed [37] for the recovery of waste heat energy from
manufacturing processes.
Along the same theme, the improvement potential in two types of manufacturing equipment
for discrete part production has been discussed [29]. Power requirements for activities in a
machine tool was investigated and classified into productive and non-productive periods.
In contrast, however, Fleschutz et al. [38] conducted an energy simulation on 12 similar

industrial robots within a workstation and found that the assigned operations strongly
influenced the energy consumption of the respective robot. Even though the operating hours
are the same for the robots, those that had more kinematic movements and little idle time
resulted in energy consumptions that were double the other robots.
Process conditions and energy consumption are not normally static but depend directly on the
specific conditions of the process and/or the production setting. The initiation of energy labels
for production machines indicating the amount of electrical energy consumed for various
production processes has been proposed [30]. Such information can be estimated by summa‐
rizing the electrical energy consumptions of single machine components (pumps and engines)
or by using energy profiles to reveal the holistic energy absorption that is needed by machine
tools.
There are, however, significant challenges in obtaining sufficient energy consumption data. It
has been proposed that in the future, both the manufacturer of equipment and the operator
should use consistent parameters to describe the energy performance of manufacturing
systems and that equipment should have standardised metering ports [39].
2.5. Energy Research on the Turret Level (Theoretical Process Energy)
The lowest and most focused manufacturing level is the turret level, which represents the
actual material transformation process itself. Energy assessment and management at this level
involves knowledge of the interactions of the mechanical and chemical processes in order to
establish theoretical energy consumption values of the process.
The research and application of improvement in energy efficiency at the turret level is highly
process specific and therefore less appropriate to general application. As a reflection of this,
less research has been published at this level. Most research is evaluative with little scope
provided for developing models. Consequently, only a few examples reviewed here are used
in further analysis in this chapter.
At this focus level, it has been shown that in machining, the ideal process energy is independent
of operating parameters such as tool speed, feed and depth of cut [40]. Instead the machining
energy is dependent on setup parameters, such as choice of cutting fluid, tool rake angle and
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part design parameters (material selection and the volume of material removed). Draganescu
et al. [41] conducted experiments to model machine tool efficiency so that the specific con‐
sumed energy could be determined for establishing cutting parameters and the consumed
energy necessary for removing a certain quantity of chips. Amongst many examples of
theoretical mathematical modelling of machine processes, Draganescu et al. [41] and Kalpak‐
jian and Schmid [42] have looked at the specific energy consumption for milling, and Ghosh
et al. [43] have modelled the specific energy requirement of deep grinding.
Other studies of theoretical energy consumption of other manufacturing process can be found
in [42] who give detailed explanations and descriptions of the energy required for cutting,
forming and deformation. A detailed analysis on the specific cutting energy for bandsawing
different work piece materials has been carried out [44]. The minimal energy required for
turning and the optimal conditions for machining a product has been studied [45] and finally
Kuzman and Peklenik [46] have done an energy evaluation of cold forming processes.
3. An Overview of the Current Scope of EM
There are clearly a large number of EM techniques that manufacturers can implement in order
to reduce their energy consumption and their generation of GHGs. These techniques focus on
many different aspects, and it can be confusing for manufacturers to decide which approaches
are best for their particular setup. One way of categorising these different EM techniques is to
define the temporal decision timescale. Within manufacturing, EM decisions can be made on
one of four timescales: real-time (minutes-hours), operational (days-weeks), tactical (months)
and strategic (years), with EM techniques at these levels being implemented by different
groups of people who operate at different management levels.
Positioning the EM techniques reviewed in this chapter into a research map (Figure 5) that has
manufacturing level and decision timescale as its axes reveals almost intuitive results. The
more focused (lower manufacturing level) an EM technique, the shorter the timescale on which
decisions can be made: adjusting machine setup parameters (turret level) can be done by one
person in a few minutes, whereas reconfiguring a supply chain (enterprise level) will take a
team of people months or even years. In the research map, this correlation seems linear, but
since the x-axis is not continuous and the y-axis is not quantitatively scaled, a strict correlation
is undefinable and inappropriate. Nonetheless, there are clear areas of the map that are not
occupied by any of the reviewed EM techniques, and it is therefore suggested that there is a
need for research to be undertaken to address these areas.
There are two areas of research in the current map (Figure 5) that would benefit from a growth
research: lifecycle process system planning and eco-intelligent manufacturing and agile supply
chains. A further area of research, not currently represented on the above map, is required to
look at the impact on energy consumption of existing and future business strategies. These
three research opportunities are discussed in the following sections, with EM at the business
strategy level given a more in-depth consideration due to the importance of its potential for
limiting GHG production (energy consumption) in order to meet a specific customer need.
12 Greenhouse Gases
Figure 5. Research map showing the relation between manufacturing level and associated decision timescale. The mid-
grey region is heavily populated, whereas EM techniques at for short-term facility and enterprise energy consumption
and long-term process level energy consumption are largely undeveloped.
3.1. Lifecycle Process System Planning
Recently, as with products, manufacturers are beginning to take a life cycle view of not just
their factories, but also the processes within the factories [47]. Primarily for economic reasons
but also from an environmental point of view they are beginning to consider how best to ensure
their machinery is maintainable and upgradeable, and what will happen to it at its end of life.
Such a task can be highly complex since it is difficult to predict the requirement of future or
long-term process capabilities, process utilisation levels and also production floor layouts. Life
cycle process planning is, therefore, heavily dependent on a company’s ability to roadmap the
sector it operates in. However from an environmental perspective, it is highly important to be
able to consider the resource intensity of processes throughout their lifetime. A host of life
cycle process planning tools are therefore required to assist manufacturers in managing their
long-term process requirements. For this, they require the development of an assessment
framework and decision support tool to understand the life cycle impact of individual
processes and process chains so that strategic decisions can be made about the purchase or
upgrade of machinery to ensure minimal environmental and economic impact.
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Such a suite of tools requires a consideration of energy consumption to ensure the processes
are able to integrate with the long-term energy supply strategy of a particular facility. Life
cycle process EM should consider flexible, reconfigurable process chains, peripheral energy
requirements (cooling, transport systems, etc) and factory layout to ensure the most appro‐
priate planning is carried out. EM tools developed in this area will need to provide manufac‐
turers with clear strategies for the minimisation of process energy consumption over periods
of many years. Such considerations will be key to the development of eco-efficient factories
for sustainable industrial systems.
3.2. Eco-Intelligent Manufacturing and Agile Supply Chains
At the short end of the temporal decision timescale on the research map, there currently exists
another area where no or very few EM techniques exist. In this region, which covers manu‐
facturing levels between cell and enterprise, manufacturers are beginning to consider new
short-term influences on their production and operations processes to improve economic and
environmental performance. As part of a holistic approach, they require techniques to help
them manage their energy consumption at this timescale.
At the production cell and factory levels, real-time consideration is required to be sensitive
to energy availability, which may come from several sources (almost certainly involving
traditional fossil-based energy) and which for any renewable component may vary in supply.
In such circumstances, it is necessary to be able to rapidly influence production scheduling
to ensure that energy intensive processes are carried out at periods of higher renewable
energy availability to maximise the environmental benefit from this type of energy. Smart
metering and smart energy grids are required to influence this eco-intelligent manufactur‐
ing. In fact, a new production planning regime, ‘environmental resource planning’, is required
to not just take into account the immediate availability of energy supply mix, but a full range
of eco-indicators, including emissions, water consumption, idle time of processes, and staff
availability.
There is also a need for industry to be able to consider and manage energy at the enterprise
level, but on the short real-time and operational timescales. Supply chains have historically
been set up to optimise for time and cost to give manufacturers the best possible competitive
advantage. However, this approach has led to disadvantages in fluctuating markets and
increasingly, manufacturers are seeking to remain resilient by creating flexible reactive supply
chains. The Triple-A Supply Chain described by Lee [48] promotes the need for agile supply
chain arrangements that are able to respond to short-term changes in supply, allowing rapidly
changing consumer demands or unforeseen disruptive events to be more easily worked
around. The energy implications in an agile supply chain need to be managed even if it might
not be a primary consideration. It is important for companies to be able to account for the
resources that are required for their products from a life cycle approach, which includes being
able to optimise the supply chain. Methods for systematically reacting to supply and demand
problems are being developed [48] and incorporated into everyday business practices. EM
techniques that are able to consider and influence these short-term reactive changes to supply
14 Greenhouse Gases
chain operation will be essential for improving and maintaining environmental performance
in the future manufacturing industry.
3.3. Energy Management at the Business Strategy Level

The preceding reviewed and hypothesised EM techniques for manufacturing are suitable for
current make-sell business models that are optimised for economic benefit. Since profit is
generated from the sale of products, successful manufacturing businesses have historically
been those that produce and sell more than their competitors: a culture that has led to a
disregard for resource consumption and pollution levels. This practice is now changing as
businesses and consumers become more aware of, and active in achieving long-term sustain‐
ability. Manufacturers are investigating and implementing radical new strategies to remain
commercially competitive whilst reducing resource consumption. It is therefore proposed here
that new EM techniques will be required to support these new manufacturing business
strategies.
The field of manufacturing has seen many improvements in sustainability performance over
the last few decades. Strategies to reduce waste, lower emissions, improve energy efficiency,
and so on have been implemented across the board but such activities have largely made
improvements for individual processes only. In the long term, industrial sustainability will
not be achieved simply by the development of new technologies or the utilisation of iterative
improvements of current production processes. Accordingly, the appropriateness of existing
business models are being challenged [49–51] for a future of industrial sustainability. The
configuration of the industrial system will evolve dramatically, introducing new concepts such
as cradle-to-cradle [52], slow manufacturing, local manufacturing [53], product service
systems [9], and product compatibility and upgradeability [54].
An additional manufacturing level is required to consider implications of cost, energy and
other resource consumption for these new business strategies [55]. Since for manufacturers the
primary consideration in choosing a business strategy will always come down to cost and
profit, it is unlikely that any manufacturing activities will be fully optimised for energy
efficiency. However, by being able to understand how energy can be considered, measured
and managed at this high level, significant energy improvements could still be made. Through
the development of new EM techniques, it is important to be able to consider the life cycle
manufacturing energy consumption of products as well as the life cycle energy consumption
of manufacturing processes and facilities used to produce these products. Figure 6 shows an
updated and simplified version of the EM technique research map, which includes the
proposed business strategy manufacturing level. Preliminary guidelines for the consideration
of energy consumption factors at this business strategy level are discussed by comparing two
different business strategies for furniture.
Two distinct and simple business strategies for manufacturing household furniture may be
described as the provision of either low-cost, short lifespan, or expensive, long lifespan
products. The decision on which strategy to take is made at the conception stage of the business
and may depend upon existing supply chain links, market opportunities or available work‐
force skill set for example. It is unlikely that such a strategic decision would ever be made
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Figure 6. Manufacturing level-decision timescale map showing positioning of required focus for EM to contribute to‐
wards industrial sustainability.
purely on the merits of energy consumption levels, but the decision itself has a significant
implication on energy use. Table 1 shows some differences between the individual approaches
for the manufacture of the furniture. EM techniques are required to assess the different impacts
of the two strategies to enable effective EM decisions to be made.
For the short life products, the manufacturer requires a rapid production throughput, and low
cost, lightweight materials are likely to be used, which can be quickly manufactured. Because
of the highly competitive low selling price of the short-life goods, profit margins are low and
therefore there is an economic need to have high volumes of production ensuring that the
market remains in constant need of new furniture. For this type of production, low manufac‐
turing costs are essential and so rapid, highly efficient and centralised manufacture is of key
importance, and therefore, the embedded energy [56] per product is likely to be relatively low.
Short-life furniture Long-life furniture
⋅ Energy efficient process ⋅ High quality processes
⋅ Rapid production ⋅ Quality-driven production
⋅ Automated production ⋅ Semi-automated production
⋅ High throughput ⋅ Low throughput
⋅ Low profit margins ⋅ High profit margins
Table 1. A comparison of different manufacturing considerations for short- and long-life furniture.
16 Greenhouse Gases
Conversely, for long life products, materials and manufacturing processes are quality driven
with less regard for cost, which will be easily recuperated by high profit margin sale prices.
As the products are intended to last a long time, the manufacturer is keen on brand awareness
and will ensure their products are of the highest quality. Slower, more energy intensive
procedures are likely to be used with additional finishing, inspection and testing processes.
Distributed manufacture from small facilities is likely to be preferred to be adaptable to
regional market requirements. For this type of product, the embedded energy per unit is likely
to be relatively high.
Since the object of manufacturing is to provide a functional unit for a particular market need,
a key indicator is the length of time a product fulfils a need. The longer the life of the product
with respect to energy consumed, the more energy efficient the manufacturing of the product.
This energy per product year, EPY, can be expressed in simple terms as EPY = energy required
for manufacture/product lifetime.
Applying this measure to the present example we can consider that the total energy consump‐
tion required for an item of furniture is the summation of embedded product energy, EE, and
amortised (i.e., per product) energy from the lifetime of the production processes (i.e., the
energy required to produce, maintain and repair the process machinery), EP, and the amortised
energy from the facility, EF, then the energy attributed to each year of the product’s life can be
expressed as EPY= (EE+ EP+ EF)/LP, where LP is the average anticipated product life in years. Note
that if the producer has responsibility for the disposal of the product at its end of life, the energy
requirement for this also needs to be considered in the above equation. Other considerations
at this business strategy level might include the possibility of remanufacture (lowering future
EE), availability of renewable energy (lowering the impact of EE), production at low energy
demand periods and maintenance contracts.
The product lifetime is of utmost importance in the case where significantly different lifetimes
of products are being considered. In this example of furniture, it is not unreasonable to assume
an order of magnitude difference in lifespan. Assuming there is no significant difference
between the production energy, the business strategy that manufactures longer life furniture
will be preferable.
Regardless of which business strategy is used, the process of considering the energy con‐
sumption factors throughout the life cycle of the products can be used to influence the selection
of manufacturing processes, facilities, facility operation times, and so on. Clearly, as with EM
techniques at lower manufacturing levels, approaches at the business strategy level require
availability of suitably reliable or indicative data, or appropriate assumptions. In addition
because of the complexity of different business models, such high level EM may require
significant input from techniques focussing at lower levels of EM (e.g., HVAC control to reduce
EE) to yield the best results.
There is a need for the development of new EM techniques at the business strategy level that
assist manufacturers not only in deciding which production models are least energy intensive,
but also in minimising energy consumption at the highest level with an integrated approach.
Importantly, such EM techniques need data for the specific stages in a product’s life cycle for
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which the manufacturer is responsible. By using energy per product year as the unit of
measure, it is possible to compare between dissimilar manufacturing and business approaches.
The general approach suggested here is a three stage consideration of energy at the business
strategy level. In the first stage, it is essential to set the boundaries and contributing factors for
energy consumption. Boundaries will include everything that a manufacturer is responsible
for or has direct control over during the entire product/s life time and could extend to the
supply chain, providing sufficient information is available. Contributing factors should focus
on high level energy consuming tasks such as embodied product energy, impact of energy
sources, embodied life cycle energy of the factory infrastructure, post-life product responsi‐
bility and life span of manufactured product.
The second stage in the approach requires an understanding of the relationship between
different energy considerations, assignment of appropriate variables and development of any
relationships between factors. In most cases, it will be useful to evaluate the total energy
consumption per product year for which the manufacturer is directly responsible (i.e., not
during use cycle). It is not important to fully understand the details of each energy contributing
factor, but it is important to understand how certain factors relate to one another. An example
of this is described in Section 4.
The third and final stage is to identify the factor(s) that have the largest energy contribution
and make improvements in these areas as appropriate.
Obviously, the current approach is generalised but is intended to give guidance for the
development of future EM techniques for decisions at the business strategy level. Of key
importance is sufficient understanding of the impact of business strategy on energy consump‐
tion and the specific actions that can be taken to reduce this reliance on energy.
4. A Case Study for EM Method at the Business Strategy Level
The life cycle approach for considering energy at the business strategy level can be applied to
any product, provided that sufficient consideration is given to the contributing factors. The
level of detail can be adjusted to allow for different levels of data availability or understanding,
but it is important to assess the need for different energy consumption factors within the life
cycle of the product.
It may be criticised that consideration of some factors are difficult at the business strategy
planning stage. However, it is not necessarily essential to have firm data in order to be able to
assess different strategies; sensible assumptions can be used to evaluate the energy implica‐
tions of business strategies. The following example compares different business strategies for
the manufacturing and provision of steel roofing material using energy data from [12].
Considerations for energy consumption should include manufacture of the sheeting, transport,
maintenance or replacement and any energy consumption or benefit from end-of-life man‐
agement. The data used for this case study is shown in Table 2.
18 Greenhouse Gases
Factor Values
Steel sheet production #

178 MJ/m2
Transport# 2 MJ/m2
Replacement section manufacture 3.6 MJ/m2 year
Maintenance of roof 3.6 MJ/m2 year
End of life management# -48 MJ/m2
#
Data from [12].
Table 2. Numerical values used for comparison between PSS and sale business strategies for steel roofing.
A manufacturer may evaluate the benefit with respect to energy consumption of supplying
galvanised steel roof sheeting under a product service system (PSS) basis as opposed to the
more common make-sell business model. Under a PSS, the building owner does not actually
own the roofing material (ownership remains with the producer) but lease it on a fixed term
basis (e.g., for the period of occupation of the building) with maintenance costs being covered
by the producer. The ‘user’ simply pays for the use of the roofing. Setting the boundaries of
the comparison between manufacturing processes carried out in-house by the manufacturer
and the end-of-life management of the galvanised steel sheeting, Table 3 shows the different
factors for consideration in this scenario.
Factor Sale PSS Values/Assumptions
Steel sheet production (MJ/m2) Ex,prod Ey,prod Ex,prod=Ey,prod = 178

Transport (MJ/m ) 2
Ex,tran Ey,tran Ex,tran=Ey,tran = 2
Replacement section manufacture (MJ/m2 year) Ex,rep 0 Ex,rep= Ex,prod/50 = 3.6
Maintenance of roof (MJ/m year)
2
0 Ey,mnt Ey,mn= Ey,prod/50 = 3.6
End-of-life management (MJ/m2)* 0 Ey,eol Ey,eol = -48
Lifetime (years) z kz z = 20 years
k, the ratio of the life of the PSS roofing to the life of the customer owned roofing.
*If the manufacturer instigates the recycling of the material, they can justify off-setting any energy benefit against their
manufacturing energy consumption.
Table 3. Energy consumption factors considered for comparison between PSS and sale business strategies for steel
roofing.
Using the factors from Table 3 in the equation EPY= (EE+ EP+ EF)/LP, the energy per product year
can be written for the sale and PSS business strategies, respectively, as Ex,py=((Ex,prod + Ex,tran)/z)
+ Ex,rep and Ey,py=((Ey,prod + Ey,tran + Ey,eol)/kz) + Ey,mnt.
These two basic expressions can be used to determine the significant contributing factors of
both the roofing sale and PSS strategies. Since from the above we can obtain the equality ((Ex,prod
+ Ex,tran)/z) + Ex,rep = ((Ey,prod + Ey,tran)/z) + Ex,mnt, then we can obtain, Ey,py= (Ex,py/k)+ (Ey,eol/kz).
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Using the values from Table 3, and given that it can be shown that Ex,py = 9.8 MJ/yr/m2, we find
that, Ey,py=(7.4/k).
Thus it can be shown that if k > 0.76, then it will always be beneficial from a manufacturer’s
energy perspective to opt for the PSS strategy. In the PSS strategy, since the manufacturer
generates income from each year the roofing material is in service, rather than from a one-off
income generated through the sale of the steel sheeting, the value of k will likely be greater
than 1. The incentive to prolong the life of the product by the manufacturer means that addition
care may be taken in the maintenance of the roofing, at the expense of Ey,mnt.
Based on the given example, to make the sale strategy more competitive in terms of energy,
manufactures could focus on methods of extending the life of the roofing (e.g., by additional
coatings) or significantly reducing the embedded product energy (which will likely have a
negative impact on life expectancy). As no actual energy is consumed at the business strategy
level, energy improvements will ultimately come from the implementation of EM techniques
at lower manufacturing levels.
In the given case study, it is possible to introduce additional terms into this comparison which
may look at energy implications such as process machinery and infrastructure life cycle energy
costs, warranty repair, supply chain PSS, for example, depending on the company’s scope and
business model.
Using the three stage approach proposed in this chapter it is possible to compare between
different business strategies using limited data or assumptions. The output will give an
indication as to the energy consumption factors that need to be considered in more detail to
ensure the overall minimisation of energy use for manufacturing activities. However, signifi‐
cant work is required by academia and the manufacturing industrial sector to develop more
focused EM techniques for the business strategy level.
5. Concluding Discussions
The need for EM and rationalisation within manufacturing has led to the development of a
very large number of EM techniques. These techniques cover issues from machine–tool
interaction to distribution logistics and supply chain management. A review of a cross-section
of EM techniques has revealed a correlation between the manufacturing levels and decision
timescale. As a consequence, there are areas of research that have not yet been addressed, such
as the life cycle evaluation of production processes and the short-term management of energy
supply and supply chain operations. This chapter asserts that there is a requirement for EM
techniques to be developed in these currently uninhabited research spaces since manufacturers
are continually searching for ways to reduce energy costs and improve environmental
performance. Considerations for approaches to developing EM for life cycle impact of
production processes include flexible, reconfigurable process chains, factory layouts and
upgradability and maintainability. For eco-intelligent factories and reactive supply chains,
energy supply security, production flexibility and supply chain agility will form the corner‐
stones of EM for manufacturers of the future.
20 Greenhouse Gases
In addition, as manufacturers consider more radical ways of reducing their environmental

impact and maintaining market share in volatile consumer markets, new business strategies
are being considered to generate income in ingenious ways. These new strategies are being
developed with economic benefit as the primary focus, but it is also important for manufac‐
turers to consider EM of these strategies to minimise the energy consumption of their activities
in the long term. Therefore, building on the existing scope of EM techniques which have
focussed on the manufacturing levels, this work suggests that new techniques need to be
developed for an additional manufacturing level, namely business strategy, which is posi‐
tioned above the enterprise level in the hierarchy. The business strategy level has been shown
to be slightly different from the other manufacturing levels in that no energy is actually
consumed at this level, but energy consumption for products and services are largely defined
by decisions at this level. It is therefore reasoned that approaches to EM for business strategies
should consider the energy expenditure that the manufacturer has direct control over for the
life cycle of the product. This approach allows different business models to be evaluated using
the same core framework, even if the strategies are markedly different.
A three stage high level procedure has been described for EM at the business strategy level,
which consists of definition of scope and energy contributing factors, identification of inter‐
relationships between energy factors and a comparison of potential strategies and finally a
focus on the largest energy consuming factors using techniques from lower manufacturing
levels. Of key importance at the business strategy level is that there is no requirement for
detailed energy data that may be difficult to obtain at a planning stage. Instead, comparisons
may be made between strategies based on a few well-grounded assumptions.
In summary, as manufacturing businesses become more energy aware and seek to remain
competitive in highly transient and environmentally focused markets, new business strategies
and increased production flexibilities are being explored. The manufacturing industry is
evolving for the better, and new EM techniques will be essential in supporting this revolution.
Author details
Elliot Woolley1*, Yingying Seow2, Jorge Arinez3 and Shahin Rahimifard1
*Address all correspondence to: e.b.woolley@lboro.ac.uk
1 Centre for Sustainable Manufacturing and Recycling Technologies (SMART), Wolfson

School of Mechanical and Manufacturing Engineering, Loughborough University, Lough‐
borough, UK
2 Jacobs, New City Court, London, UK
3 Manufacturing Systems Research Lab, General Motors R&D Center, Michigan, USA
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[52] Braungart, M., Mcdonough, W., and Bollinger, A., 2007. Cradle-to-cradle design: Cre‐
ating healthy emissions – A strategy for eco-effective product and system design,
Journal of Cleaner Production, 15, 1337–1348.
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[53] Kumar, K., 2004. From Post-industrial to Post-modern Society: New Theories of the Con‐
temporary World, 2nd ed. Hoboken: Wiley-Blackwell.
[54] Li, Y., Xue, D., and Peihua, G., 2008. Design for product adaptability, Concurrent En‐
gineering, 16, 221–232.
[55] Woolley, E., Sheldrick, L., Arinez, J., and Rahimifard, R., 2013. Extending the boun‐
daries of energy management for assessing manufacturing business Strategies, Pro‐
ceedings of the 11th Global Conference on Sustainable Manufacturing, Berlin, Germany.
[56] Seow, Y., Rahimifard, S., and Woolley, E., 2013. Simulation of energy consumption in
the manufacture of a product, International Journal of Computer Integrated Manufactur‐
ing, 26 (7), 663–680.
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Chapter 2
The Choice between Economic Policies to Face

Greenhouse Consequences
Donatella Porrini
http://dx.doi.org/10.5772/62255
Abstract
In the past few years, unstable and extreme weather patterns are increasingly
occurring as phenomena of climate change, and the link to greenhouse gas (GHG)
emissions is scientifically accepted. From an economic point of view, extreme weather
patterns are causing major damage to health, property, and business.
In this chapter, following an economic analysis of law (EAL) approach, the issue of
the comparison between the alternative environmental economic policies is analyzed
starting from the consideration that the emissions of GHGs originate market failures:
the environment appears as a “public good” that may not be appropriated and has
no market price; the damage to the environment is a case of “externality,” where it is
fully or partly a social cost that is not internalized into the accounts of the parties
causing it. In the EAL literature, an environmental policy instrument has been seen
as it may play a role in correcting malfunction and subsequent inefficiencies.
In the first part of the chapter, we intend to revise the traditional analysis of the choice
of environmental policies. The following part deals with the comparison between tax
and tradable permit systems. Then the role that can be played by the insurance sector
is considered. The different policy instruments are considered in the framework of
climate as an economic global public good. And, finally, some conclusive remarks are
presented in relation to the COP 21 conference in Paris in terms of the future policies
against GHG effects.
Keywords: climate change, environmental policy choice, insurance, greenhouse gasses,

COP 21
28 Greenhouse Gases
1. Introduction
Over the last centuries, climate change has been raised as a very important issue all over the
world. The change in climate results from an increase in the earth’s average atmospheric
temperature, which is usually referred to as global warming. It may be due to both natural
and human causes, especially greenhouse gas (GHG) emissions.
In response to increasing scientific evidence that human activities are contributing significantly
to global climate change [1], decision makers are devoting considerable attention to public
policies to reduce GHG emissions and thereby prevent or reduce such change.
The policies span a range of regulatory approaches. The main alternative is between command
and control (CAC) and market-based (MB) instruments, and a relevant role can also be played
by the insurance sector.
This chapter aims to describe the traditional theory on the choice of environmental policies
following an economic analysis of law (EAL) approach (Section 2) to analyze the comparison
between tax and tradable permit systems (Section 3), to outline the role of the insurance sector
(Section 4), and to consider the different policy instruments in a context of economic global
public goods. The final objective is to take into account the future COP 21 conference in Paris
in terms of the choice of policy instruments against GHG effects.
2. The traditional issue of the choice of environmental policies
The problem of the choice of environmental policy instruments has been an issue since Pigou
[2] analyzed the need for state intervention when private costs diverge from social costs and
suggested that the solution would be to internalize the externalities through taxation.1 Coase
[4] criticized the proposed state intervention and affirmed that there is no reason to suppose
that governmental regulation is called for simply because the problem is not very well handled
by the market or the firm.
The ensuing debate has been conducted along these two opposite views: on the one hand, the
supporters of the idea that the choice of policy instruments is to be applied as a public matter
and the state, as policy designer, should select the optimal instruments and take responsibility
for their imposition in the public interest, but, on the other, the supporters of MB instruments
are trying to fight a battle against a sort of “anti-market” mentality based on a reluctance to
apply MB instruments [5].
So the problem would be to compare the instruments that can be considered public oriented
and those that can be considered market oriented, where the former is characterized by a public
agency that defines a conduct rule and provides an enforcement system and the latter is
characterized by instruments based on market mechanisms stimulating the conduct of the firm
indirectly and by a private administration and enforcement system.
1 See the documents of the “Pigou club” [3].
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The Choice between Economic Policies to Face Greenhouse Consequences 29
http://dx.doi.org/10.5772/62255
Following an EAL approach, traditionally regulatory systems originate from the presence of
market failure: in our specific case, the environment appears as a “public good” that may not
be appropriated and has no market price; the damage to the environment is a case of “exter‐
nality,” in that it is fully or partly a social cost that is not internalized into the accounts of the
parties causing it.2 So the comparison of different instruments can consider how they may play
a role in correcting malfunction and subsequent inefficiencies [7].
In this way, we can move from the theoretical definition of the efficiency of different instru‐
ments to their practical, and so direct, potential to achieve concrete objectives. In particular,
the objectives that emerge as relevant in judging the practical efficiency of environmental
policies are the following: first is the prevention in the sense of providing incentives for firms
to improve safety standards, and second is the connection with technological change in the
sense of encouraging firms to adopt lower risk technologies.
The first kind of environmental instrument is the so-called CAC that is characterized by a
public agency that provides a definition of conduct rules and enforcement system. Thus, they
could be defined as public-oriented instruments, which require the use of a particular tech‐
nology or the observation of a performance standard, authorizing for the maximum amount
that a source can emit.
CAC is divided into two phases as follows: “command”, which sets a standard based on the
maximum level of permissible emissions, and “control”, which monitors and enforces the
standard.
Regarding standards, they can be classified into two: ambient standards, which fix a minimum
desired level of air or water quality or a maximum level of emissions that must be maintained,
and emission standards, which fix a maximum level of permitted emissions that can be
performance based, setting emission limits that each firm is allowed, or technology based,
specifying the best technology to be used.3
As to the US experience with this kind of regulation, the activity of the Environmental
Protection Agency (EPA) provides a clear example of regulation by an independent environ‐
mental authority. This agency performs its tasks through the setting of preventive standards,
the enforcement of polluting emission thresholds, and the performance of inspections and,
possibly, of actions brought to the federal courts. We cannot mention the European Commun‐
ity experience given that a standard setting system has not been established at a European
level (but at national level) and that the European Environmental Agency (EEA) has only a
very limited role.4
2 Economists consider environmental policies within the framework of the category of externalities, as evidenced by
Cropper and Oates [6]: “The source of basic economic principles of environmental policy is to be found in the theory of
externality.”
3 As Cropper and Oates [6] explain“…The determination of environmental policy is taken to be a two-step process: first,
standards or targets for environmental quality are set, and, second, a regulatory system is designed and put in place to
achieve these standards. This is often the environmental decision making proceeds. Under the Clean Air Act, for example,
the first task of the EPA was to set standards in the form of maximum permissible concentration of the major air pollutants.
The next step was to design a regulatory plan to attain these standards air quality.”
30 Greenhouse Gases
The choice to develop a CAC regulatory system is based on the advantage of centralized
agencies to assure a cost-effectiveness calculation on the base of the expected damage and of
the marginal cost of different level of preventive care. The centralized structure presents the
advantage to provide a continual oversight of problems and a broad array of regulatory tools.
Following the traditional EAL approach, well-defined standards generate the correct incentive
for the firm to act with caution and make the best production and prevention decisions [8, 9].
CAC instruments use to be compared with MB instruments that are characterized by a private
administration and enforcement system and stimulate indirectly the behavior of the firm.
There are essentially two different types of those instruments: taxes that are fees imposed on
emitters proportionate to the total amount of emissions released into the environment (they
could be divided into emission charges, product charges, and user charges) and marketable
(or tradable) permit systems that provide a fixed number of permits equal to the allowed total
emissions, distributing them among polluting firms in a specific area.
The two types of MBI instruments can be seen in the following two different approaches: on
one side, taxes follow a price approach because producers adjust the quantity, given a fixed
price put on emissions; on the other side, a tradable permit system follows a quantity approach
because the price is adjusted according to supply and demand, given a maximum quantity of
emissions allowed.
3. Carbon tax versus tradable permit system
A carbon tax is a particular tax based on GHG emissions generated by burning fuels and
biofuels, such as coal, oil, and natural gas. It has been introduced with the main goal to level
the gap between carbon intensive (firms based on fossil fuels) and low carbon intensive (firms
that adopt renewable energies) sectors. Due to the introduction of that form of taxation, the
relative prices of goods and services will change; the emissions of intensive goods will be more
expensive, whereas the emissions of less intensive goods will be lower. Thus, carbon tax
provides a strong incentive for individuals and firms to adjust their conduct, resulting in a
reduction of the emissions themselves. Hence, by reducing fuel emissions and adopting new
technologies, both consumers and businesses can reduce the entire amount they pay in carbon
tax.
A tradable permit system is defined as quantity-based environmental policy instrument. The

regulatory authority stipulates the allowable total amount of emissions (cap) and the right to
emit becomes a tradable commodity. Under a cap-and-trade system, prices are allowed to
fluctuate according to market forces. Thus, the price of emissions is established indirectly.
Permits could be allocated to firms through auction or free allocation.
4 The EEA was set up as a legally independent community body under council regulation (EEC) 1210/90. The EEA’s core
task is to provide decisionmakers with the information needed for making sound and effective policies to protect the
environment and support sustainable development.
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Similarly to other environmental taxes, carbon taxes are defined as priced-based policy
instruments for the correlated effects to increase the price of certain goods and services, thereby
decreasing the quantity demanded. On the other side, tradable permits are defined as quantity-
based environmental policy instrument. Although both policy instruments are MB, their
implementation is different: carbon taxes fix the marginal cost for carbon emissions and allow
quantities emitted to adjust, whereas tradable permits fix the total amount of carbon emitted
and allow price levels to change according to market forces.
Which is better? There is no simple yes or no answer, and the policies are not necessarily
mutually exclusive. Several important advantages and drawbacks of the respective policies
are outlined later.
A well-functioning emission trading system allows emission reductions to take place wherever
abatement costs are lowest, regardless of international borders. As costs associated with
climate change have no correlation with the origin of carbon emissions, the rationale for this
policy approach is that an emission trading system allows to fix a certain environmental
outcome and the companies are called to pay a market price for the rights to pollute. This is
the reason why an emission trading system is suitable for international environmental
agreements, such as the Kyoto Protocol, specifically for the characteristic that a defined
emission reduction level can be easily agreed between states.
Emission trading is more appealing to private industry because, by decreasing emissions, firms
can actually profit by selling their excess GHG allowances. Creating such a market for pollution
could potentially drive emission reductions below targets.
A carbon tax would offer a broader scope for emission reductions [10]. A system of tradable
permits entails significant transaction costs, which include search costs, such as fees paid to
brokers or exchange institutions to find trading partners; negotiating costs; approval costs; and
insurance costs. Conversely, taxes involve little transaction cost over all stages of their lifetime.
Carbon taxes are dynamic economic instruments that offer a continuum incentive to reduce
emissions. In fact, technological and procedural improvements and their subsequent efficient
diffusion lead to reductions in tax payment. In addition, trading systems are able to self-adjust
because emission goals will be easier to meet; there will be a decrease in permits’ demand and
in their price but not as rapidly as taxes.
The implementation of an emission trading system is very complicated and requires technical
steps, including treatment of sinks, monitoring, and enforcement. On the other hand, taxation
is a very well-known instrument by policy makers, not very costly because it does not require
monitoring and enforcement organization.
The revenue from carbon taxes can be used into the economy to reduce income taxes or levies
on labor or capital investment. This may be part of a national or international reform of the
taxation systems with the effects to shift the tax burden from “goods” like labor to “bads” like
pollution.
In Table 1, we have summarized the main differences among CAC, carbon tax, and tradable
permit system.
32 Greenhouse Gases
Command and control Carbon tax Tradable permit system
No. But price volatility can be

Certainty over CO2 Yes. The tax establishes a well- limited by design features, such
No
price or cost? defined price as a safety valve (price cap) or
borrowing
No. Regulating the rate of No. Emissions vary with Yes, in its traditional form. No,
Certainty over
emissions, the level uncertain prevailing energy demand and with the use of additional cost
emissions?
leaves fuel prices containment mechanisms
Efficiently encourages No, but tradable standard is

least-cost emission more efficient than non- Yes Yes
reductions? tradable standard
Yes. Results in maximum

Ability to raise
No revenue generation compared Traditionally no
revenue?
with other options
Yes and no. Standards

Yes. However, uncertainty over
Incentives for R&D in encourage specific Yes. Stable CO2 price is needed
permits’ prices could weaken
clean technologies? technologies but not Brod to induce innovation
innovation incentives
innovation
Somewhat. Regulations
Yes, though if other taxes are
increase the cost of Yes (as with a tax), but giving
reduced through revenue
Harm to manufacturing, but, unlike firms free allowances offsets
recycling, competitiveness of
competiveness? taxes of tradable permits, do potentially harmful effects on
the broader economy can be
not raise the price of fossil profitability
improved
energy
Practical or political
Yes. Setting the level of Yes. New taxes have been very Yes. Identifying a reasonable
obstacles to
standards is difficult unpopular allocation and target is difficult
implementation?
Yes, but experience with existing

New institutional trading programs suggests that
Minimal (unless tradable) Minimal
requirements? markets arise quickly and
relatively inexpensively
Source: Parry and Pizer [11].
Table 1. Command and control versus carbon tax versus tradable permit system
4. Insurance as an environmental policy instrument
A relevant role could be played by the insurance sector in the choice of political economic
instruments for climate change.
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As mentioned in Section 1, following the EAL approach, the emitters of GHGs externalize the
true costs of their contribution to climate change, and this implies the need to recover these
costs, which manifest through both the costs of impacts and the costs to prevent impacts.
Because the insurance sector is the world’s largest industry, the response of insurers to the
broader climate change challenge will no doubt be the key to, at least partially, solve this
internalization problem.
Generally, insurers can indirectly stimulate prevention behavior in their customers. In the case
of climate change, they can play two primary roles through their insurance products. The first
role is played in supplying and pricing traditional insurance coverage for damage deriving
from climate change by the promotion of actions of businesses and individuals to align policy
holders with climate-positive behaviors. The second is played in providing capital to new
ventures and reducing the financial risk to investors by facilitate the creation of new markets
and services that will help to solve the climate change problems.
In both the roles, insurance companies deal with the management of risk activities. In fact,
climate change risk is managed by the insurers through the risks they accept from clients, given
that climate change causes an increase in intensity and spreading the distribution of extreme
weather events with resultant effects on property claims that could be catastrophic.5
Traditionally, insurance is the main mechanisms available to individuals and business to
manage the financial consequences of risky events, such as natural hazards like windstorms
and floods. Insurance companies used to work making each individual or business pay a
premium to protect themselves against an uncertain loss. The premium is calculated by pooling
risks across a large and diverse population considering the pool’s expected losses.
In this way, the insurance industry provides a coverage for climate change consequences
because climate experts predict changes in the intensity and the distribution of extreme
weather events and of the resulting risk of catastrophic property claims.
But specifically, for what concerns the consequences of climate change, many problems arise
to provide insurance coverage [13].
First, climate change is connected to global weather patterns that may increase the potential
for losses so large. As more severe weather becomes more common and overall variability of
conditions increases, there is a threat for the solvency of insurance companies.
Second, because uncertainties in assessing climate change’s impacts are high and affect
property, casualty, business interruption, and health; as a result, risk has significant ambiguous
components and insurers are both likely to charge a significantly higher premium or avoid
insuring the risk entirely.
Third, climate change–related risks may be correlated and create a skewed risk pool that could
increase the probability of extremely large losses and also risks not well-distributed across
existing insurers.
5 Insurance coverage can be also connected with the liability system. But, for what concerns the consequences of climate
change, such as impacts of property damage from extreme weather events, the assignment of liability is a very complex
topic. See Reference [12].
34 Greenhouse Gases
Finally, as a result of insurers’ uncertainty aversion and need to protect against extremely large
losses from single or related events, it is not clear that insurers will be willing to insure against
some climate change–related risks at a price that policy holders are willing to pay.
Climate change will affect, and in some cases is already affecting, most major types of insurance
products. Insurers will feel the impact of climate change on property and casualty insurance,
where the insurer bears the risk of a loss suffered directly by the policy holder. These property
and casualty claims include not only damage to insured property as a direct result of weather
but also claims for business interruptions and other consequences of weather-induced events.
Also, health and life insurers are going to face increasing costs.
Sometimes, insurance companies are involved in the systems of compensation fund that have
been established in some countries. This is the case of special government disaster funds within
the target to promote framework of contingency measures to cover the economic costs of
natural disasters [14].
Other insurance products are the so-called “financial responsibility” products. This term
includes the tools that require companies to demonstrate to have sufficient financial resources
for eventual future environmental damage that may arise through their activities. In its
common implementation, financial responsibility implies that a production activity is author‐
ized only if companies can prove that they will be able to financially cover economic claims,
for example, using surety bonds, cash accounts, deposit certificates, self-insurances, and
corporate guarantees.
In the past few years, the insurance industry has developed financial products suitable for
dealing with climate change-related risks in the direction to play a role far beyond simply
compensating climate change’s victims for their losses ex post. The activity of the insurance
has become relevant as a political economic instruments within an ex ante strategy to finan‐
cially manage large-scale catastrophes, as a complement of ex post instruments for the
compensation of disaster losses.
Insurance industry is also developing alternative risk transfer products, given that conven‐
tional reinsurance arrangements may in future cover a smaller proportion of total losses, and
there may be insufficient capital available to insurance markets to cover these losses [15].
A first kind of these insurance products are called “catastrophe bonds” and consist in securi‐
tizing environmental risks in bonds, which could be sold to high-yield investors. The catas‐
trophe bonds are able to transfer risk to investors that receive coupons that are normally a
reference rate plus an appropriate risk premium. By these products, insurance companies limit
risk exposure transferring natural catastrophe risk into the capital markets. In this way, with
the involvement of the financial markets, their global size offers enormous potential for
insurers to diversify risks.
Weather derivatives are another kind of financial instrument used by companies to hedge
against the risk of weather-related losses. Weather derivatives pay out on a specified trigger,
for example, temperature over a specified period rather than proof of loss. The investor
providing a weather derivative charges the buyer a premium for access to capital. If nothing
happens, then the investor makes a profit.
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With this kind of financial products, the insurance industry tries to reach two goals. First, there
is the need for extra capital and to spread risks beyond the insurance sector. Particularly, cat
bonds are used to spread insurance risk in the financial sector. The second goal is to improve
the accuracy and the resolution of hazard data and the likely impacts on climate change with
the involvement of financial market forecast ability.
The insurance industry can act to tackle the consequences of climate change by playing its part
in climate change mitigation, through the promotion of ways to reduce GHG emissions.
Insurers are also well placed to help society to adapt to the impacts of climate change, by
promoting the effective limitation and management of risks from extreme weather-related
hazards.
Individuals and companies that buy insurance products could be stimulated to address climate
change-seeking mechanism to facilitate mitigation of GHG emissions and adaptation to the
inevitable impacts of climate change [16]. In addition, the insurance companies themselves are
motivated to take significant actions to mitigate GHG emissions and increase adaptive capacity
to reduce overall uncertainty and other barriers to insurability and are also motivated to limit
the insurers’ potential exposure to catastrophic risks in excess of their capacity to avoid the
potential for property and liability claims in excess.
The insurance industry is also developing new products that would have the consequences to
stimulate the adaptation to climate change. On the one hand, products help to create the
conditions for active adaptation to build physically resilient communities; on the other hand,
products provide capital and liquidity to help communities to cope with losses caused by
climate change catastrophes.
Insurance products can be designed in a way for which simply their price reflects the level of
climate change-related risk assumed by the insurer. These products, rewarding behavior that
reduces risk of financial losses, encourage adaptive behavior. For example, insurance products
that incorporate these features provide a premium discounts on property insurance for
climate-resilient commercial or residential buildings.
The recent tendency to supply coverage with differential premiums to customers depending
on their level of protection from losses caused by weather-related disasters can be seen as a
clear opportunity for insurers to reduce their own overall and maximum possible loss exposure
while promoting communities overall resilience in the face of climate change’s impacts. So,
more often, policies include discounts for businesses or homeowners that have taken specific
steps to ensure their buildings resistant to floods or other hazards. Moreover, insurance
companies also condition their policies on compliance with laws such as building codes, thus
playing a role in enforcing laws that promote climate change resilience.
The second kind of insurance products that stimulate adaptation is based on the availability
of capital to cope with catastrophes. These are financial arrangements intended to bring needed
capital that will reduce the risk that could derive from future climate-related hazards for those
who are most likely to be in peril. These products can be defined as adaptation oriented because
they help to build the capacity of nations, communities, and businesses to cope with climate
change impacts.
36 Greenhouse Gases
Figure 1 shows the different roles that can be played by insurance sector as a form of environ‐
mental policy instruments.
Source: MCII [17].
Figure 1. The different roles of the insurance sector in the framework of climate change consequences
5. Policies choice in the case of climate change and the concept of “economic
global public goods”
Dealing with the consequences of GHG emissions in terms of climate change implies a
definition of “economic global public goods” that can be defined as goods with economic
benefits that extend to all countries, people, and generations [18]. Following the EAL approach,
they are special case of externalities with a global dimension.
Climate is clearly “global” in both causes and consequences; moreover, the emissions of GHG
have effects on global warming independently of their location, and local climatic changes are
completely linked with the world climate system.
In addition, global warming is characterized by other important features that imply some
difficulties in the implementation of the instruments provided by the standard economic
theory of policy choice. First, we cannot determine with certainty both the dimension and the
timing of climate change and the costs of the abatement of emissions. Second, the effects of
GHG concentration in the atmosphere on climate are intergenerational and persistent across
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time. Finally, it emerges a relevant equity issue among countries because industrialized
countries have produced the majority of GHG emissions, but the effects of global warming
will be much more severe on developing countries. In other words, the countries that have
more responsibilities will face less consequence in the future and vice versa.
There are major governance issues involved in dealing with global public goods because global
coordination is required [19]. With economic public goods, it is difficult to determine and reach
agreement on efficient policies because they involve estimating and balancing costs and
benefits where neither is easy to measure and both involve major distributional concerns.
When dealing with economic public goods like global warming, it is necessary to reach through
governments to the multitude of firms and consumers who make the vast number of decisions
that affect the ultimate outcomes.
Because global warming is a global public good, the key environmental issue is global
emissions, and the key economic issue is how to balance costs and benefits of global emission
reductions. Climate change depends only on total GHG emissions and the time path of
emissions not on the geographic location of emissions. Moreover, the impacts depend
primarily on cumulative emissions that remain in the atmosphere not on the annual flow of
emissions.
It is a global issue to decide what the distribution of emission reductions among countries
should be and how the costs should be allocated, together with the need for differences among
high- and low-income countries, high- and low-emitting countries, and high- and low-
vulnerability countries.
Given the global nature of climate change, it is easy to understand the necessity of an action
at international level, in order to efficiently implement the different policy instruments that
we have analyzed earlier in this chapter.
First, the instruments based on tax mechanism need a method of coordinating policies among
countries. In the international environment, it could assume the form of either an international
tax or a harmonized domestic tax system. In the case of an international tax, the nations (and
not the firms) pay the tax to an international agency, which receives and redistributes the tax
revenues. On the other hand, in the case of harmonized domestic tax, the international
community should negotiate an agreed level of a domestic emission tax, establishing adequate
compensation for the losing countries from the gaining countries.6
Second, it is possible to establish an agreement that sets quantitative limits of emissions and
allocates emission permits to firms (or States) but allows to trade among countries, in order to
minimize abatement costs. The starting allocation of permits can be set through either an
auction or a grandfather allocation. Under an auction, government (or the international
community) sells the emission permits, whereas under the grandfather rule, the allocation of
emission permits is based on historical records.
6 Nordhaus [20] hypothesizes the institution of an harmonized carbon tax (HCM), essentially equivalent to a “dynamic
Pigouvian pollution tax for a global public good” and points out 10 different reasons to prefer it to a quantitative approach.
38 Greenhouse Gases
In the global-warming context, quantitative limits set targets on the time path of GHG
emissions of different countries. Countries then can administer these limits in their own
fashion, and the mechanism may allow transfer of emission allowances among countries, as
is the case under the Kyoto Protocol.
The European Union Emissions Trading Scheme (EU-ETS) – the world’s most extensive carbon
pricing market – has now been in operation for 10 years. The EU-ETS was developed as a way
of meeting the EU’s GHG emission reduction targets in the most efficient and cost-effective
manner. To do so, the EU-ETS sets a limit (a cap) on the total emissions; certain EU sectors
(mostly heavy industry and aviation) are allowed to use during predefined trading periods.
Permits are then distributed among polluters where one permit equals one ton of carbon
dioxide equivalent. These permits can then be traded between market participants. As such,
the total amount of pollution is set by an external authority, but market participants determine
the permit allocation, thereby optimizing efficiency.
In addition, the involvement of the insurance sector as an efficient policy instruments needs a
global approach.
Insurance sector can contribute to develop risk management strategy to minimize climate
change consequences on an urgent basis to prevent further escalation of global warming.
However, insurance needs to be a part of the overall policy of mitigation and adaptation that
aims at reducing the severity of many impacts that could result from climate change if current
adverse conditions prevail.
In order to organize their own operations to the new challenge, the insurance industry should
include climate change risk in its internal governance procedures, in line with the existing
financial corporate risk identification. To enable insurance companies to play a responsible
role in tackling climate change consequences, they require a reliable, transparent, and inter‐
national coordinated policy framework as well as long-term, appropriated GHG emission
reduction goals coordinated at an international level.
6. Final remarks: COP 21 and the issue of the linkage of different national
policies
In the COP 21 meeting in Paris at the end of the 2015, global climate policy has faced the tension
between the efficiency benefits of uniform global policy and national and regional variation
in tastes for differing policies. Although climate negotiations, going back to the framework
convention, have had a coordinated global policy as their goal, it could be that we will head
toward a less coordinated system of local, national, or regional policies.
In reality, as we have analyzed in the chapter, different countries are undertaking different
policies ranging from CAC to MB approaches, such as carbon tax and tradable permit systems.
Variations in policies, although catering to local tastes and preferences, can lead to substantial
inefficiencies, and the target will be to reach an optimal degree of policy homogenization.
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There is a large literature on the importance of linking economic policies to face GHG conse‐
quences [21].
Some authors argue that the basic approach underlying emission reduction credit systems like
the Kyoto Clean Development Mechanism (CDM) can be extended to create linkage oppor‐
tunities in diverse emission control systems in ways that do not necessarily suffer from the
shortfalls of the current CDM. Moreover, while emission reduction credit systems are designed
to work with MB systems like tradable permits, they describe ways in which it can interact
with tax systems as well as certain regulatory systems [22].
By clarifying the opportunities and challenges of insurance as an instrument for adaptation

and outlining a practical way forward, it is hoped that this discussion contributes to the
opportunities in adopting a comprehensive adaptation strategy that enables risk management
and insurance through the funding of a global adaptation strategy [17].
In the near future, the challenge for COP 21 to reduce GHG emissions is to try to link hetero‐
geneous climate policy instruments as a way to reach the solution of climate change issue in
the long term.
Author details
Donatella Porrini*
Address all correspondence to: donatella.porrini@unisalento.it
Università del Salento, Lecce, Italia
References
[1] IPCC. Guidelines for national greenhouse gas inventories. Available from www.ipcc-
nggip.iges.or.jp/public/2006gl [Accessed: 2015-10-10].
[2] Coase R. The problem of social cost. Journal of Law and Economics. 1960;3:1–44.
[3] Mankiw G. The Pigou Club Manifesto. Available from http://gregmankiw.blog‐

spot.it/2006/10/pigou-club-manifesto.html [Accessed: 2015-10-10].
[4] Pigou AC. The Economics of Welfare. 4th ed. London: McMillan & Co; 1932.
[5] Lewis T. Protecting the environment when costs and benefits are privately known.
RAND Journal of Economics. 1996;27:819–47.
[6] Cropper ML, Oates WE. Environmental economics: A survey. Journal of Economic
Literature. 1992;30:675–740.
40 Greenhouse Gases
[7] Porrini D. Environmental policies choice as an issue of informational efficiency. In:

Backhaus JG, editor. The Elgar Companion to Law and Economics. 2nd ed. Chelten‐
ham: Edwar Elgar; 2005. p. 350–63.
[8] Calabresi G. The Cost of Accident. New Haven, CT: Yale University Press; 1970.
[9] Shavell S. The Economic Analysis of Accident Law. Cambridge, MA: Harvard Uni‐
versity Press; 1987.
[10] Kaplow L, Shavell S. On the superiority of corrective taxes to quantity. American

Law and Economics Review. 2002;4:1–17. DOI:10.1093/aler/4.1.1
[11] Parry WH, Pizer WA. Emissions Trading versus CO2 Taxes versus Standards. Re‐
sources for the Future, Issue Brief. 2007;5. p. 80-6.
[12] Faure M. Climate Change Liability. Cheltenham: Edwar Elgar Pub; 2011.
[13] Charpentier A. Insurability of Climate Risks. The Geneva Papers of Risk and Insur‐
ance. 2008;33:91–104. DOI:10.1057/palgrave.gpp.2510155
[14] Porrini D, Schwartze R. Insurance models and European climate change policies: An
assessment. European Journal of Law and Economics. 2014;38:7–28. DOI:10.1007/
s10657-012-9376-6
[15] Mills E, Lecomte E. From Risk to Opportunity: How Insurers Can Proactively and
Profitably Manage Climate Change. Boston, MA: Ceres Report; 2006.
[16] Agrawala S, Fankhauser S. Economics Aspects of Adaptation to Climate Change.

Paris: OECD; 2008.
[17] Munich Climate Insurance Initiative (MCII). Insurance solutions in the context of cli‐
mate change-related loss and damage. Policy Brief. 2012;6. p. 15.
[18] Kaul I, Conceicao P, Le Goulven K, Mendoza RU. How to improve the provision of
global public goods. In: UNDP. Providing Global Goods – Managing Globalization.
Oxford: Oxford University Press; 2003.
[19] Nordhaus DW. To tax or not to tax: Alternative approach to slowing global warming.
Review of Environmental Economics and Policy. 2007;1:26–40.
[20] Nordhaus DW. After Kyoto: Alternative Mechanisms to Control Global Warming.
FPIF Discussion Paper; Washington, DC: Institute for Policy Studies2006.
[21] Metcalf GE, Weisbach D. Linking Policies When Tastes Differ: Global Climate Policy
in a Heterogeneous World. Harvard: Harvard Kennedy School. Discussion Paper;
2010. p. 10–38.
[22] Jaffe J, Ranson M, Stavins R. Linking tradable permit system: A key element of
emerging international climate change policy architecture. Ecology Law Quarterly.
2009;36:789–808.
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Chapter 3
Energy for Sustainable Development: The Energy–

Poverty–Climate Nexus
Melanie L. Sattler
http://dx.doi.org/10.5772/62254
Abstract
Worldwide, 1.4 billion people lack access to electricity, and 2.7 billion people rely on tra‐
ditional biomass for cooking. Most people living in energy poverty—without electricity
access and/or using traditional biomass for cooking—are from rural areas of Sub-Saharan
Africa, India, and other developing Asian countries (excluding China). At the same time,
the poorest people are the most likely to suffer from the impacts of climate change.
Fortunately, innovative, sustainable energy technologies can allow developing countries

to leapfrog to low-carbon renewable energy, while at the same time alleviating extreme
poverty. Increasing energy access, alleviating rural poverty, and reducing greenhouse gas
emissions can thus be complementary, their overlap defining an energy–poverty–climate
nexus. Transitioning to more efficient low-carbon energy systems in rural areas can gen‐
erate greater returns than similar efforts in industrialized areas.
Accordingly, this chapter provides an overview of: a) The linked problems facing devel‐
oping countries of energy access, poverty, and climate change, and how these problems
interact and compound each other. b) Potential renewable energy solutions, including
off-grid solar, wind, clean biomass, micro-hydro, and hybrid systems. For each energy
option, benefits and challenges will be discussed, along with examples of successful
small-scale use in rural areas of developing countries.
Keywords: Sustainable energy, climate change, developing countries, renewable energy,

energy–climate–poverty nexus
1. Introduction
Most of the world’s people without access to electricity or clean energy are from rural areas of
developing countries. At the same time, a person in a developing country is 79 times more
42 Greenhouse Gases
likely to suffer from a climate-related disaster than a person in a developed country, according
to the United Nations Development Programme [1].
Fortunately, for developing countries, increasing energy access, alleviating poverty, and
addressing climate change can all be accomplished via sustainable energy. In fact, implement‐
ing renewable energy in rural areas can generate greater returns in terms of reduced green‐
house gas emissions than similar efforts in industrialized areas. Accordingly, this chapter will
provide an overview of the current energy access problem in developing countries and
potential innovative sustainable solutions. Off-grid renewable electricity options to be
discussed include solar, wind, clean biomass, micro-hydro, and hybrid systems.
2. The Problems
The problems of energy access, poverty, and climate change are intertwined in the developing
world. The poor often lack access to energy at all or have access only to inefficient and
unhealthy forms of energy. Lack of energy makes it more difficult to address other aspects of
poverty, such as lack of education or health care (imagine operating a school or hospital
without access to electricity). As the poor gain access to energy, their contribution to climate
change will increase, unless they leapfrog to renewable energy technologies. Unfortunately,
the poor are the most vulnerable to many impacts of climate change, including increased food
insecurity and amplified health risks. These interrelationships that constitute the energy–
poverty–climate nexus problem are discussed in more detail below.
2.1. The Energy–Poverty Nexus
Worldwide, 1.4 billion people (20% of the world’s population) currently lack access to
electricity, and 2.7 billion people (40% of the world’s population) rely on inefficient and
unhealthy forms of biomass [2]. Air pollution levels indoors from 3-stone fires or inefficient
stoves using biomass are many times higher than typical outdoor levels, even those in highly
polluted cities. The World Health Organization (WHO) estimates that over 1.5 million die
prematurely each year from household air pollution due to inefficient biomass combustion [2].
These deaths from cancer, respiratory infections, and lung diseases account for 4% of the global
burden of disease—more deaths than those from malaria (1.2 million) or tuberculosis (1.6
million) [1]. Many of those who die are young children, who spend hours each day breathing
in smoke from the cookstove [2].
Moreover, in regions where households rely heavily on unhealthy forms of biomass, women
and children are typically responsible for fuel collection—a time-consuming and exhausting
task. This strenuous work without sufficient recuperation can cause serious long-term physical
damage for women. Heavy reliance on biomass can also cause land degradation, including
deforestation, and local and regional air pollution [2].
As shown in Table 1, most of the people living in energy poverty—without electricity access
and/or using traditional biomass for cooking—are from rural areas of developing countries,
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Energy for Sustainable Development: The Energy–Poverty–Climate Nexus 43
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the majority in Sub-Saharan Africa, India, and other developing Asian countries (excluding
China) [2]. At current growth rates, about half a billion “energy poor” will be added over the
next 20 years [1].
Number of people lacking access to Number of people relying on the traditional

Region
electricity (millions) use of biomass for cooking (millions)
Africa 587 657
Sub-Saharan Africa 585 653
Developing Asia 799 1937
China 8 423
India 404 855
Other Asia 387 659
Latin America 31 85
Developing countries* 1438 2679
World** 1441 2679
*Includes Middle East countries.
**Includes Organisation for Economic Co-operation and Development (OECD) and transition economies.
Table 1. Number of people lacking access to electricity and relying on the traditional use of biomass for cooking, 2009
(million) [2]
Improving access to cost-effective, sustainable energy technologies is critical for addressing

poverty in developing countries [1]. Although improving energy access is not one of the 8
globally agreed Millennium Development Goals (MDGs), it is a cross-cutting issue that directly
impacts achievement of the goals [1]. More and better energy services are needed to end
poverty, hunger, educational disparity between boys and girls, the marginalization of women,
major disease and health service deficits, as well as environmental degradation [1, 2]. Without
modern energy services, basic social goods such as health care and education are more costly
in both real and human terms, and economic development is harder to perpetuate [1]. A clear
correlation exists between energy and the Human Development Index (HDI) [3]. As the
International Energy Agency and United Nations state, “Access to modern forms of energy is
essential for the provision of clean water, sanitation and healthcare and provides great benefits
to development through the provision of reliable and efficient lighting, heating, cooking,
mechanical power, transport and telecommunication services” [2].
For the 1.4 billion people that lack access to electricity, they either live in locations too remote
to be connected or cannot afford the fee to connect [4]. For locations that are off-grid, fossil
fuels are often unaffordable due to the cost of delivery to remote locations [5].
2.2. The Energy–Climate Nexus
The climate change problem is largely a fossil fuel problem. According to the Intergovern‐
mental Panel on Climate Change (IPCC) 2007 report, at least 57% of greenhouse gas emissions
44 Greenhouse Gases
globally stem from burning of fossil fuels [6]. For carbon dioxide (CO2), the most important
anthropogenic greenhouse gas, 74% of emissions are due to combustion of fossil fuels [6].
When fossil fuels are burned for energy, the carbon stored in them, originally from biomass
such as algae, is emitted almost entirely as CO2. These fossil fuels include coal, oil, and natural
gas, which are burned in electric power plants, automobiles, industrial facilities, and other
sources.
2.3. The Poverty–Climate Nexus
The poorest people in the world are the most likely to suffer from impacts of climate change.
According to the United Nations Development Programme (UNDP), a person in a developing
country is 79 times more likely to suffer from a climate-related disaster than a person in a
developed country [2]. The poor are especially vulnerable to the impacts of climate change,
including reduced agricultural productivity and increased food insecurity; heightened water
stress and insecurity; rising sea levels and increased exposure to climate disasters; loss of
ecosystems and biodiversity; and amplified health risks [1]. According to the Human Devel‐
opment Report (HDR) 2007–2008, failure to address climate change will consign and trap the
poorest 40% of the world’s population, some 2.6 billion people, in downward spirals of
deprivation [7]. Providing energy access will help poor areas adapt in the face of a changing
climate [8].
Reductions in greenhouse gas emissions must include both developed and developing
countries, including those with significant numbers of people living in poverty. According to
the U.S. Environmental Protection Agency (EPA), greenhouse gas emissions from developing
countries are expected to exceed those from developed countries in 2015 [9]. According to
Casillas and Kammen [8], every dollar spent on the transition to more efficient low-carbon
energy systems in rural areas has the potential to produce greater carbon mitigation returns
than in more industrialized areas.
3. Potential Solutions
Since the problems of energy access, poverty, and climate change are interrelated in developing
countries, solutions can be designed to solve all 3 problems simultaneously. Innovative
sustainable energy technologies can allow developing countries to leapfrog to low-carbon
renewable energy, while at the same time alleviating extreme poverty. Increasing energy
access, alleviating poverty, and reducing greenhouse gas emissions can thus be complemen‐
tary, their overlap defining an energy–poverty–climate nexus solution.
As mentioned above, according to the article published by Casillas and Kammen [8] recently
in Science, transitioning to more efficient low-carbon energy systems in rural areas can generate
greater returns than similar efforts in industrialized areas. Urban cities of developing countries
may have access to electricity for lighting. Rural areas typically lack access altogether; hence,
the need in these areas is the greatest [9]. Access to electricity in rural areas, even at modest
consumption levels, can dramatically improve a community’s quality of life. For example,
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electric lamps can allow children to study at night, and radios and cellular phones can greatly
improve communication pathways [10]. This section will accordingly focus on renewable
energy solutions for rural areas of developing countries.
Centralized electrification requires massive amounts of capital [10]. The dispersed nature of
houses and low potential demand create little incentive for power companies to provide access
to rural areas. In addition, extending the grid may be unrealistic due to transmission line costs
or hard terrain [5]. Thus, in rural areas, off-grid and mini-grid solutions make the most sense.
Such systems can consist of a single home or several small homes and businesses. The systems
can be incremental and scalable and applied to many different conditions and environments
[10]. Off-grid and mini-grid options for renewable electricity include solar, wind, clean
biomass, and micro-hydro. These options for renewable power will be discussed in more detail
below.
3.1. Solar Power
Solar energy is abundant in many locations in the developing world [5]. Many regard it as the
most promising renewable source for developing countries [5, 11, 12]. The use of solar energy
produces no on-site air pollutants [although pollutants are typically generated in the process
of manufacturing photovoltaics (PV) cells].
Solar energy can be utilized in two ways: direct heat energy for various purposes (heating
water, heating space) and direct current electricity generation using PV system. Electrical
energy can be used immediately to pump water for irrigation or for refrigeration, lighting, or
other purposes; alternatively, it can be stored in a rechargeable battery for later use [5]. This
can help solve problems associated with its intermittency [12].
Individual houses can have their own PV system for lighting and small appliances, such as
radio and mobile phone charging. A village can benefit from a larger PV system, with a micro-
grid structure.
3.1.1. Solar Challenges
The primary barrier to widespread implementation of the solar PV technology is its cost, due
to the high cost of the silicon base material and associated manufacturing processes [1]. In
addition, production of solar cells currently requires sophisticated and expensive manufac‐
turing facilities and highly trained personnel, which may not be available in developing
countries. Nicole Kuepper, a Ph.D. student, won the Eureka Prize for Young Leaders in
Environmental Issues and Climate Change for developing a simple, inexpensive way of
producing solar cells in a pizza oven. The process uses a low-cost inkjet printing process,
aluminum spray, and a low-temperature pizza oven, meaning that the solar cells can be made
without high-tech environments or high-cost inputs [1].
Solar water heaters (SWHs) are relatively expensive to install ($500–$2100), although the initial
investment can be recovered through future electricity savings [1]. For many families in rural
areas, the purchase of a solar lighting set, even for lighting service only, is so hard that a
46 Greenhouse Gases
systematic approach has to be designed, which enables them to pay only for the lighting service
received instead of owning the whole hardware [5].
3.1.2. Solar Success Stories
Solar lanterns. Typically, solar-powered lanterns use solar energy to charge a battery that
powers a solid-state light-emitting diode (LED), the most efficient lighting technology on the
market. One solar lantern, the Mighty Light, costs around US$ 45 and lasts up to 30 years. It
has replaced polluting dangerous kerosene lamps for thousands of households in Afghanistan,
Guatemala, India, Pakistan, and Rwanda [1]. As of November 2010, around 9000 versions of
a solar lantern called the “solar tuki” had been installed in Nepal [1].
Solar home systems. A solar home system is a PV system with capacity of 10–40 Wp (peak Watts).
By 2007, Grameen Shakti had installed 100,000 solar home systems to power lights, motors,
pumps, televisions, mobile phones, and computers in Bangladesh [1].
SELCO of India is an organization successfully installing solar home and business systems to
provide electricity for lighting, SWHs, solar inverter systems (for use in communications and
computing), and small business appliances. Since 1995, SELCO has been providing solar
energy solutions to underserved households and businesses in India, based on the ideas that
poor people can afford sustainable technologies, poor people can maintain sustainable
technologies, and social ventures can be run as commercial entities [1].
Community solar systems. Community solar PV systems are commonly used for pumping water
for drinking and irrigation. The solar panel may vary between 130 Wp and 40 kWp. The
Promethean Power project promotes a version of community solar systems using concentrated
solar thermal power rather than PV. The system, which can be manufactured locally, concen‐
trates solar thermal energy to heat a fluid refrigerant. The solar thermal system is combined
with a unique microscale generator adapted and scaled to suit the needs of underserved
communities. The heated fluid expands through a rotary vane turbine (an automobile power-
steering pump) to make mechanical energy that spins a generator (an automobile alternator).
Massachusetts Institute of Technology (MIT) is installing the systems in Lesotho in Africa [1].
3.2. Wind Power
Like solar, the fuel source for wind power is free and unlimited. The use of wind turbines to
generate electricity via a generator produces no on-site air pollution, although a small amount
of emissions is produced during manufacture of the turbines. One life-cycle assessment found
that off-grid wind turbines reduce greenhouse gas emissions by 93%, compared to off-grid
diesel power generation systems [13]. An additional advantage is that wind turbines are simple
mechanical systems that can be easily maintained and repaired [10].
3.2.1. Wind Challenges
One of the challenges associated with wind power is its intermittency. Researchers are
developing solutions to this problem for off-grid wind systems. Short term, the electrical
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energy generated by the turbine can be stored in a battery [14]. Researchers have developed
controllers that maximize capture of wind energy and avoid battery overcharge [15, 16]. Other
researchers have proposed a hybrid energy storage system that can provide uninterrupted
power, according to simulations. In the hybrid storage system, a battery is used for short-term
energy storage, and a water electrolysis hydrogen system is used for long-term energy storage
due to hydrogen’s high mass energy density and very low leakage [17].
Another challenge is selecting an appropriate location for the turbine, due to the highly
localized nature of wind. Low-cost anemometers may help alleviate this problem, but time
must be spent to collect a sufficient amount of data [10]. Areas particularly suited to wind
power because of their typical high wind velocities include coastlines, high ground, and
mountain passes [12]. Wind power does not need water, so it is suitable for dry areas.
A third challenge is the need for a tower, so that the turbine is at least 10 m above the nearest
obstacle. The tower itself could cost more than the wind turbine. Researchers are examining
towers made from bamboo and other common and low-cost materials [10].
3.2.2. Wind Success Stories
The cost of commercially available wind turbines is several thousand US dollars per kilowatt,
which is out of reach for most rural residents of developing countries [10]. Low-cost wind
turbines with timber blades have been demonstrated successfully in Nepal [18]. Low-technol‐
ogy wind turbine generators, which can be made by people with limited technical skills, no
advanced machining equipment, low capital cost, and limited exotic materials, have also been
demonstrated [10]. The low-technology wind turbine was constructed in a joint effort by the
IEEE Power & Energy Society Community Solutions Initiative and the Puget Sound Profes‐
sional Chapter of Engineers Without Borders, USA.
3.3. Clean Biomass
Biomass sources in rural areas include human excrement, animal manure, and agricultural
wastes. Biomass can be burned directly to produce heat energy or electricity via a microturbine,
or it can be degraded by anaerobic microbes to produce biogas. Although burning biomass in
inefficient cookstoves contributes to illness via indoor air pollution, as described above,
biomass can be burned using clean technologies or used to generate clean-burning biogas.
Biogas, typically 60–70% methane, can be used directly in natural gas-powered appliances or
burned to generate electricity via a microturbine and generator [19]. It is expected that
microturbines powered by biogas might eventually be competitive with diesel engines for
village-scale power applications, with relatively low maintenance costs, high reliability, long
lifetimes, and low capital costs [1]. Fuel cells might ultimately prove able to generate power
at village scales from biogas, at very high efficiencies [1].
Anaerobic processes that produce methane from waste solve 2 problems at once: waste and
energy. Anaerobic processes provide some of the simplest and most practical methods for
minimizing public health hazards from human and animal wastes. Pathogens such as
schistosome eggs, hookworm, flat/tape worm, dysentery Bacillus, poliovirus, Salmonella, and
48 Greenhouse Gases
Bacillus for paratyphoid are destroyed. A residence time of 14 days at >35°C in a small-scale
system in a developing country can provide 99+% removal of pathogens, with the exception
of roundworm [20, 21].
In addition, the solid residue from anaerobic waste treatment processes is a valuable fertilizer,
which is stabilized and almost odorless. This fertilizer is especially a benefit in developing
countries, due to its potential to boost crop yields.
3.3.1. Biomass Challenges
Ideally, energy should be produced from biomass that is not edible and that cannot be grown
in places where edible crops could be grown, so that competition between uses of crops for
energy and food does not become an issue. Producing energy from wastes avoids this issue.
Because of limits on the amount of land accordingly available for growing plants that can be
used for energy, bioenergy cannot be viewed globally as the sole replacement or substitute for
fossil fuels, but rather as one element in a broader portfolio of renewable energy sources [1].
In rural locations in developing countries without current access to electricity, however,
biomass can provide a transformative local power source.
3.3.2. Biomass Success Stories
An improved biomass cookstove designed by Prakti Design Lab to meet the cooking require‐
ments of rural households is around 40% percent more fuel efficient than traditional cook‐
stoves and emits 70–80% less smoke [1].
In Senegal, proliferating invasive aquatic plants are being transformed into combustible pellets
that can be used for cooking, replacing wood and charcoal. By impacting lake water quality,
the plants’ proliferation caused an increase in waterborne diseases. The plants are also created
problems for fishermen, by jamming their nets, and farmers, by reducing access to water for
livestock. Local fishermen and farmers will be recruited as plant removers, and 20 additional
local workers will be hired and trained to manage the pellet production process. Based on
capacity production of the compaction machine (4,000 kg/week) and a local price of US$ 0.28/
kg, the pellets could generate income of about US$ 1,120/week for the local population [1].
3.4. Micro-Hydro
Micro-hydro systems use the natural flow of water to yield up to 100 kW output of electrical
energy [22]. Simplicity, efficiency, longevity, reliability, and low maintenance costs make these
systems attractive for rural development [23]. Like solar and wind, the fuel source for micro-
hydro power is free, and the use of hydro-powered turbines to generate electricity produces
no on-site air pollution.
Unlike large hydroelectric plants, micro-hydro systems do not require a dam and reservoir,
which minimize their environmental damage. A portion of the river’s flow is diverted to the
micro-hydro intake. A settling tank may be used to allow silt to settle out of the water. A screen
or bars screen out floating debris and fish. The water then flows through a channel, pipeline,
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or pressurized pipeline (penstock) to the powerhouse, which houses a turbine or waterwheel.

The turbine turns a generator to produce electricity [22]. A variety of turbines may be used,
including a Pelton wheel for high head, low-flow water supply, or a propeller-type turbine for
low-head installations [24, 25].
3.4.1. Micro-Hydro Challenges
Micro-hydro systems obviously are limited to locations with a stream or river. The flow volume
must be sufficient to supply local energy needs. In addition, a sufficient quantity of falling
water must be available, which usually means that hilly or mountainous sites are best. A drop
of water elevation of at least 2 ft is required or the system may not be feasible; the water does
not “fall” enough distance to produce enough head [22, 24]. Another limitation is that the
distance from the stream or river to the site in need of energy may be considerable [23].
The power produced may fluctuate depending on how much water is flowing in the stream
or river and the velocity of flow [23]. Energy can be stored in batteries, so additional reserve
energy available for time of low generation and/or high demand. However, because hydro‐
power resources tend to be more seasonal than wind or solar resources, batteries may not be
able to provide enough energy storage for summer or other seasons with severely limited water
flow. Integrating the hydropower with a hybrid wind or solar system can help in areas where
water flow is highly seasonal.
3.4.2. Micro-Hydro Success Stories
The main micro-hydro programs in developing countries are in mountainous regions, such as
Nepal (around 2,000 installations, including both mechanical and electrical power generation)
and other Himalayan countries [25]. In South America, micro-hydro programs are located in
countries along the Andes, such as Peru and Bolivia. Smaller programs have been initiated in
hilly areas of Sri Lanka, the Philippines, China, and elsewhere [25]. In a variety of locations,
micro-hydro systems have been shown to increase employment opportunities in rural areas,
which encourage young people to stay in the villages rather than drifting to the cities [25].
Maher et al. [26] describe the successful implementation of pico hydro (<5 kW) systems in two
communities in Kenya. Costs for these systems were considerably less than comparable PV or
auto battery systems. The systems were constructed locally using available materials and
community labor.
3.5. Hybrid Systems
According to a report issued in 2010 by the International Energy Agency, UNDP, and United
Nations Industrial Development Organization, combining solar, wind, biomass, and mini-
hydro into an integrated/hybrid system supplying a mini-grid is probably the most promising
approach to rural electrification [2]. A combination of technologies in an integrated system can
promote reliability. A small backup generator may be operated on diesel, biogas, or biodiesel
[5]. Hybrid village electrification systems have been implemented in various countries,
including China, India, Ghana, South Africa, and Tanzania [1]. A number of studies have
50 Greenhouse Gases
examined the feasibility of various kinds of hybrid off-grid systems: wind–diesel [14, 27],
wind–solar [28, 30], wind–PV–diesel [31–33], hydro–PV–wind [34], wind–hydrogen [35], and
solar–wind–biomass–hydro [36].
4. What Now? Next Steps
At the global level, a new development paradigm—a pro-poor global climate change agenda
—should be embraced. National climate change adaptation and mitigation strategies should
be directly linked with poverty reduction and sustainable development goals [1].
To ensure that every person in the world benefits from access to electricity and clean cooking
facilities by 2030, the International Energy Agency, UNDP, and United Nations Industrial
Development Organization estimate that investment of $36 billion per year will be required.
To meet the more ambitious target of achieving universal access to modern energy services by
2030, an additional cumulative investment of $756 billion, or $36 billion per year, is needed.
Although this sounds like a large number, it represents only 0.06% of average annual global
gross domestic product (GDP) over the period. The resulting increase in primary energy
demand and CO2 emissions would be modest: in 2030, global electricity generation would be
2.9% higher, and CO2 emissions would be only 0.8% higher [2]. Given that the up-front cost of
new energy technologies is prohibitively expensive for poor communities, targeted financing
and incentives are needed so that low-income communities, households, and entrepreneurs
can invest in new energy technologies.
Students and young entrepreneurs in collaboration with nongovernmental organizations

(NGOs) have done some of the most innovative work in new low-cost sustainable energy
applications. Such partnerships should be promoted. The World Bank’s Development
Marketplace Grants, for example, provide global recognition and seed funding for creative
ideas, technologies, and services that matter for development, so that they may grow and
replicate.
5. Summary
The problems of energy access, poverty, and climate change are intertwined in the developing
world. The poor often lack access to energy at all or have access only to inefficient and
unhealthy forms of energy. As the poor gain access to energy, their contribution to climate
change will increase, unless they leapfrog to renewable energy technologies. Unfortunately,
the poor are the most vulnerable to many impacts of climate change, including increased food
insecurity and amplified health risks. Access to energy can reduce their vulnerability to climate
change impacts.
Fortunately, increasing energy access, alleviating rural poverty, and reducing greenhouse gas
emissions can all be complementary, their overlap defining an energy–poverty–climate nexus.
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http://dx.doi.org/10.5772/62254
Solar, wind, biomass, and micro-hydro systems have all been used successfully in various
locations to provide off-grid renewable power to rural areas. Each has advantages and
drawbacks, depending on the particular location. Combining solar, wind, biomass, and mini-
hydro into an integrated/hybrid system supplying a mini-grid is probably the most promising
approach to rural electrification.
Providing universal access to modern energy services by 2030 would cost only 0.06% of
average annual global GDP during the period. What else could be a more worthwhile
investment?
Author details
Melanie L. Sattler*
Address all correspondence to: sattler@uta.edu
University of Texas at Arlington, Arlington, TX, USA
References
[1] Cherian A. Bridging the Divide between Poverty Reduction and Climate Change
through Sustainable and Innovative Energy Technologies; 2009.
[2] International Energy Agency, United Nations Development Programme, and United
Nations Industrial Development Organization. Energy Poverty: How to Make Mod‐
ern Energy Access Universal? Special Early Excerpt of the World Energy Outlook
2010 for the UN General Assembly on the Millennium Development Goals; 2010.
[3] Sopian K, Ali B, Asim N. Strategies for renewable energy applications in the organi‐
zation of Islamic conference (OIC) countries. Renewable and Sustainable Energy Re‐
views. 2011; 15(9): 4706–4725. DOI:10. 1016/j. rser. 2011. 07. 081.
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[10] Louie H. Experiences in the Construction of Open Source Low Technology Off-Grid
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[21] Office of the Leading Group for the Popularisation of Biogas (OLGPB) in Sichuan
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2012-03].
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[24] Oregon Department of Energy. Micro Hydroelectric Systems [Internet]. Available at:
www. oregon. gov/ENERGY/RENEW/Hydro/Hydro_index. shtml [Accessed
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hydro [Accessed 2012-03].
[26] Maher P, Smith NPA, Williams AA. Assessment of pico hydro as an option for off-
grid electrification in Kenya. Renewable Energy. 2003; 28(9): 1357–1369. DOI:10.
1016/S0960-1481(02)00216-1.
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[31] Morea F, Viciguerra G, Cucchi D, Valencia C. Life cycle cost evaluation of off-grid
PV-wind hybrid power systems. In: 29th International Telecommunications Energy
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Chapter 4
Native Forest and Climate Change — The Role of the

Subtropical Forest, Potentials, and Threats
Silvina M. Manrique and Judith Franco
http://dx.doi.org/10.5772/62030
Abstract
The subtropical rainforest of Argentina, called Yungas, has been subjected to rapid de‐
forestation and degradation processes in recent years, especially in the lower district:
"Pedemontana Jungle" (PJ; ≤900 m.a.s.l.). In Salta, in the north of the country, the rate
of deforestation is around three times higher than the world average. The disappear‐
ance of PJ significantly limits the area of contact between Yungas and Chaco forest,
which could have important consequences for natural and cultural biodiversity in the
region (the largest number of aboriginal ethnic groups live here, most of which de‐
pend on native forest for their existence and identity). In addition, the loss and degra‐
dation of forests is the second largest sector of greenhouse gas (GHG) emissions to the
atmosphere (about 18%), affecting the world climate. We present a synthesis of differ‐
ent studies developed in PJ forests, observing its role as reservoirs of carbon and dis‐
cussing issues that could influence the total capacity of carbon sequestration of the
same. This will contribute to build the reliable database on the sequestration potential,
which will facilitate standardization of units, reduction of uncertainties, and contribu‐
tion to a more efficient strategy to limit the GHG emission to the environment, provid‐
ing some learning and useful recommendations.
Keywords: biomass, carbon sequestration, edge effect, fragmentation, native forest
1. Introduction
1.1. Deforestation, fragmentation, and climate change
According to recent studies, the forests covering about 30% of the earth's surface [1] contain
80% terrestrial biomass and provide habitat for about half of the world's known species of
plants and animals [2]. Forests provide a wide range of ecological, economic, and social assets,
as well as services such as climate regulation through the storage of carbon in complex physical,
56 Greenhouse Gases
chemical, and biological processes [3–5]. Despite a wide recognition of the importance of native
forests, recent data show that the loss of forest cover over the planet (deforestation) in 2000–
2012 was 2.3 million km2, while the gain (grown or planted) was 0.8 million km2 [6]. Conversely,
Keenan et al. reported a rate of 0.08% of forest loss in 2010–2015, while farmland continued
expanding in 70% of the countries [1].
Native forests have been affected in terms of not only the total amount of existing surface
(deforestation) but also the quality of the remaining fragments (degradation) [5, 7], therefore
the biomass availability and its derived flow, which means a source of ecosystem goods and
services, has been doubly modified. Several of them, such as soil protection, gas and climate
regulation, water regulation, nutrient cycling, providing habitat and refuge, food production,
raw materials and genetic resources, the provision of medicinal and ornamental resources, and
others related to culture (recreation, aesthetics, and spirituality), are associated with biomass
existence and generation [2, 4, 5]. Similarly, there are an increasing number of studies showing
the interrelationship between the aboveground and subterranean processes, and particularly
among the aboveground biomass (AGB) and soil, links that determine the abundance of
species, coexistence, and succession [8, 9]. Therefore, any changes in the biomass, including
degradation – although it is a hardly measureable phenomenon [10] – will affect soil charac‐
teristics, which, in turn, will modify reproduction patterns and survival of typical plants in the
ecosystem in question and their associated fauna [2, 8, 9].
Deforestation and fragmentation of forests, have been an object of study of the scientific
community for many years, but attention to these phenomena has begun to rise from the
perspective of their contribution to global warming by greenhouse gas emissions [3, 10–15]. It
is recognized that the change in land use (including forest degradation and deforestation) is
the second sector of global importance in terms of GHG emissions (so-called LULUCF or land
use, land use change and forestry) and is responsible for 20% of total emissions [16]; therefore,
it is an important component of human impact on global climate.
Variations in the soil cover are one of the natural and anthropogenic forces that operate on
different scales, influencing changes in regional and global climates [3, 13, 16]. Malhi et al. [13]
document some interrelations in the Amazon forests, noting that they have a great influence
on regional and global climates. They mention that the extraction of water from the soil,
through the tree roots up to 10 m depth, and its return to the atmosphere (“perspiration
service”) is, perhaps, the most important regional ecosystem service. Therefore, the removal
of trees through deforestation can become a driver for climate change and a positive feedback
for externally forced climate change. In agreement with the other authors, forest loss also
results in (i) decreased cloud cover and an increase in insulation; (ii) increase in the reflectance
of the earth's surface, approximately offsetting the effect of clouds; (iii) changes in the aerosol
loading of the atmosphere from a hyperclean “green ocean” atmosphere to a smoky and dusty
continental atmosphere that can modify rainfall patterns; and (iv) changes in the surface
roughness (and therefore the wind speed) and a large-scale convergence of atmospheric
humidity, which generates precipitation [14, 15]. These large-scale interrelations repeat on
lesser scales, although they have not been sufficiently studied.
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Native Forest and Climate Change — The Role of the Subtropical Forest, Potentials, and Threats 57
http://dx.doi.org/10.5772/62030
Deforestation and fragmentation could increase the vulnerability of forests to climate change
[2, 3, 17, 18], being two interlinked processes, since deforestation to open up new land for
cultivation is concentrated in the periphery of existing forest fragments, reducing them in size
and/or making them disappear. Both processes have been recognized as important drivers of
biodiversity loss [2, 4, 5, 19–21].
1.2. Climate change in Argentina
In 2015, Argentina presented its Third National Communication (TNC) on Climate Change
[22], with an updated GHG inventory as part of the fulfillment of their assumed commitments
to the United Nations Framework Convention on Climate Change (UNFCCC). They inform
that national emissions in 2012 imply a 0.88% participation in global emissions (429,437 Gg
CO2eq). The six sectors surveyed were as follows: (1) energy (43% of total emissions), (2)
industrial processes (3.6%), (3) use of solvents and other products (0%), (4) agriculture and
livestock (27.8 %), (5) land use change and forestry (LUCF) (21.1%), and (6) waste (6%). Within
the LUCF sector – the third most important – the subsector of “forest and other land conver‐
sion” contributes 67% of emissions.
Of the total native forests, in 2002 (33 million ha), Yungas occupied 11.2% of the surface (3.7
million ha). A TNC report mentions that the loss of native forests in 2002–2010 was 3.5 million
hectares (computed in “conversion of forests and other land”) corresponding to the 8% loss of
Yungas (280,300 ha), which caused a reduction of 7.5% of the total area. The rest of the removed
area corresponded to the Chaco region, whose surface involved 70% of the total forests in the
country (larger ecosystem) that year.
In effect, the Intergovernmental Panel on Climate Change (IPCC), in which more than 300
scientists from all over the world participate, warned that, in 2014, 4.3% of global deforestation
occurred in Argentina [16]. At a local level, the Secretary of Environment for the Nation
published, in the same year, the report “Monitoring of the area of native forest in Argentina,”
pointing out that between November 2007 (when the National Forest Act was enacted) and
the end of 2013, 1.9 million hectares were removed – an average of 1 ha/2 min. Eighty percent
of the deforestation is concentrated in four provinces: Santiago del Estero, Salta, Formosa, and
Chaco [23].
At the same time, variations in local and regional climate had begun to be noticed in the
country. The average annual temperature increased from 1960 to 2010 in almost all the
northwest subregions (and Cuyo); in many areas (more than 0.5°C), the most notable changes
were observed in spring. From 1950 to 2010, the annual average temperature, through the
region was 0.6ºC and it reached 0.7°C in Salta and Jujuy [22]. At a national level, the average
temperature increases from ½ to 1ºC. The possibility of increasingly intense heat waves has
been forecast. In the northwest, an increase of 4–5º is projected by 2030, one of the highest on
the planet. In the west and, notably, in the north of the country, there has been a shift toward
the extension of dry winters. This could be generating problems with water availability for the
populace, more favorable conditions for wildfires in forests and grasslands, as well as stress
on livestock. This could bring implications on the biodiversity of the native forest remnants in
58 Greenhouse Gases
Yungas [22], and, at the same time, the disappearance of such remnants, which could provide
feedback for those changes that are taking place at an atmospheric level.
Improving the understanding of biomass and carbon stocks in forests, therefore, provides
valuable information for use land planning and designing comprehensive strategies in the
context of global climate change. The purpose of this chapter is to present a synthesis of some
of the different works developed in the subtropical forest of the Pedemontana Jungle, based
on years of studies in the area. Studies were focused on the northern of the country, noting its
role as carbon reservoirs and discussing factors that could influence the carbon sequestration
total capacity of the same. The information presented here, without doubt, will contribute to
the construction of a reliable database of this potential, which will facilitate standardization of
units, reduction of uncertainties, and contribution to a more efficient strategy to limit GHG
emissions, providing some learning and useful recommendations. Inasmuch as this ecosystem
extends to Venezuela, the results obtained will provide a frame of reference for future studies
on this ecological zone. This information is also necessary to improve the understanding of
the distribution patterns of biomass and carbon at the global level and to describe patterns of
land use. The results presented could guide in designing plans and management policies for
these types of forests, at national and international levels.
2. Materials and methods
2.1. The Yungas ecosystem: Pedemontana Jungle
The phytogeographic Yungas province borders the Andes mountain range from Venezuela to
Argentina [24]. The Argentine Yungas, which constitute a vital habitat for the fundamental
role in the regulation of the water basins and protection against erosion, have been subjected
to a long history of anthropogenic interventions, especially in low-lying areas, called the
Pedemontana Jungles, which have a high agricultural potential [25].
The history of Pedemontana Jungle in the north of Argentina has been closely tied to the
railway expansion, necessary for the transport of precious wood, tropical crops, and sugar.
More recently, from the 1990s, soybeans won the major role, expanding rapidly in the foothills
landscape and its transition to the Chaco plain. The deterioration from the advance of the
agricultural frontier, coupled with logging, the commercial bird catching and poaching –
among others – are causes for concern because of the almost 5 million hectares that cover the
Argentine Yungas, the effectively protected area is only 5% of the total [21].
The Pedemontana Jungle, which stretches from 450 to 900 m.a.s.l. – other authors mention
minor ranges [24] – and which represents 25% of the Yungas, has been considered as an
ecosystem in danger of extinction, and its deforestation would eliminate 30% of the total
Yungas biodiversity [25]. In this region, 120 species of mammals and 8 of the 10 species of
neotropical cats are represented. Also, approximately 583 species of birds inhabit it, which
represent 60% of the species in Argentina [26]. Likewise, in the Pedemontana Jungle of
Argentina and Bolivia, they were identified 18 AICBA (Areas of Importance for the Conser‐
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http://dx.doi.org/10.5772/62030
vation of the Birds of Argentina), noting that the AICBA including sectors of the Pedemontana
Jungle, have a diversity of birds comparable to the cloud mountain forests (ecological zone of
higher altitude than the PJ) and higher than the Chaco forests that surround them [27].
The physiography varies from submountain foothills to alluvial descents, presenting a hilly
and wavy topography. The soils present in the study area are according to the taxonomic
classification of FAO soils of the Phaeozem Haplic and Luvic type [28]. Soils of luvisol calcium
were recorded only on the Coronel Moldes site.
The climograph and altitude for each of the studied sites are shown in Figure 1.
Temperature (°C) Altitude (m)

Precipitation (mm)
Precipitation (mm) and altitude (m)

25 1200
Temperature (°C)
20 1000
800
15
600
10
400
5 200
0 0
Figure 1. Annual average rainfall (mm), annual average temperature (°C), and altitude (m.a.s.l.) for different sites stud‐
Figure 1. Annual average rainfall (mm), annual average temperature (°C), and altitude (m.a.s.l.) for
ied in the Pedemontana Jungle in northern Argentina (Salta and Jujuy provinces). Source: http://es.climate-data.org/
different sites studied in the Pedemontana Jungle in northern Argentina (Salta and Jujuy
location/145171/
provinces). Source: http://es.climate‐data.org/location/145171/
2.2. Case studies

All the studies
80 summarized in this chapter were carried out in the province of Salta, in northern
Argentina, with the exception of case II, which was developed in the province of Jujuy.
Yungas The
forest
province of70Salta has an area of 155,500 km², occupying the sixth position at the national level,
Chaco forest
and with a value similar to the surface of Nepal, has a population of 1.2 million, making it the
eighth most populous out of 23 at the national level.
60
Carbon Stored (tC/ ha)
Of the entire
50 surface occupied by the Yungas ecosystem in the country, 61% of it extends
through this province, making it essential to focus on studies in this particular region. Also,
Salta has 23%
40 of the total surface of the country’s native forests, and deforestation in this
province is triple the world average [29].
30
Some of the assumptions, which have been evaluated from various case studies (always
focusing on20the Pedemontana Jungle), are as follows (more detailed in Table 1):
10
0
AGB‐10 AGB‐0 BGB LUV HUV LI SOC
Figure 2. Carbon stock and contribution of each carbon pool studied. The acronyms AGB10, AGB0,
60 Greenhouse Gases
i. The subtropical rainforests of the country have a greater capacity for carbon seques‐
tration than subtropical dry forests at identical latitude.
ii. Carbon sequestration in forests disturbed by human activity is lower than in forests
less seized by humans, releasing the difference of carbon into the atmosphere.
iii. The carbon stock, in legally protected forest sectors, is higher than in other sectors
without protection located at identical latitude and under similar conditions.
iv. The potential for carbon sequestration in the Pedemontana Jungle is less if latitude
increases.
v. The fragmentation of the Pedemontana Jungle generates microclimatic changes at the
edges, which could affect carbon sequestration.
Case I II III IV V
Legal protection No Yes Yes and no No No
Site Coronel Moldes National Park Wildlife Reserve of Aguaray and Colonia Santa Rosa
Calilegua Acambuco and General Pizarro
Campo Pizarro
Plot number 23 main plots 20 main plots 50 main plots 50 main plots 78 main plots
(AGB10) for each (AGB10); 20 plots of (AGB10); 50 plots of (AGB10); 50 plots of (AGB10); 78 plots of
ecosystem; 23 plots 50 m2 (AGB0); 40 50 m2 (AGB0); 250 50 m2 (AGB00); 250 50 m2; 468 soil plots
of 50 m (AGB0); 23
2
plots of 1 m (HUV
2
soil plots (SOC) soil plots (SOC) and (SOC); 156
plots of 5 m2 (LUV); and LI); 120 soil 500 microclimatic microclimatic
46 plots of 1 m2 plots (SOC) instantaneous instantaneous
(HUV and LI); 138 records (MIC) records (MIC)
soil plots (SOC)
Carbon pool AGB0 AGB0 AGB0 AGB0 AGB0

AGB10 AGB10 AGB10 AGB10 AGB10
LI LI BGB BGB BGB
HUV HUV SOC SOC SOC
LUV BGB MIC MIC
BGB SOC
SOC
The acronyms AGB10, AGB0, HUV, LUV, LI, SOC, MIC are explained in the text.
Table 1. Methodological differences and similarities between the case studies.
2.3. Sampling design

The methodology used for each of the case studies presented in the next section shows some
differences that are summarized in Table 1. In most cases, the data were collected following a
random sampling design. Only in case V, the sampling was systematic.
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The experimental design used was nested plots. Main plots had a total area of 100 m2 and were
rectangular plots. The criterion used to determine sample size for each stratum was an
estimation of AGB of trees with a diameter at breast height (dbh) ≥ 10 cm during pre-sampling
(90% probability and 20% mean standard error).
Carbon represents about 50% of the total oven-dried biomass present in forests [32]. Estimation
of carbon pools in forests necessarily involves studying the different strata of biomass present
in them. In the different studies, the following carbon pools and variables were measured:
a. Aboveground tree biomass: AGB refers to the total amount of aboveground living organic
matter in trees and shrubs (≤1 cm dbh and ≥50 cm height) expressed as oven-dried tons.
Total height (from ground level up to crown point) and dbh were measured in all trees
with dbh ≥ 10 cm (called AGB10) in 100 m2 plots. When 1 ≤ dbh ≤ 10 cm and height ≥ 50 cm
(called AGB0), trees were measured in 50 m2 plots. In multiple-stemmed trees, only the
longest stem was measured. If neither shoot was dominant, an average of similar shoots
was calculated. The basal diameter was registered only when the stem was shorter than
the dbh. Standing dead trees with dbh ≥ 1 cm and fallen trees with dbh ≥ 10 cm were
measured in the same way as living trees. However, correction factors of 0.8 and 0.7,
respectively, were applied to the biomass values obtained. For hollow or ill trees, a factor
of 0.9 was applied.
b. Lignified understory vegetation (LUV): All shrubs shorter than 50 cm were collected in 5
m2 plots within the corners of the main 100 m2 plots.
c. Herbaceous understory vegetation (HUV): This fraction was removed in two 1 m2 plots.
These plots were located in opposite corners within the 100 m2 plots used to measure
AGB10.
d. Litter (LI): Organic debris on the soil surface (including freshly fallen parts of plants,
decomposing organic matter, and deadwood) with a diameter no greater than 10 cm were
collected in the same plots used for HUV.
e. Belowground biomass (BGB) (tree roots): Due to the difficulties involved in the measure‐
ment of this fraction, it was estimated indirectly as a proportion of AGB10 for Chaco and
Yungas.
f. Soil: Bulk density and percentage of organic carbon were determined in soil samples
collected at a depth of 30 cm [30]. Vegetation and litter were removed from the soil surface
prior to sampling. Bulk density was determined in two samples per plot using the cylinder
method. Results from these samples were averaged. The percentage of organic carbon was
measured following the method described in Walkley and Black. This measurement was
performed on a composite sample built from four samples taken at identical distances
within a linear transect along the longest axis of the 100 m2 plots (dimensions of these plots
were 5 m × 20 m).
Wet weight was recorded on site for LUV, HUV, and LI fractions. Dry weight was determined
in the lab (registered after drying in an oven at 80°C until constant weight). The equation
introduced by Cairns and coworkers [31], for tropical forest and lower latitudes than 25°, was
used. The AGB fraction, also called as “biomass density” when expressed as tons of oven-dried
62 Greenhouse Gases
weight per ha [32], is the main source of total biomass in a forest ecosystem. Its relevance as a
GHG mitigation option is therefore crucial [11–13]. This fraction was thoroughly assessed
using a nondestructive methodology: allometric equations (Table 2).
g. Solar radiation intensity (W/m2): A LICOR 250 pyranometer was used with a silicon sensor
with a resolution of 0.1 W/m2. The measures of global radiation readings are precise to
±5%.
h. Air relative humidity (%): This was recorded using a psychrometer or hygrometric probe
Vaisala HM 34. Reading is immediate and accuracy is ±2%. The sensor is the Humicap
type. Measurements were taken at 1.5 m from ground level.
i. Air relative temperature (°C): This was registered with a Vaisala HM 34 probe, with
temperatures ranging from −20 to +60°C. Measurements were taken at 1.5 m from ground
level.
j. Soil temperature (°C): This was measured with a FLUKE 54 II digital thermometer with
accuracy ranging from 0.05% + 0.3°C. Measurements were taken at 10 cm depth.
k. Soil humidity (%): This was estimated by two soil samples taken at 10 cm depth per plot.
Authors Carbon pool Equation No.

Chave et al.
AGB10 and AGB0 AGB = exp( − 2.977 + ln(S.D2.H)) (1)
(2005)
Brown et al.
AGB10 and AGB0 AGB = exp( − 2.4090 + 0.9522 ln(S.D2.H.)) (2)
(1989)
Chave et al.
AGB = 0.112(S.D2.H.)
0.916
AGB10 and AGB0 (3)
(2005)
Gehring et al. Diameter (30 cm) = 1.235 × dap + 0.002 × (dap)2
AGB (4)
(2004) AGB = exp( − 7.114 + 2.276*ln(D30))
Cairns et al.
BGB BGB = exp( − 1.0587 + 0.8836 × ln(AGB)) (5)
(1997)
Macdicken,
SOC SOC = OC × BD × D (6)
(1997)
Sevola (1975) V V = − 2.2910 + 0.0558 × log (D 2 × H ) (7)
Sevola (1975) V V = − 3.2794 − 0.0734 × logH + 1.0580 × log(D 2 × H )
2 (8)
Sevola (1975) V V = − 2.4385 + 0.9560 × log(D 2 × H ) − 0.80350 × log(H / D ) (9)
Chave et al.
AGB = 0.0673 + (S.D 2.H )
0.976
AGB10 and AGB0 (10)
(2014)
AGB = tree aboveground biomass (kg oven-dry); SB = stem biomass; S = wood density (oven-dried biomass per green
volume, in t/m3); D = diameter at breast height (1.3 m above ground, in cm); D30 = diameter at 30 cm above ground; H
= total height (m); BGB = belowground biomass (t/ha); OC = concentration of organic carbon in the soil (%); BD = soil
bulk density (g/cm3) and D = depth of soil (cm); V = total tree volume, in dm3, included stem, bark, and branches.
Table 2. Allometric equations used in this chapter.
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The last five parameters called “microclimate factors” were measured in each preset distance,
for each transect study, always at midday between 12 p.m. and 2 p.m. In the case of values per
site, the different measurements taken were averaged per plot.
2.4. Estimation of biomass and carbon
Once field measurements were carried out, the data were computed clerically, carrying out
the biomass estimate for each compartment, transforming it into carbon values (factor of 0.5
[32]) and achieving the sum of all the carbon pools. All equations used are shown in Table 2.
Equation (1) was developed by Chave et al. [33] for “moist forest stand,” while equation (3),
by the same authors, was developed for “dry forest stands” (applied to the Chaco). Equation
(10) was recently developed by these authors and was applied to the Anadenatnhera colubrina
and Cedrela angustifolia species, for which no specific equations were found. Equation (4) was
applied only in vines and required converting the dbh into diameters at 30 cm height, and then
entering that value into the equation [34]. In the case of volumetric equations (7, 8, and 9) [35],
the total biomass conversion was carried out by multiplying the total volume by the basic
density of each species. Equation (7) was then applied to the Calycophyllum multiflorum species,
equation (8) to Phyllostylon rhamnoides, and equation (9) to Astronium urundeuva, all equations
being developed in the region.
The basic wood densities (dry) for different species were obtained from Ref. [36]. A basic
density value obtained from the weighted average of the densities of each site’s species was
used for the species that for various reasons could not be identified. For estimation of SOC
(soil organic carbon), equation (6) was used [30]. For data analysis, the nonparametric type test
was chosen. We used the INFOSTAT® software, and a value of 0.05 was considered significant.
3. Results and discussion
3.1. Effect of temperature and humidity on the carbon stock: dry and humid subtropical
forests at the same latitude
Contributors: Manrique, S.M. and Franco, J.
The subtropical moist forests of the country have a greater capacity of carbon sequestration
than subtropical dry forests at identical latitude.
As was mentioned, the Chaco ecosystem is the largest surface area at the national level. It was
interesting to compare facets of this ecosystem with the Yungas Pedemontana Jungle with
regard to the potential for carbon sequestration at the same latitude. The work was carried out
in the municipality of Coronel Moldes (25°16′00″ South latitude and 65°29′00″ West longi‐
tude), 60 km south of the capital of the province of Salta.
The province’s climate is defined as subtropical mountainous with a dry season. However, the
topography does allow the development of contrasting environments. Thus, the moist winds
from the southeast enter the province and release their moisture from submountainous ranges
64 Greenhouse Gases
that make up the sub-Andean hills in the north-central region of the country. This allows the
spread of vegetation, which is a unique environment that runs along elevations in different
altitudes, forming a north–south strip. The Chaco ecosystem develops on the plain that extends
from the center of the country to the East, and in Salta two districts are exhibited: the semiarid
Chaco and the mountain Chaco. Precipitation decreases as it moves eastward, shrinking from
more than 650–700 mm per year in the Pedemontana Jungle ecosystem to values of less than
460 mm in the Chaco ecosystem. Temperatures also suffer a slight increase as it moves west
away from the mountains, which have the moisture [37], marking isotherms in the range of
tenths of degrees, as the distance between the mountains and the eastern point increases.
The starting points are corroborated in this study: the most humid ecosystem shows a carbon
stock 43% larger than that stored in the driest ecosystem (Table 3). In the case of Yungas, the
AGB fraction means almost 80% of the total biomass, although the greater fraction (AGB10)
alone implies 71%, leaving the AGB0 a reduced participation. The BGB means more than 16%
of total biomass, and the rest if divided between the LI (about 3%), the LUV (with almost 2%)
and lastly, the negligible participation of HUV (0.1%). For the Chaco, the fraction AGB provides
more than 71% of the total biomass, where the trees of larger diameters (AGB10) mean 66% of
Figure 1. Annual average rainfall (mm), annual average temperature (°C), and altitude (m.a.s.l.) for
this contribution. In this environment, the BGB takes on greater importance (with more than
21%),provinces).
and is followed
Source:by – in the identical order shown in the Yungas environment – LI fraction
http://es.climate‐data.org/location/145171/
(3.2%), LUV (2.6%), and HUV (0.6%) (Figure 2).
80
Yungas forest
70
Chaco forest
60
50
40
30
20
10
0
AGB‐10 AGB‐0 BGB LUV HUV LI SOC
Figure 2. Carbon stock and contribution of each carbon pool studied. The acronyms AGB10, AGB0, BGB, HUV, LUV, LI
Figure
and SOC are2.explained in the and
Carbon stock text. contribution of each carbon pool studied. The acronyms AGB10, AGB0,
BGB, HUV, LUV, LI and SOC are explained in the text.
Clearly, the AGB and SOC fractions are the two largest contributors in the two ecosystems. In
Yungas, the AGB represents 48% of the total fixed carbon, while the SOC contributes 39%. In
the case of the Chaco, 33% of the total carbon in the ecosystem is concentrated in AGB, while
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54% remains captured in SOC. Soil is an important reservoir of carbon, becoming the most
important fraction in dry environments. However, when we compare the absolute values of
SOC in both environments, the soil shows a significant relationship with the vegetation found
on the surface. In Yungas, it is 63 tC/ha, while in Chaco it is 50 tC/ha.
Sector Average Standard deviation
Yungas forest (Selva Pedemontana) 162 85
Chaco forest (Chaco Serrano) 92 42
Table 3. Carbon stock (tC/ha) in both ecosystems, Chaco and Yungas, in Coronel Moldes, Salta, Argentina.
Viglizzo and Jobbágy [21] point out that the carbon stocks in the biomass and in the organic
fraction of the soil in Argentina vary from one ecoregion to another. The carbon stock in
biomass is directly associated with the availability of vegetation biomass. In the tropical and
subtropical regions of Argentina (e.g., Yungas), more than 50% of total carbon is found stored
in the AGB fraction, which makes this element vulnerable and easily appropriable by humans.
This relationship falls dramatically in areas dominated by grasslands/pastures (e.g., Chaco),
and even more (without reaching 10%) in intensively cultivated ecosystems.
In Yungas, the average height was 11 m and average dbh was 17.6 cm, both higher than those
for Chaco, although still lower than figures cited for pristine Yungas ecosystem [24, 25, 38].
Estimations made for tropical humid forests around the world range from 150 to 192 t/ha for
closed, undisturbed forests and around 50 t/ha for open forests [39]. Certainly, different factors
may be influencing these differences (rainfall, soil type and site features, topography, etc.) [32,
33, 39, 40]. Moreover, the structure of the forest in the Yungas area included in this study was
clearly disturbed by humans and livestock. Numerous recent and decomposing stumps were
found and there were unambiguous signs of wandering animals and persons. Solanum
riparium was also abundant in this area, a species normally dispersed by wild animals or cattle.
The appearance of typically Chaco species in sections of Yungas forest is probably a sign of
human intervention in this region [24, 38].
Our results suggest that forest degradation is detectable not only in Yungas but also in Chaco.
In environments similar to Chaco, discrepancies between these results (lower) and estimations
made in similar environments in other forests of the world might be due to structural differ‐
ences, altitude, latitude and humidity, gradients (24, 32, 33). However, in our case the level of
degradation exerted by human activity in this environment might also be responsible for the
discrepancies [20, 21, 41] (further details refer to [43]).
Economic activities such as agriculture and logging, which take place in these ecosystems, are
arguably not respecting their carrying capacity. Local institutions do not seem to be capable
of stopping, controlling, or regulating these activities. Whether entering into a market-based
system like the one promoted by the Kyoto Protocol will be part of the solution to the problem
of deforestation and conservation of local native forests remains to be seen. Decisions are
highly political and many times the relevant decision makers are thousands of kilometers
66 Greenhouse Gases
away. No decisions affecting the future of these forests should be taken until agreements on
this issue are reached or until judiciary processes are properly finished. Competing claims on
the ownership of the forestland, the products of the forests, and the provision of ecosystem
services must be taken into consideration in a comprehensive forest management.
3.2. Effect of human influence on the carbon stock in forests
Contributors: Gallucci, G.B. and Manrique, S.M.
Carbon sequestration in forest disturbed by human activity is lower than in forests less
seized by humans.
In case I, we identified that studied forest sectors clearly show human influence as a factor of
degradation of the original structure of the same type. In this case study, it was interesting,
particularly, to assess this difference and try to quantify it for samples of the same Pedemon‐
tana Jungle ecosystem, but this time as a protected area: Calilegua National Park (23°27’–23°45’
South latitude and 64°33’–64° 52’0” West longitude). The park was created in 1979 to protect
a representative sector of the Yungas and to protect the headwaters of the Calilegua streams,
which are a part of the San Francisco River basin, and provide water to neighboring crops in
the protected area. With an area of 76,320 ha, it is the largest national park in the Argentine
Northwest. It is approximately 165 km from the city of Salta.
We studied two areas of the park (north and south sectors) separated by only 50 km but which
have different accessibility to human influence. The north sector surrounding the town of
Caimancito has been invaded by oil companies, which have conducted exploration activities
in the area, and therefore have dissected the forest, leaving open “choppings” or paths of
prospecting. This has led to the accessibility of nearby residents who have taken advantage of
the forest and even have led their animals to graze there. In the south, on the other hand,
exploration activities were not carried out and therefore, even if villagers could have accessed
the site, on its more sheltered side (the other side of rivers that flow through the park), a better
conservation has been maintained, which can be seen in the large, heavily wooded trees, and
the high forest value that is still there. Surely, the presence of Park Rangers (Aguas Blancas
section) in this sector has helped much in this protection.
Two sectors that maintain homogeneous topographic, edaphic, and climatic conditions were
selected. Both sectors were compared through analysis of average annual rainfall records (56
years series) without finding statistically significant differences (H = 0.01, p > 0.999). Records
of minima and maxima were also analyzed. The series of annual average temperatures were
not statistically different (H = 0.16, p = 0.686). In the case of edaphic variables, existing carto‐
graphic studies allowed us to associate both sectors with the same series of soils. Organic
matter samples taken in the area showed no significant differences (H = 4.71, p=0.210). It was
assumed that both sectors had identical site conditions.
We evaluated the same carbon pools as in case I with the exception of LUV, which had no
relevant participation in the previous case, and therefore it was not included in the pursuit of
reducing the fieldwork effort and costs.
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Figure 1. Annual average rainfall (mm), annual average temperature (°C),http://dx.doi.org/10.5772/62030
and altitude (m.a.s.l.) for
provinces). Source: http://es.climate‐data.org/location/145171/
The obtained results allow us to advance with the basic assumption: the north sector, subject
to anthropogenic influence, it showed a carbon stock 23% lower than the south sector, which
had less accessibility and a better state of conservation (Table 4). These differences were
statistically significant (H = 11.20, p < 0.001) only for the AGB stratum, but not for the other
strata studied nor for the total carbon stock. Under similar conditions of climate, soil, geo‐
morphology, altitude, and latitude, the human influence could explain these differences, as
the AGB stratum is the easiest to appropriate by humans [10, 17, 19, 21]. The AGB make the
Figure contribution
largest 2. Carbon stock
in and
bothcontribution
sectors to of
the carbon
each carbonstock
pool(53, 55%),The
studied. followed byAGB
acronyms SOC (28–31%)
10, AGB0,
BGB, HUV, LUV, LI and SOC are explained in the text.

and finally BGB (8–10%) depending on the sector analyzed (Figure 3).
180
North Sector
160
South Sector
140
120
100
80
60
40
20
0
AGB‐10 AGB‐0 BGB HUV LI SOC
Figure 3. Carbon stock and contribution of each carbon pool studied. The acronyms AGB10, AGB0, BGB, HUV, LI and
Figure
SOC 3. Carbon
are explained in the text.and contribution of each carbon pool studied. The acronyms AGB10, AGB0,
stock
BGB, HUV, LI and SOC are explained in the text.
Protected forest degraded (north sector) 221 116
Protected forest better preserved (south sector) 272 129
Table 4. Carbon stock (tC/ha) in both sectors, north and south, in Calilegua, Jujuy, Argentina.
Against the results, there is an urgent need to review the administration and safeguards for
the Calilegua National Park, with a reinforcement of the Corps of Rangers in the area (currently
with few people that must patrol the whole park). Other authors are agreed that the declaration
to protect does not always mean adequate protection [43, 44]. The acquisition of more financial
resources for the protected areas should be carried out in the light of a strict management plan
68 Greenhouse Gases
and monitoring. Poaching, livestock grazing, and logging without authorization – with the
thinning out of valuable wood species – must be eradicated from the core area, so that the Park
can fulfill its role with the conservation of biodiversity, which has been included in the
international statement “Yungas Biosphere Reserve.”
3.3. Effect of legal protection on the ecosystem
Contributors: Manrique, S.M.; Vacaflor, P.; Fernández, M. and Franco, J.
The carbon stock in legally protected forest sectors is higher than in unprotected sectors
located at the same latitude and under the same conditions.
In case II, two sectors of the legally protected Pedemontana Jungle were analyzed, which
clearly show differences between them in their accessibility to human influence. It became
interesting to continue in this line of study, exploring if the trend found in the former case
could be due to a particular situation in the Calilegua National Park. In this case study, we
sought to observe comparative sectors inside and outside legally protected regions located at
the same latitude and altitude, and under the same conditions. We started to identify protected
areas in the province which shelter samples from the Pedemontana Jungle. We finally worked
in and out of the Provincial Reserve of Flora and Fauna of Acambuco (PRFFA) (22°12'38.5"
South latitude and 63°56'23.1" West longitude) and in the National Reserve of Campo Pizarro
(NRCP) (24°11'54.87 and 24°14'21.7" South latitude, and 64° 7'27.00" and 64° 9'23.79" West
longitude). The creation of PRFFA dates back to 1979, and currently has an area of 32,000 ha.
It is approximately 470 km from the city of Salta to PRFFA. In the case of NRCP, it was created
in late 1995 with an area of 25,000 ha, and soon after a process of reversal and social conflict,
the NRCP ended up with an area of 21,000 ha. It is approximately 280 km from Salta. In this
study, efforts were concentrated in the carbon pools considered most significant in the prior
cases, eliminating HUV and LI from the samples.
The results show that, on average, the carbon stock is similar in protected and nonprotected
areas (Table 5). Having considered the average of all sectors included in the Reserves and the
average of all the studied sectors not protected in them, no significant differences were found
(H = 0.85, p= 0.356), by even analyzing just AGB separately (H = 0.98, p = 0.322). The initial
assumption cannot be confirmed: no case shows that the legal protection has caused differences
in the ecosystem it protects, neither favoring nor against. Yet we see different values if we
consider the samples of the north sector and south sector separately, as will be discussed in
the following section.
Protected forest 203 74
Unprotected forest 213 82
Table 5. Carbon stock (tC/ha) in both sectors, protected and unprotected forest, in Acambuco and Campo Pizarro,
Salta, Argentina.
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Figure
In terms3.ofCarbon
the importance of each of the
stock and contribution studied
of each carboncarbon pools (Figure
pool studied. 4), theAGB
The acronyms carbon fixed
10, AGB 0, at
the fraction of AGB
BGB, HUV, returns
LI and toexplained
SOC are be largerinthan the fixed carbon in the soil (SOC).
the text.
140
Unprotected forest
120
Protected forest
Carbon stored (tC/ha)
100
80
60
40
20
0
AGB‐10 AGB‐0 BGB SOC
Figure 4. Carbon stock and contribution of each carbon pool studied. The acronyms AGB10, AGB0, BGB and SOC are
explained in the text.
The inclusion of Pedemontana Jungle sectors within legal protection figures has not resulted
in benefits in terms of their ability to sequester carbon in the different carbon pools. However,
this consideration is not conclusive in the role of protected areas. Pedemontana Jungle sectors,
within and without the protected areas, could be similar in their capacity to sequester carbon
in two possible situations: (i) a good general ecosystem condition level, which still remains a
certain continuity of ecosystem, and therefore, either inside or outside the Reserve, is of similar
forest samples and show no particular features nor different structural configurations; (ii) a
poor state of conservation, which has equally affected protected and nonprotected areas,
imprinting similar features in the different sectors, by simultaneous intervention in the
different forest sectors. A more in-depth study of other ecosystem variables would perhaps
lean toward one alternative or another. However, the different log of measured carbon stock
in case II in Calilegua National Park, or the degradation features in the two types of ecosystems
(Yungas and Chaco), which were observed in case I, clearly indicates that the forests have not
received the attention they should have over the years.
Therefore, these thoughts should be a trigger to continue with deeper and more comprehensive
evaluation and to draw attention to the need to review and update control schemes and
monitoring of native forests – mainly protected areas. The global community has recognized
the importance of forests for biodiversity, and has prioritized the preservation of forest
biodiversity and ecosystem functions through multiple multilateral agreements and processes.
For example, the Aichi Biodiversity Targets established by the Convention on Biological
70 Greenhouse Gases
Diversity (CBD) in its strategic plan include halving the rate of loss of natural habitats including
forests (target 5) and conserving 17% of terrestrial areas through effectively and equitably
managed, ecologically representative, and well-connected systems of protected areas (target
11). Currently, designating protected areas is one of the primary strategies for conserving
biodiversity. Different authors have discussed the increase in protected areas over the past
century; however, they find that many key biodiversity areas are not adequately covered by
protected area status [44].
The always-protected system areas will be limited to preserve all the original diversity, but
even so, it is imperative that these areas exist and continue to expand with scientific criteria.
3.4. Effect of latitude and altitude on the carbon stock
Contributors: Manrique, S.M.; Vacaflor, P. and Fernández, M.

The potential of carbon sequestration in the Pedemontana Jungle is less if the latitude
increases.
In case III, the average carbon stock in protected and unprotected areas was approximately
similar, although with different values from cases I to II. This led to the analysis of the position
within the ecosystem of the studied sites. In case I, with 162 tC/ha, the forest is at 25°16 and
65°29. In case II, with 221–272 tC/ha, the forest is approximately between 23°27 and 64°33.
Analyzing other sectors located at different latitudes could confirm the trend of higher values
of biomass and the north sector of the Pedemontana Jungle (e.g., Calilegua showing a value
100% greater than the Coronel Moldes value) and values that decrease toward the south. It
was interesting, therefore, to explore case III results separately, taking as a northern sector, the
plots carried out near Aguaray (22°12 and 63°56) and, as a southern sector, those carried out
near General Pizarro (24°11 and 64°7).
Sector RI (W/m2) RH (%) RT (°C) SM (%) ST (°C)
North sector 0.065 a 43.55 a 26.94 a 9.9 a 22.09 a
(0.02–0.44) (21.7–86.7) (16.6–36.55) (3.15–17.25) (20.15–25)
South sector 0.065 a 36.9 a 31.66 b 7.24 ab 24.2 b
(0.02–0.13) (16.35–55) (25.4–37.8) (2.3–14.4) (22.85–30.8)
RI = radiation intensity; RH = relative humidity; RT = relative temperature; SH = soil moisture; ST = soil temperature.
Mean and range for each variable. Means followed by different letters (a, b) within the same column indicate statistically
significant differences (P <0.05).
Table 6. Average climatic conditions.
The loss of species diversity and conditions of humidity and altitude from north to south, along
the gradient in which the Pedemontana Jungle extends within Argentina, has been previously
documented [27, 40]. Therefore, it was interesting to know in this case if this trend was also
clearly reflected in the carbon stocks of the studied sectors of the Pedemontana Jungle. If the
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previous studies, the participation of the HUV and LUV strata was between 0.01% and 0.02%
and the LI carbon pool was between 1.5% and 3%. Therefore, in this study efforts were
concentrated in the strata of AGB, BGB, and SOC. The chosen sectors show the average weather
conditions (for the same season, day, and year), which differ significantly in air relative
temperature (RT), moisture and soil temperature (SM and ST, respectively) (see Table 6).
Studies of carbon stock results show that the two sectors are clearly separated in terms of their
potential. The northern sector has the largest records of total carbon with an average of 242 tC/
ha, while the southern sector registers an average 28% lower (Table 7) with statistically
significant differences (H = 12.38; p < 0.01). These values can be associated with different
microclimates, possibly generated by a latitude effect, whose influence on climatic variables
can be seen in Table 6. In all cases, the differences are in favor of a cooler, more humid climate
in the northern sector and warmer and drier in the southern. Although the number of analyzed
sectors in a latitudinal gradient in the Pedemontana Jungle (narrow strip of north–south
direction), are not representative of the whole distribution, the data can be interpreted in light
of the existing scientific studies in the area [25, 27, 40].
Once again, the two carbon pools that make a greater contribution to the total ecosystem carbon
stock are AGB and SOC, being greater in the case of the northern sector, meaning 52% and
34% of the total carbon stock, respectively (Figure 5). This implies that more than 86% of total
carbon is concentrated in these two fractions. In the southern sector, the participation of these
carbon pools is 47% and 38% for AGB and SOC, respectively, but with greater involvement of
the SOC carbon pool in this case.
140
120
100
80
North Sector
60
South Sector
40
20
0
AGB‐10 AGB‐0 BGB SOC
Figure 5. Carbon stock and contribution of each carbon pool studied. The acronyms AGB10, AGB0,
FigureBGB,
5. Carbon stockare
and SOC andexplained
contribution
in of
theeach carbon pool studied. The acronyms AGB10, AGB0, BGB, and SOC are
text.
explained in the text.
Radiation Intensity (RI) Relative Humidity (RH)

Soil Temperature (ST) Soil Moisture (SM)
800 Relative Temperature (RT)
700
72 Greenhouse Gases
Forest in the north (22° latitude) 242 96
Forest in the south (24° latitude) 174 68
Table 7. Carbon stock (tC/ha) in both sectors, north and south, in Salta, Argentina.
However, always considering the altitude of the Pedemontana Jungle, as the latitude increases,
the altitude decreases in general terms. It has been recognized that the floral changes are
influenced by complex interactions of weather and edaphic variables in Yungas altitude ranges
[24, 25, 40]. Beyond the fact that the associated variables of increasing altitude (which in this
study varies between 22° S and 24° S) and/or altitude (which varies between 500 and 700 m.a.s.l.
in the southern sector and between 700 and 900 m.a.s.l. in the north) would more or less
determine overt changes at the level of species and ecosystems, such variations exist without
doubt, and they are defining two sectors of the same forest in terms of carbon sequestration
potential.
These observations indicate that it is essential to preserve sectors of different latitudes and
altitudes in the Pedemontana Jungle, since there are intrinsic factors that are defining differ‐
ential features in the biomass and carbon stock, as well as, in every ecosystem functions
associated with these particular conditions [40]. Other authors have already pointed out that
the recommendation in all cases is to maintain connectivity of Yungas in distribution, safe‐
guarding different sectors of the Pedemontana Jungle, varying in latitude and altitude [27].
Human influence, not analyzed in this study, will, no doubt, imprint differential features over
time if their presence is not restricted, since we have observed signs of livestock and logging
in the different studied areas. In the southern sector, where the Pedemontana Jungle has been
deeply fragmented and immersed in an array of crops, it is considered that there might be a
microclimatic influence on the fragments by the existence of rough edges [7, 18]. This aspect
will be dealt with in the following section.
3.5. Effect of fragmentation on the carbon stock
Contributors: Manrique, S.M.
Fragmentation of the Pedemontana Jungle generates microclimate changes at its edge,

which could affect the sequestration of the carbon stock.
The fragmentation of forests, reducing surface and insulation, exposes organisms, which
remain in the fragment, to conditions differing from their ecosystem, which is primarily
manifested in the contact between two different environments, which has been defined as
“edge effect” [18], and that impact toward the forest interior.
Microclimatic changes caused as a consequence of contrasting conditions between the

remnant forest and the adjacent field, subjected to different uses (cultivation, planting, and
pastures), would seem to be the most immediate and apparent fragmentation changes [7].
Several authors have recognized that, at the edge of the fragments is an environmental
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gradient toward the interior: generally brightness, evapotranspiration, temperature, and

wind speed decrease, while soil moisture and humidity increase toward the interior of the
fragment. Biological changes could then arise as a result of these changes in the microcli‐
mate of the fragment edges [7, 18].
This study sought to analyze and quantify the possible microclimatic changes generated in the
fragment edges of the Pedemontana Jungle, also observing the distribution of five represen‐
tative tree species (by their frequency [24]). The studied species were as follows: (i) Calyco‐
phyllum multiflorum Griseb, Castelo, (ii) Phyllostylon rhamnoides J.Poiss., Taub, (iii)Astronium
urundeuva Engl., (iv) Anadenanthera colubrina Vell., Brenan, and (v) Cedrela angustifolia DC. It was
estimated that the typical species, “climax” or more conservative ones of the population (e.g.,
those that have higher demands for their germination or growth requirements and with low
tolerance for humidity fluctuations), could be more easily eliminated like those selected for
this study. These species, which have a high degree of integration, complexity, and efficient
energy use, are recognized as more susceptible to edge changes [18]. Therefore, in fragmented
environments, the survival advantage is given to those pioneer species with a maximum
tolerance for a wide range of environmental conditions.
Five forest sectors in the Colonia Santa Rosa municipality were worked (23°20’00 south latitude
and 64º 30’15” west longitude): four, clearly turned into fragments, and one continuous (not
fragmented) taken as a standard for comparison. The fragments were of distinct sizes: two
large (sites 1 and 2 between 160 and 180 ha) and two small (3 and 4 between 3 and 5 ha). The
distance from the city of Salta is 250 km.
The results of microclimatic records (taken from the edge toward the inside of the fragments,
except in the site 5 as it was not considered the same edge but worked in an inside sector,
looking for original ecosystem conditions) suggest that (Figure 6):
• High radiation intensity (RI) values are recorded at the edge (around 800 W/cm2 on average)
and almost constant values under cover (forest interior), which mean, almost, only up to 2%
of that value. The differences were statistically significant (H = 16.19; p < 0.01).
• Soil moisture (SM) in the interior is twice that of the edge (with maximum values of up to
16%) showing significant differences (H = 29.20; p < 0.001).
• Air relative humidity (RH) increases toward the interior, reaching values up to 7 times
higher than those at the edge (up to 53% relative humidity (RH)). The differences are
significant (H = 5.41; p = 0.048).
• Soil temperature (ST) is one of the most stable variables, although differences can be
detected: considering 100% at the edge (18°C on average) is reduced to 25% in the interior.
The differences are not statistically significant (H= 5.94; p = 0.311).
• Air relative temperature (RT) decreases by 12% in the interior, showing nonsignificant
values (H = 5.69; p = 0.337).
Changes are not manifested with identical magnitude in all cases. The smaller fragments tend
to register values higher or lower for the measured variables (results not shown).
74 Greenhouse Gases
Radiation Intensity (RI) Relative Humidity (RH)

Soil Temperature (ST) Soil Moisture (SM)
800 Relative Temperature (RT)
700
600
Percentage (%)
500
400
300
200
100
0
0 13 26 52 105 210
Distance from the edge (m)
Figure
Figure 6. Microclimatic
6. Microclimatic variables
variables studied
studied in in fragments
fragments from
from edge to edge
inside. to inside.
Values Values in
are expressed arerelative
expressed
termsin
as a
percentage of value
relative at the
terms as edge (considered
a percentage of as 100%).
value The edge
at the units are the following:
(considered RI= W/cm
as 100%). The ; ST= °C; RT=°C; RH= %;
2 units are the
SM= %. following: RI= W/cm2; ST= °C; RT=°C; RH= %; SM= %.
Microclimatic
100 variables are interrelated. Thus, for example, the RH and the RT are inverse and
Site 1
strongly 90
related; the RI and RT relate directly and the RH and RI in reverse. This means that
Site 2
the intensity
80 of radiation reaching the edge of the plot is influencing the relativeSite
temperature
directly (higher radiation and higher relative temperatures) and inversely with3 relative
70 Site humidity
4
humidity (greater radiation and lower relative humidity). In addition, the relative
and temperature inversely influence themselves (where there are higher values of5 relative
60 Site
temperature,
50 there are lower values of relative humidity).
In the AGB 40 case, the relative participation of each species to the biomass stock varies according
to site between
30 9% and 22 % for C. multiflorum, 5% and 79% for P. rhamnoides, 0% and 15% for
A. urundeuva,
20 11% and 48% for A. colubrina, and between 0% and 23% for C. angustifolia. In
general, the best-represented species is P. rhamnoides, followed by A. colubrine, and C. multi‐
10
florum. The fraction of ≤10 cm dbh (“sprout”) contributes to their maximum values up to 6%
of total AGB0 per site. AGB decreases significantly (H = 53.66; p < 0.001) from site 5 (179 ± 36 t/
ha) to site 1 (116.4 ± 32.2 t/ha), site 2 (106 ±AGB‐0
AGB‐10 44.6 t/ha), site 4 (16 ±SOC
6.7 t/ha), and lastly site 3 (10.37
± 4.1 t/ha). The studied species represent approximately 86–90% of the total in the case of the
Figure
forest 7. Carbontostock
(according plot).
andIncontribution
the fragments, thecarbon
of each five studied species
pool studied (AGBnotincludes
only have
onlylower AGB
five species
studied). The acronyms AGB10, AGB0 and SOC are explained in the text.
but also have proliferated heliophyllum species, typical of open environments, and species
composition has changes (results not shown). It cannot be concluded that carbon sequestration
in vegetation is less because of the microclimatic edge effect. Although there are clear differ‐
ences in the AGB10, the correlation of different distance values does not give significant values
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(r = 0.03; p = 0.804), nor in the AGB0 (r = 0.20; p = 0.134). The AGB of key species differs among
fragments, but it cannot be said that a whole biomass has declined, since other shrubs and
herbaceous species have proliferated. Larger studies are necessary to evaluate this aspect in
depth.
Carbon sequestration in SOC, estimated up to 10 cm depth, increases from 19.3 ± 5 tC/ha in
the site 3 (small forest fragment) to 23.4 ± 5 tC/ha in the site 4 (small forest fragment), 28.8 ±
7.5 Figure
tC/ha in6.
the site 1 (large forest fragment), 28.9 ± 12.2 tC/ha in the site 2 (large forest fragment),
Microclimatic variables studied in fragments from edge to inside. Values are expressed in
and 34.8relative
± 8.8 tC/ha
terms in
as athe forest orofsite
percentage 5 (Figure
value 7). (considered as 100%). The units are the
at the edge
following: RI= W/cm2; ST= °C; RT=°C; RH= %; SM= %.
100
Site 1
90
Site 2
80 Site 3
70 Site 4
60 Site 5
50
40
30
20
10
0
AGB‐10 AGB‐0 SOC
Figure
Figure 7. Carbon
7. Carbon stock and contribution
stock of each carbon
and contribution of each pool studied
carbon (AGB
pool includes
studied onlyincludes
(AGB five species
onlystudied). The
five species
acronymsstudied).
AGB10, AGB 0 and
The SOC are explained
acronyms AGB10, AGBin the text. SOC are explained in the text.
0 and
It can be assumed that the influence of these changes will affect, in the middle or long term,
the composition and facilitate the establishment the different species, according to their
requirements. Mainly, the dominant tree species (climax) could result in changes in its
germination and survival, promoting
Table 1. Methodological the success
differences and of pioneers
similarities species
between the implantation, and altering
case studies.
the original composition and structure of the forest [18].
Case I II III IV V
Legal No Yes Yes and no No No
4. Main remarks
protection
Site Coronel National Park Wildlife Aguaray and Colonia Santa
Moldes Calilegua Reserve of General Pizarro Rosa
The studies presented in this chapter offer insight into the varied potential of the Pedemontana
Acambuco and
Jungle for sequestration of atmospheric carbon, and howPizarro
Campo this potential can be influenced by
human intervention
Plot number 23 main plots 20 main plots 50 main plotsand
in processes of deforestation, degradation, 50 fragmentation.
main plots 78 main plots
(AGB 10) for (AGB 10); 20 (AGB 10);
The carbon stock estimated for the Pedemontana Jungle ranges from 50 (AGB10 ); tC/ha
162 50 (in
(AGB 10);
Coronel 78
each ecosystem; plots of 50 m2 plots of 50 m2 plots of 50 m2 plots of 50 m2;
Moldes) to 272 tC/ha (in Calilegua). In all cases, greater carbon storage occurs in the AGB
23 plots of 50 (AGB0); 40 plots (AGB0); 250 soil (AGB00); 250 468 soil plots
fraction (from 47% to2 55% of the total), where AGB0 fraction provides between 6 and 10% of
m (AGB0); 23 of 1 m2 (HUV plots (SOC) soil plots (SOC) (SOC); 156
plots of 5 m2 and LI); 120 soil and 500 climatic
(LUV); 46 plots plots (SOC) climatic instantaneous
76 Greenhouse Gases
the total stock. Soil (SOC) constitutes the second most important carbon pool. Its contributions
range from 28% to 39% according to the site.
The Pedemontana Jungle sequesters 43% more carbon than the Chaco forest at the same
latitude. Moreover, the potential of carbon sequestration in the Pedemontana Jungle increases
as the latitude decreases, sequestrating 28% more carbon at 22° than 24° south latitude.
Carbon sequestration in the Pedemontana Jungle sectors least affected by humans (degrada‐
tion) is 23% higher than in more degraded areas. There are no advantages for sites that are
legally protected (i.e., carbon sequestration is approximately similar). Forest degradation
practices such as unsustainable timber production, overharvesting of fuel wood, extensive
cattle ranching, and fires at the edge of forest fragments are less easily observed than defor‐
estation, but they can contribute substantially to emissions. Forest degradation can also be a
precursor to deforestation. These multiple changes in land use and forest area need to be
monitored at the national level.
The Pedemontana Jungle sectors that have been left isolated are subject to edge effect, with
changes clearly visible in microclimatic variables. The AGB in fragments is notably reduced
for the main five tree species studied, but the species composition has also changed.
The potential impact of climate change on forest remnants is still unpredictable and depends
on each one’s resilience, on the remnant’s adaptive capacity to climate change, and the
magnitude and intensity of the phenomenon manifested in each area. At the same time,
deforestation, degradation, and fragmentation of the Pedemontana Jungle could be affecting
its ecological and social integrity, and the ability to provide ecosystem services of supply and
regulation in the long term, and therefore its ability to respond to the global climate change
impact.
Human management has taken over the ecosystem services that sustain the most important
production systems from an economic standpoint. For example, irrigation water for cattle
pastures and soil for agriculture. In many forests, such as the Pedemontana Jungle, other
ecosystem services, for example, cultural or climatic regulation, are subordinated to these
major objectives. The consequences of this imbalance in handling are shown negatively in the
middle and long term, whereas in the short term, it cannot be seen most of the time. Vulnerable
ecosystems are thus generated from the biophysical and social point of view, with a reduced
capacity to respond to additional disturbances such as global climate change.
Forests require immediate support, with long-term policies independent of the ideologies, and
management plans developed on technical bases, which are based on compliance with Article
41 of the National Constitution, “All citizens enjoy the right to a healthy and balanced environment,
suitable for human development and for productive activities that meet present needs without compro‐
mising those of future generations; and have the duty to preserve it...” Land use plans should
prioritize the conservation of ecosystems of high ecological value, such as the Pedemontana
Jungle or Chaco, moreover, in a province where the natural biodiversity is accompanied by
cultural biodiversity (with nine aboriginal ethnic groups), and where the forests are the
principal sustainers of life.
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Acknowledgements
Supported by the Erasmus Mundus Action 2 Programme of the European Union. Special
thanks to CONICET and the Research Council of National University of Salta, both of Argen‐
tina, and National University of Salamanca, Spain. The Municipality of Coronel Moldes and
Colonia Santa Rosa are gratefully acknowledged. The authors thank Sandra Brown, Milena
Segura, and Angelina Martínez-Yrízar for information, suggestions, and comments. Andrés
Tálamo is acknowledged for his statistical advice. Thanks to the National Parks Administration
and Environment Secretary of the province of Salta, for entry permits to protected areas and
logistical support. This work could not have been completed without the invaluable help of
the students who assisted during field trips.
Author details
Silvina M. Manrique and Judith Franco
*Address all correspondence to: silmagda@unsa.edu.ar
Non Conventional Energy Resources Investigation Institute (INENCO) of National Univer‐

sity of Salta (UNSa) and National Council of Scientific and Technical Research (CONICET),
Salta, Argentina
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Chapter 5
Greenhouse Gas Emissions – Carbon Capture, Storage

and Utilisation
Bernardo Llamas, Benito Navarrete, Fernando Vega, Elías Rodriguez,

Luis F. Mazadiego, Ángel Cámara and Pedro Otero
http://dx.doi.org/10.5772/63154
Abstract
According to the recent information, CO2 concentration in the atmosphere reached 402
ppm at the beginning of 2016. On the other hand, fossil fuels remain as the major source
to produce energy. The International Energy Agency estimate that those fuels will remain
as the most used source during coming decades.
Carbon capture and storage technology is the most promising technology to significantly
decrease CO2 emissions. Nevertheless, it may be possible to use CO2 as a raw material for
other industrial uses. In this chapter, authors explain both ways to decrease CO2 emis‐
sions.
Keywords: CCS technology, CO2 capture technologies, CO2 storage, CO2 uses, macrofoul‐
ing
1. Introduction
The Fifth Assessment Report from the Intergovernmental Panel on Climate Change states that
human influence on the climate system is clear [1]. The CO2 concentration in the atmosphere
is continuously growing. The latest value is 402.52 ppm (January 2016, Mauna Loa Observa‐
tory), which is 2 pmm higher than the value registered in January 2015 [1].
Carbon capture and storage (CCS) is a way of ‘decarbonising’ fossil fuel power generation. It
involves capturing carbon dioxide (CO2) emitted from high-producing sources, transporting
it and storing it in secure geological formations deep underground, to mitigate the effect of
greenhouse emissions on climate change [2].
82 Greenhouse Gases
The transported CO 2 can also be reused in processes such as enhanced oil recovery (EOR) or
in the chemical industry, a process sometimes known as carbon capture and utilisation (CCU).
The transported CO2 can also be reused in processes such as enhanced oil recovery (EOR) or in the
CCS can be applied to fossil fuel power plants (coal and gas-fired power stations) and to
chemical industry, a process sometimes known as carbon capture and utilisation (CCU). CCS can be
industrial CO2-emitting sources such as oil refineries or cement, chemical and steel plants.
applied to fossil fuel power plants (coal and gas-fired power stations) and to industrial CO2-emitting
Rather than being a single technology, CCS is a suite of technologies and processes. While
sources such as oil refineries or cement, chemical and steel plants. Rather than being a single technology,
some of these
CCS is a suite have beenand
of technologies operated successfully
processes. While someforofdecades,
these haveprogress in applying
been operated large-scale
successfully for
CCS to power generation globally has been slow (Figure 1).
decades, progress in applying large-scale CCS to power generation globally has been slow (Figure 1).
Figure 1. Shares
Figure of global
1. Shares anthropogenic
of global greenhouse
anthropogenic gasgas
greenhouse emissions (GHG)
emissions and
(GHG) world
and COCO
world 2 emissions from fuel
2 emissions from fuel com‐
combustion
bustion bybyfuel
fuel(Mt
(Mtofof
COCO 2) [3, 4].
2) [3, 4].
Carbon capture and storage (CCS) is likely to be a crucial part of the least-cost path to decarbonisation. It
Carbon capture and storage (CCS) is likely to be a crucial part of the least-cost path to decar‐
can provide a back-up role for variable renewables and help to manage swings in demand. CCS also has a
bonisation.
crucial It can provide
role in decarbonising a back-up
heavy industryrole for there
where variable renewables
are limited and
options, help
and to manage
in the swings
longer term would
in demand. CCS also has a crucial role in decarbonising heavy industry where there are limited
help to maximise the emission reduction obtained from scarce supplies of sustainable bioenergy as well as
options,
opening and in
up other the longer term
decarbonisation would help to maximise the emission reduction obtained from
pathways.
scarce supplies of sustainable bioenergy as well as opening up other decarbonisation path‐
Theways.
European Commission has also emphasised that ‘CCS may be the only option available to reduce
direct emission from industrial processes at the large scale needed in the longer term’.
The European Commission has also emphasised that ‘CCS may be the only option available
to reduce
In this direct
chapter, emission
authors reviewfrom industrial
the carbon processes
capture, storageattechnology
the large scale needed
(including thein
COthe longer term’.
2 transport
In this
through chapter,and
pipeline), authors review technologies.
CO2 utilisation the carbon capture, storage technology (including the CO2
transport through pipeline), and CO2 utilisation technologies.
2. CO2 capture
This process consists of the separation of CO2 from flue gas produced during the combustion of fossil fuels
and2.can
CO capture
be applied to large flue gas stationary sources as thermal power stations and industrial processes.
2
Current CO2 capture technology (first generation) is adapted from gas separation processes already in
This process consists of the separation of CO2 from flue gas produced during the combustion
industrial use. There are several technologies and strategies to capture CO2 from stationary sources: pre-
of fossil fuels and can be applied to large flue gas stationary sources as thermal power stations
combustion, post-combustion and oxy-fuel (Figure 2).
and industrial processes.
Current CO2 capture technology (first generation) is adapted from gas separation processes
already in industrial use. There are several technologies and strategies to capture CO2 from
stationary sources: pre-combustion, post-combustion and oxy-fuel (Figure 2).
www.ebook3000.com
Greenhouse Gas Emissions – Carbon Capture, Storage and Utilisation 83
http://dx.doi.org/10.5772/63154
Figure 2. Summary of CO2 capture technologies (adapted from IPCC) [2].
3. First generation of capture technologies
3.1. Post-combustion capture

Post-combustion capture follows the conventional application of a specific purification unit
applied for a particular pollutant removal (CO2 in this case). Figure 3 illustrates a typical block
diagram of the post-combustion process that offers a great feasibility and versatility in terms
of operating conditions and process integration.
Figure 3. Simplified scheme of a fossil-fuel power plant using a post-combustion capture unit [5].
CO2 concentration in the flue gas from a combustion process varies from 4 to14% in natural
gas and coal-power plants, while other industries such as cement, iron and steel and petro‐
84 Greenhouse Gases
chemical produce flue gas ranging between 14 and 33%. The key drawbacks hindering the
large-scale implementation of this technology lies in the large volume of gas that should be
treated and the low CO2 concentration of the flue together with high energy requirements,
mainly related to CO2 desorption process. The presence of large amounts of dust, O2, SOx, NOx
and trace pollutants such as Hg and the relatively high temperature of the flue gas, typically
between 120 and 180°C, are also design challenges that have significant impact on the capture
costs.
The technologies currently available for post-combustion capture are classified into five main
groups: absorption, adsorption, cryogenics, membranes and biological separation. The most
mature and closest to market technology and so, the representative of first generation of post-
combustion options, is capture absorption from amines.
3.2. Chemical absorption from amines
Post-combustion capture using chemical absorption by aqueous alkaline amine solutions has
been used for CO2 and H2S removal from gas-treating plants for decades [6]. Amines react
rapidly, selectively and reversibly with CO2 and can be applied at low CO2 partial pressure
conditions. Amines are volatile, cheap and safe in handling. They show several disadvantages
as they are also corrosive and require the use of resistant materials. Furthermore, amines form
stable salts in the presence of O2, SOX and other impurities such as particles, HCl, HF and
organic and inorganic Hg trace compounds that extremely constrain the content of those
compounds in the treated gas.
The most widely used amine is monoethanolamine (MEA), which is considered as a bench‐
mark solvent because of its high cyclic capacity, significant absorption-stripping kinetic rates
at low CO2 concentration and high solubility in water. Some other amine-based solvents such
as diethanolamine (DEA), triethanolamine (TEA), diglycolamine (DGA), N-methyldiethanol‐
amine (MDEA), piperazine (PZ), 2-amino-2-methyl-1-propanol (AMP) and N-(2-aminoeth‐
yl)piperazine (AEP) have also traditionally been utilised.
A typical chemical absorption scheme is shown in Figure 4. A low CO2 concentrated flue gas
is introduced in the absorber in crosscurrent with lean solvent from the stripper at 50–55°C
and ambient pressure. CO2 reacts with amines in the absorber according to the overall reaction:
CO2 + 2 R1R2 NH « R1R2 NCOO - + R1R2 NH 2+ (1)
As CO2 is absorbed, rich amine from the absorber bottom is fed into a cross-exchanger with
lean amine before it is introduced into the stripper. The stripping temperature varies between
120 and 150°C, and the operating pressure reaches up to 5 bar. A water saturated CO2 stream
is released from the top and is subsequently ready for transport and storage, while lean amine
leaving the stripper is pumped back into the absorber.
The high energy penalty related to amines regeneration (a high-intensive energy process
because of the stripper operating conditions and solvent used) and solvent degradation are
the issues most hindering a large deployment of this technology.
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Figure 4. Diagram of a conventional CO2 capture process using amine-based chemical absorption.
3.3. Pre-combustion capture
In pre-combustion CO2 capture, CO2 separation occurs prior to fuel combustion and power
generation (Figure 5). The fuel reacts at high temperature and pressure with either oxygen or/
and steam under sub-stoichiometric conditions, and thereby a gas stream primarily composed
of CO and H2 is obtained. This CO/H2 gas mixture is commonly known as synthesis gas or
syngas.
In general, steam is utilised in case fuel is solid, namely gasification, whereas sub-stoichio‐
metric oxygen is used with liquid and gaseous fuels. Both reactions occur at elevated temper‐
ature (1,400°C) and pressure (3–7 Mpa), as seen in Equations 2 and 3.
Steam reforming:
æ yö
C x H y + xH 2O « xCO + ç x + ÷ H 2 ; DH r > 0 (2)
è 2 ø
Partial oxidation:
æyö
C x H y + xO2 « xCO + ç ÷ H 2 ; DH r < 0 (3)
è2ø
Steam reforming needs a secondary fuel to provide the energy supply necessary for the
reaction that occurs and a catalysts to improve the kinetic of this process. In Equation (3), the
primary fuel is partially oxidised by a limited amount of oxygen. Partial oxidation produces
less H2 per fuel unit than stream reforming, but the kinetic reaction is faster, it requires smaller
reactors and neither catalyst nor energy supply from a secondary fuel.
86 Greenhouse Gases
Once particulate matter is removed, the syngas passes through a two stages catalytic reactor,
where CO reacts with steam to produce CO2 and further yield H2: water-gas-shift (WGS) reaction.
WGS reaction:
CO + H 2O « CO2 + H 2 ; DH r = -41 kJ mol (4)
The syngas resulted is mainly composed of CO2, ranging from 15 to 40%v/v, and H2 at elevated
pressure from which CO2 can be easily separated by a physical absorption mechanism and
then CO2 can be easily released by simply dropping pressure.
Before the syngas from WGS reactor is separated into its primary components, the sulphur
compounds, mainly in COS and H2S form, are removed to avoid its emission to the atmosphere.
Sulphur is then recovered in either as solid in a Claus plant or as sulphuric acid.
The sulphur-free syngas has a high CO2 concentration and an elevated pressure (2–7 MPa),
thus making physical absorption highly recommended for CO2 separation, although adsorp‐
tion process such as pressure swing adsorption (PSA) is also utilised.
The remaining nearly pure H2 stream could be burned in a combined cycle power plant to
generate electricity, but H2 turbines require further development. Power fuel cells and
transportation fuels are alternative options for using H2 in the future, currently under devel‐
opment.
Figure 5. Simplified scheme of an integrated gasification combined cycle (IGCC) coupled with a pre-combustion CO2
capture and storage unit using a physical absorption process [5].
3.4. Oxy-combustion capture
Oxy-combustion or oxy-fuel capture is considered as one of the most promising CCS technol‐
ogies that would be economically competitive in fossil-fuel power plants and industrial
facilities. It has been developed for both new designs and retrofitting of existing plants,
although it is best adapted to newly designed power plants. A basic process flow diagram is
given in Figure 6. Oxy-combustion technology is based on the use of high purity O2 as oxidiser
in an O2/CO2 mixture instead of air during the combustion process. It has been first proposed
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for coal boilers and gas turbines but can be applied to any type of fossil fuel utilised for thermal
power production. As burning with O2 at high concentration can produce high flame temper‐
atures in the boiler, part of the exhaust gas from the boiler, mainly CO2 and water vapour (FGR
flue gas recirculation stream), is recycled to control temperatures to levels compatible with
available boiler materials. The flue gas obtained from this system consists mainly of CO2 and
H2O and are accompanied by minor quantities of N2, SOx, NOx, Ar and Hg. Water can be easily
removed by condensation, producing a highly CO2 concentrated flue gas. The CO2 content
varies from 70 to 95%v/v, depending on the process configuration, air in-leakages, fuel
characteristics and the purity of O2.
Figure 6. A simplified scheme of a fossil-fuel power plant based on the oxy-combustion concept [5].
Oxy-combustion requires large amounts of high purity (95–99%) O2 for power production. A
typical 500 MWe fossil-fuel power plant would need 9,000–10,000 t/d to operate under oxy-
combustion conditions [7]. Currently, cryogenic distillation is the only available technology
that can supply those amounts of O2. An air separation unit (ASU) can provide around 4,500–
7,000 t/d of oxygen, while other alternative technologies such as vacuum pressure swing
adsorption (VPSA) units and membranes can only produce one order of magnitude below
ASU production.
The ASU would consume up to 60% of the total electricity required for carbon capture and
reduces the overall efficiency of the power plant by about 7–9%, reaching up to 15% in some
cases. Furthermore, the availability and rapid response of the ASU to load changes have been
noted as crucial challenges for the global oxy-combustion plant operation and feasibility. New
technologies for O2 production as ion transport membranes (ITM) or VPSA have shown
promising results related to energy consumption, but the large amounts of O2 required in
power plant operation avoid currently its commercial deployment.
The CO2 stream obtained from oxy-fuel combustion shows high levels of water vapour,
sulphur compounds, N2, O2 and impurities such as mercury in the flue gas. NOx emission is
low when compared with air combustion.
88 Greenhouse Gases
The CO2 gas quality has significant impact on the capture cost by this technology, and
uncertainties on the future regulatory requirements of CO2 quality for its transport and storage
has influence on the process configuration of the oxy-combustion plant, gas cleaning unit
performance, overall CO2 recovery capacity and on the energy requirements for CO2 com‐
pression and purification.
4. Emerging technologies for CO2 capture
The most promising emerging technologies applied to carbon capture are discussed in this
section to complete the overview of the CO2 capture technologies currently under research.
4.1. Chemical looping combustion
Chemical looping combustion (CLC) is a promising technology for fuel combustion, which
can be beneficial in carbon capture applications. It is based on the use of an oxygen carrier,
typically a metal oxide, to supply the O2 needed for the fuel combustion process, producing a
highly CO2 concentrated exhaust gas. Iron, nickel, cobalt, copper, manganese and cadmium
are commonly used as oxygen carriers in CLC.
Oxygen
Depleted Air Combustion Products
N 2 , O2 CO2 , H 2 O
MeO
Air Fuel
Reactor Reactor
Me
Air Fuel
O2 , N 2 CnH m
Figure 7. A simplified scheme of a chemical looping for oxy-combustion.
CLC consists of two fluidised bed reactors, namely reducer and oxidiser. In the reducer reactor,
fuel is fed along with the metal oxide containing oxygen, which is transferred from the metal
oxide to the reactor as the combustion occurs (Figure 7). A flue gas containing over 99%v/v of
CO2 can be obtained by a simply condensation stage because of the fact that the exhaust gas
at the reducer outlet is primarily formed by CO2 and water vapour. This stream is then sent to
further compression and permanent storage.
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Reducer:
( 2n + m ) M yOx + Cn H 2 m « ( 2n + m ) M yOx -1 + mO + nCO2 . (5)
Oxidiser:
1
M yOx -1 + O2 « M yOx + N 2 + O2 ( excess ) . (6)
2
4.2. Hydrate-based separation
This separation approach is based on the hydrate formation from high pressure water in
contact with the flue gas containing CO2. Hydrates are crystalline under suitable low temper‐
ature and high pressure conditions. A pure CO2 stream is then obtained as CO2 is released
from the hydrates, achieving up to 99% of CO2 recovery.
4.3. Calcium looping
Calcium looping is based on the reversible reaction between CaO and CO2 to form calcium
carbonate.
Calcium looping consists of two fluidised bed reactors, namely carbonator and calciner. In the
carbonator, primary fuel is burned and CaO reacts with the CO2 formed from the fuel com‐
bustion following the reaction seen in Equation (7). Carbonator temperature is within 650–
700°C, depending on the system pressure.
Carbonator:
CaO ( s ) + CO2 ( g ) « CaCO3 ( s ) . (7)
Calciner:
CaCO3 ( s ) « CaO ( s ) + CO2 ( g ) . (8)
CaCO3 is then heated by secondary fuel combustion in the calciner. CaO is regenerated and
CO2 is released for storage according to the reaction in Equation (8). The calciner temperature
can reach 900°C, depending on the CO2 partial pressure.
This technology shows benefits for carbon capture. Limestone is cheap and widely available,
and there is a potential for process integration, which can lead to low energy penalties, i.e.,
heat released from carbonisation can be utilised in a steam cycle or the heat used in the calciner
reactor can be recovered in the carbonation process.
90 Greenhouse Gases
4.4. Partial oxy-combustion
The energy consumption required for solvent regeneration and high purity oxygen production
is the major drawback of post-combustion and oxy-combustion technologies. A new hybrid
concept has been proposed to reduce the energy requirements associated with CO2 capture
step combining a partial oxy-fuel combustion (using oxygen-enriched air instead of high purity
oxygen as oxidiser) and a CO2 separation process treating a flue gas with a higher CO2
concentration than in conventional air combustion (Figure 8).
CO2 to
Cleaned Gas
secuestration
CO2 Heat CO2

Exchanger
Absorption Stripping
O2 enriched Air
Boiler Energy
Rich Amine Lean Amine
Fuel
Figure 8. A simplified scheme of a partial oxy-combustion plant.
The combination of a less-constrained ASU for oxygen production and a carbon capture
process using membranes instead of amine solvents can conduce to a minimal energy require‐
ment associated with an oxygen purity ranging between 0.5 and 0.6 molar fraction.
4.5. Biological CO2 capture
Biological CO2 capture from a gas mixture is based on natural reactions of CO2 with living
organism, mainly enzymes, generally proteins and (micro)algae. Enzymes catalyse CO2
chemical reaction and enhance CO2 absorption rate in water. Enzymes can be also immobilised
at the gas-liquid interface to promote CO2 dissolution from the bulk gas. In this sense, carbonic
anhydrase enzyme supported in a hollow fibre with liquid membrane has been reported as a
potential method applied to CO2 capture, achieving up to 90% CO2 capture associated with
low energy requirements in the regeneration process at laboratory-scale experiments. Carbonic
anhydrase promotes carbonic acid formation from dissolved CO2 and enhances CO2 absorp‐
tion from gas phase using and extremely low CO2/enzyme ratio. CO2 separation using enzymes
must incorporate a tailored regeneration process to produce a high concentrated CO2 exhaust
stream. Membrane boundary, fouling, long-term operation and pore wetting are identified as
the most relevant technical issues to be addressed before the scale-up of this CO2 capture
approach.
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The use of algae is also considered a promising CO2 capture option among natural occurring
reactions. Algae consume CO2 through photosynthesis mechanism. The use of algae in CO2
capture would avoid subsequent CO2 compression and storage stages, but there are some key
issues that must be addressed for its large-scale deployment. In fact, algae require excessive
amount of water and large gas-liquid interface surfaces that drastically limit their application
in carbon capture. Algae are also highly susceptive to changes in operating conditions and to
the presence of impurities such as vanadium and nickel.
4.6. Ionic liquid absorption
Significant progress has been made in the application of ionic liquids (ILs) as alternative
solvents to CO2 capture because of their unique properties such as very low vapour pressure,
a broad range of liquid temperatures, excellent thermal and chemical stabilities and selective
dissolution of certain organic and inorganic materials. ILs are liquid organic salts at ambient
conditions with a cationic part and an anionic part.
ILs have the potential to overcome many of the problems of associated with current CO2
capture techniques. ILs are particularly applicable in absorption of CO2 while effectively
avoiding the loss of sequestering agents. Other advantage of ILs is that they can be combined
into polymeric forms, increasing the CO2 sorption capacity compared with other ILs and
conventional solvents and greatly facilitates the separation and ease of operation.
5. CO2 transport
Currently there are more than 6,500 km of CO2 pipelines worldwide. Most of them deliver
CO2 to EOR operations in the United States, but there is also a growing number under
development for CO2 storage projects
The relative development of the infrastructure to transport CO2 is still in its early stages. This
is reflected by the low number of existing infrastructures developed to transport CO2 from
stationary sources into geological structures. Table 1 provides an overview of the current
developments for CO2 transportation globally. All of these examples have been developed in
relation to the EOR technique, where the CO2 source is found mainly in natural reserves. In
Europe, only a few projects are in operation, but there are plans to deploy an extended CO2
pipeline network along Europe to optimise CO2 storage structures.
These examples may be used to study CO2 conditions; in addition, many CO2 pipeline projects
are based on well-known designs and materials commonly used in natural gas pipeline
specifications. The most profitable way to transport CO2 is in its dense phase [9].
To avoid two phases, it has been suggested that the most efficient way to transport CO2 is as
its supercritical phase [8, 9], which occurs at a pressure higher than 7.38 MPa and a temperature
of more than 31.1 °C. To maintain these conditions, this type of transportation may require the
use of booster stations in the pipeline layout to maintain the required pressure and tempera‐
ture.
92 Greenhouse Gases
Pipeline Location Length (Km) Diameter (inches) Estimated

maximum (106t/
year)
Cortez US 808 30 23.6
Sheep Mountain US 656 NA 11.0
Bravo US 351 20 7.0
Dakota Gasification/Weyburn US/Canada 328 14 2.6
Choctaw US 294 20 7.0
Bairoil US 258 NA 23.0
Central Basin US 230 16 4.3
Canyon Reef Carriers US 224 16 4.3
Comanche Creek US 193 6 1.3
Centerline US 182 16 4.3
Delta US 174 24 11.4
Snohvit Norway 153 NA 0.7
Borger US 138 4 1.0
Coffeyville US 112 8 1.6
OCAP The Netherlands 97 NA 0.4
Beaver Creek US 85 NA NA
Anton Irish US 64 8 1.6
El Mar US 56 6 1.3
Chaparral US 37 6 1.3
Doliarhide US 37 8 1.6
Lacq France 27 NA 0.1
Adair US 24 4 1.0
Cordona Lake US 11 6 1.3
Table 1. Current CO2 pipelines. The first long distance CO2 pipeline was in the 1970s. Main utilisation of the natural &
anthropogenic CO2 is EOR activities [8].
Material selection should be compatible with all states of the CO2 stream. They should be
defined to prevent corrosion and maximum material stress. In addition, eligible materials need
to be qualified for the potential low temperature conditions that may occur during a pipeline
depressurisation situation.
The design of a pipeline should meet the requirements set by appropriate regulations and
standards. CO2 pipelines shall be designed according to applicable regulatory requirements.
The Recommended Practice for Design and Operation of CO2 refers to the following pipeline
standards: ISO 13623:2009, DNV-OS F101:2012 and ASME B31.4 or ASME B31.8.
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Usually CO2 pipelines are designed using existing national standards for gas and liquid
transportation pipes, while additional CO2 specific design issues are taken into consideration
by the pipeline construction/operation companies to guarantee the reliable and safe operation
of a given pipeline.
The use of carbon steels (e.g., with API X-60 and X-65) for the transportation of CO2 streams
has been ongoing for more than 30 years, as required in EOR projects. During the 2002–2008
period, 18 incidents were reported with no fatalities and/or injuries.
Range
Length (km) 1.09–808
External diameter (mm) 152–921
Wall thickness (mm) 5.2–27
Capacity design (Mt/y) 0.06–28
Pressure min (bar) 3–151
Pressure max (bar) 21–200
Compressor capacity (MW) 0.2–68
Table 2. Summary of the current parameters considered in the CO2 transport phase.
The cost of pipeline transportation will be determined by the pipeline route, in which physical
and social geography will be crucial conditions.
The three major cost elements for pipelines are (1) construction costs (e.g., materials, labour,
booster station, if needed, and others), (2) operation and maintenance costs (e.g., monitorisa‐
tion, maintenance, energy costs) and (3) other costs (design, insurance, fees, and right-of-way).
6. CO2 storage
At present, there are three possible geological structures that may be considered for CO2
storage: depleted hydrocarbon and production, deep saline aquifers, and coal seams.
6.1. Depleted hydrocarbon fields
The CO2 can be stored in supercritical conditions, rising by buoyancy and can be physically
held in a structural or stratigraphic trap, the same way as the natural accumulation of hydro‐
carbons occurs. The advantage of the capacity of containment system has been demonstrated
by the retention of oil for millions of years. If the site is in production, it is used to increase the
recovery of oil or gas (EOR recovery – enhanced oil, gas-enhanced recovery – EGR). These
operations, EOR/EGR, provide an economic benefit that can offset the costs of the capture,
transport and storage of CO2.
94 Greenhouse Gases
6.2. Deep saline aquifers
They are the best options for storing large volumes of CO2 because of its size and found more
than 800 meters below the surface. The supercritical CO2 is 30–40% less dense than typical
saline water from these formations, which means that the CO2 naturally rise by buoyancy
through the reservoir until it is caught or becomes longer solution term. They require an
impermeable cap rock to ceiling (shales or layers of evaporites) and a porous and permeable
rock store (sandstone or limestone) that promotes the injection, migration and trapping.
6.3. Coal seams
CO2 in gaseous form is injected into the coalbed, 300 to 600 metre depth, and adsorbed on the
matrix pores, releasing the existing CH4 in the same (two molecules of CO2 adsorbed by each
CH4 molecule that travels). This has led to the possibility of storing CO2 in coal seams, while
CH4 recovered is valued. This technique is called ‘enhanced coalbed methane production’
(ECBM).
Coal properties (range, degree and permeability) determine the suitability of the site, either
for storage or storage with only CH4 recovery.
6.4. Site selection and exploration
Figure 9 represents a proposed work flow for any CO2 storage project. It is possible to
determine three mayor phases: pre-injection, injection and post-injection phases.
Figure 9. Work flow proposed for basin screening (Definition phase) [10].
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In general, most of the areas that could be suitable for storing CO2 are not well explored
geologically. For this reason, pre-injection phase is crucial to decrease the inherent risk in
subsurface exploration.
Screen phase could be differentiated by the data recompilation task and the multicriteria
decision tool. It is integrated as a preliminary phase, and it is connected with a second phase
called characterisation phase, which corresponds to site maturation and testing.
Those criteria should comprise both technique and socio-economic criteria, and they should
answer several questions such as where, how much quantity, and which conditions. All of
these criteria and questions will contribute to solve and select the most suitable emplacement
for storing CO2 [10].
There are different examples and analogues that can be useful for the definition of criteria.
Analogues can be natural (releases and resources) and industrial.
Assess or characterisation task is related to three major ways to explore the sub-surface:
outcrops, geophysics and wells.
To decrease the inherent risk of exploration, it is necessary to consider all of the three sub-
phases:
• Outcrops exploration provides samples of seal and storage formation, to evaluate some
properties such as hydrogeology and geomechanical properties (permeability, porosity,
etc.)
• Geophysics survey will provide and describe geological structures, and in some cases
hydrogeology parameter (i.e., total dissolved solid, TDS).
• Few techniques may be used if the structure should be 1,000 m deep: seismic reflection is
the most important technology (Figure 10), but other technologies such as magneto-telluric
or gravimetric may provide relevant information regarding to the geological structure and
resistivity of the original fluid.
Figure 10. Seismic survey based on vibroseis. Example of a seismic profile.

Figure 10. Seismic survey based on vibroseis. Example of a seismic profile.
 Wells will provide real information of the storage and caprock formation in sub-surface
conditions. Test will provide information about geomechanical, hydrogeological properties and it may be
possible to test interaction between the rock and CO2.
7. Monitoring techniques
Considering the injection phase, control of the behaviour of injected CO2 is one of the most important
tasks. For instance, the control and monitoring strategy must:
96 Greenhouse Gases
• Wells will provide real information of the storage and caprock formation in sub-surface
conditions. Test will provide information about geomechanical, hydrogeological properties
and it may be possible to test interaction between the rock and CO2.
7. Monitoring techniques
Considering the injection phase, control of the behaviour of injected CO2 is one of the most
important tasks. For instance, the control and monitoring strategy must:
• Demonstrate that the injected CO2 is stored in the selected reservoir and therefore must be
a guarantee that the company responsible for fulfilling its commitment to reducing emis‐
sions.
• Check that no intrusion occurs in other exploitable aquifers and water resources.
• Check for surface environmental effects occur, and therefore, you must provide the affected
population security and peace on the operations of injection.
The monitoring strategy should not be limited to the operational and post-operational periods
but has an important role during the pre-operational stage by conducting the baseline of the
injection site [11]. This baseline defines the set of physical, geochemical and biological
processes operating in the storage area before any activity injection. The baseline is critical
because especially in the early stages of injection, the changes are not evident, both in depth
and on the surface, and comparison with the undisturbed condition is needed. The develop‐
ment of the baseline may have added value; for example, building trust and showing the
population from the beginning that the project is under control and that any anomaly is
detected. Numerous methods have been proposed for monitoring CO2 in geological reposito‐
ries. Of these, one can clearly distinguish two types: (a) to detect the evolution of CO2 injected
into deep and (b) for leakage from storage. In the first type, these methods are generally based
on geophysical techniques, while in the second type, the range of methods is broader, including
geochemical, physical and biological techniques. Therefore, the final selection of the monitor‐
ing strategy should take into account the following aspects [12, 13]:
• Efficiency in detecting small changes in behaviour warehouse

• Implementation in large tracts of land
• Reasonable economic cost
Compliance with these requirements will be conditioned by the type of store and its area of
influence. Clearly, monitoring techniques will be very different in stores on-shore and off-
shore, and within a storage type, geological, hydrological and even ecological characteristics
will favour the implementation of a methodology or other.
The monitoring deployment is based on the following aspects: (a) characterisation of the area,
(b) establishing a base line CO2, (c) establishment of potential areas of migration and release
of CO2 (and other gases) and (d) validation and development of techniques for monitoring CO2.
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Emission Leakage Description/Comments Phases of the CO2

Storage
Leak paths through Operating or abandoned It is important to identify all abandoned ⋅ Characterisation
wells and boreholes wells at the site (or close to it) wells ⋅ Injection
These wells can become the main roads ⋅ Post-injection
of leakage
Blowouts (uncontrolled May cause leakage of high flows in short ⋅ Injection
emissions from injection periods of time.
wells) It is considered that it is unlikely
incidents if safety standards are met
during drilling
Future removal of Can be a problem in the reservoirs of ⋅ Post-injection
reservoirs of CO2 can be a coal deposits
problem in the reservoirs of
coal deposits
Leak paths and natural Through faults and May origin leak high flows ⋅ Characterisation
migrations through fractures Proper site characterisation can reduce ⋅ Injection
faults and fractures the risk of leakage ⋅ Post-injection
By dissolving CO2 in a fluid Proper site characterisation (evaluation ⋅ Characterisation
and subsequent transport of hydrogeology) can reduce the risk of ⋅ Injection
natural circulation of fluid leakside of gas ⋅ Post-injection
Through the pore system in Proper site characterisation can reduce ⋅ Characterisation
low permeability rocks the risk of leaks ⋅ Injection
when the capillary inlet An exhaustive control of the injection
pressure is exceeded or if pressure is needed
the CO2 has been in
solution
By a stroke if the reservoir Proper site characterisation overflows ⋅ Injection
can reduce the risk of leakage ⋅ Post-injection
Another type of leak Methane release could It happens in depleted oil and gas ⋅ Characterisation
occur as a result of the ⋅ Injection
displacement of CH4 by ⋅ Post-injection
CO2
Table 3. Possible types of leakage of CO2 in a geological storage [13, 14, 15].
8. CO2 uses
8.1. Current uses of CO2
Nowadays different applications are known that can be used for demonstrating that CO2 is a
useful, versatile and safe product. Figure 11 illustrates most of the current and potential uses
of CO2.
98 Greenhouse Gases
Figure 11. CO2 uses. Different pathways for utilisation CO2.
There are many classifications that can be made about the use or valuation of large-scale
CO2 and including the three categories proposed by Vega [16] for type of uses, which also is
used by the PTE-CO2, 2013 (Technology Platform Spanish CO2). To wit:
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1. Direct or technology use: use of CO2 with different technologies and market applications
such as use for oil recovery, for dry cleaning, waste carbonation, food, water treatment or
extraction with supercritical CO2 compounds, including others.
2. Improved biological use: CO2 fixation in biomass by growing microalgae and carbonic
fertigation.
3. Chemical use: artificial photosynthesis and chemical conversion to high added value
products and fuels.
8.2. Direct use of CO2
8.2.1. Enhanced oil recovery (CO2-EOR)
As much as two-thirds of conventional crude oil discovered in U.S. fields remain unproduced,
left behind because of the physics of fluid flow. In addition, hydrocarbons in unconventional
rocks or that have unconventional characteristics (such as oil in fractured shales, kerogen in
oil shale or bitumen in tar sands) constitute an enormous potential domestic supply of energy.
Carbon dioxide is used in oil wells for oil extraction and to maintain pressure within a
formation.
There are many methods for EOR and each has differences that make it more useful based on
specific reservoir challenges and other parameters. Choosing the right method by screening
the reservoir and fluid properties can ultimately reduce risk by eliminating inefficiencies.
CO2 EOR is an ‘EOR’ technology that injects CO2 into an underground geologic zone (oil/
hydrocarbon containing ‘reservoir’) that contains hydrocarbons for the purpose of producing
the oil. The CO2 is produced along with the oil and then recovered and re-injected to recover
more oil.
When the maximum amount of oil is recovered from the reservoir, the CO2 is then ’sequestered’
in the underground geologic zone that formerly contained the oil and the well is shut-in,
permanently sequestering the CO2.
CO2 injection is a technology successfully used from more than 50 years. The first patent for
CO2-EOR appeared in 1952 and in 1964 began field trials. In the first commercial project of
CO2-EOR in Texas, in 1972 (SACROC project), CO2 was supplied from a gas plant, where the
CO2 was eliminated in the production of ammonia At present the CO2 is sent from geological
formations (natural) from Bravo Dome in Colorado, and Mc Elmo Dome in New Mexico.
Nowadays, two techniques are largely used for CO2-EOR:
• Miscible water-alternating-gas (WAG) process. Injection alternates between gas (usually

natural gas or CO2) and water; the miscible gas and oil form one phase. The WAG cycles
improve sweep efficiency by increasing viscosity of the combined flood front (Figure 12).
• Cyclic gas injection. Most gas-injection EOR projects today use CO2 as the injected gas.
When CO2 is pumped into an oil well, it is partially dissolved into the oil, rendering it less
100 Greenhouse Gases
Figure 12. CO2-EOR operation diagram. CO2 injection into reservoir to ‘flood’. Diagram courtesy of Dakota Gasifica‐
tion Company.
viscous, allowing the oil to be extracted more easily from the bedrock. The CO2 used to
increase oil recovery can be naturally occurring, or an effective means of sequestering an
industrial by-product. In this case, carbon dioxide, under pressure, is injected between oil
wells to freeing the stranded oil. CO2 is a superior agent in recovering stranded oil as the
CO2 naturally reduces the surface tension that traps the liquid oil to in the oil reservoir.
When the oil is recovered from the production well, CO2 is also produced, but is easily
separated from the crude oil because the CO2 reverts back to its gaseous state when the
pressure is removed.
8.2.2. Fire suppression
Some fire extinguishers use CO2 because it is denser than air. Carbon dioxide can blanket a
fire, because of its heaviness. It prevents oxygen from getting to the fire and as a result, the
burning material is deprived of the oxygen it needs to continue burning.
8.2.3. Supercritical CO2 uses
When CO2 is at suitable temperature and pressure above the critical point (Figure 13), it is
called supercritical CO2.
This state emphasises its capacity to dissolve chemicals and natural substances of similar
way as do different organic solvents such as hexane, acetone or dichloromethane. There‐
fore, the first applications focused on the extraction of natural substances as an alterna‐
tive to using organic solvents. Thus, removal of caffeine (coffee or tea) with supercritical
CO2 is the most mature application at industrial level and is also used in the extraction of
hops or cocoa fat.
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Figure 13. CO2 phases diagram.
The dry cleaning with CO2 is one of the most popular applications of supercritical fluids in the
textile sector. This method is characterised by removing stains from the fabrics and garments
where no harmful organic solvents for the average ambient, such as perchlorethylene (PER),
common in conventional dry cleaning processes are used and without causing discoloration
or shrinkage and without leaving odour.
One of the main advantages of supercritical CO2 is that its solubility can easily be controlled
suitably adjusting the pressure and temperature, allowing fractionate mixtures where all
components are soluble.
Supercritical CO2 extraction coupled with a fractional separation technique is used by pro‐
ducers of flavours and fragrances to separate and purify volatile flavour and fragrance
concentrates. Like any solvent, supercritical CO2, it allows processing chemicals by precipita‐
tion or recrystallisation, obtaining particles of controlled size and shape, without excessive
fines without thermal stresses and controlling the shape of a polymorphic substance.
It is, therefore, a cutting-edge technology with great potential, because it is a new way to obtain
natural products; it allows the adaptation of new high quality products with appropriate value
to consumer habits; enables the development of new non-polluting processes and initiate the
development of a tertiary sector led to the new technology.
8.2.4. Food and beverages
Liquid or solid CO2 is used for quick freezing, surface freezing, chilling and refrigeration in
the transport of foods. In cryogenic tunnel and spiral freezers, high pressure liquid CO2 is
injected through nozzles that convert it to a mixture of CO2 gas and dry ice ‘snow’ that covers
the surface of the food product. As it sublimates (goes directly from solid to gas states),
refrigeration is transferred to the product.
Carbon dioxide gas is used to carbonate soft drinks, beers and wine and to prevent fungal and
bacterial growth. CO2 has an inhibitory effect on bacterial growth, especially those that cause
discoloration and odours.
COan
CO2 has 2 has an inhibitory
inhibitory effect
effect on on bacterial
bacterial growth,growth, especially
especially those
those that that
cause cause discoloration
discoloration and
and odours
odours
(Figure 14). (Figure 14).
Figure 14. CO2 applications in food.

Figure 14. CO2 applications in food.
It is used as an inert ‘blanket’, as a product-dispensing propellant and an extraction agent. It can also be
used to It displace airan
is used as during
inert canning.
‘blanket’, as a product-dispensing propellant and an extraction agent. It
can also be used to displace air during canning.
Cold sterilisation can be carried out with a mixture of 90% carbon dioxide and 10% ethylene oxide, the
carbonCold sterilisation
dioxide can be carried
has a stabilising effect onout
thewith a mixture
ethylene oxide of
and90% carbon
reduces thedioxide and 10% ethylene
risk of explosion.
oxide, the carbon dioxide has a stabilising effect on the ethylene oxide and reduces the risk of
8.2.5.explosion.
Water treatment
Carbon dioxide
8.2.5. can
Water change the pH of water because of its slightly dissolution in water to form carbonic
treatment
acid, H2CO3 (a weak acid), according to Equation 9:
Carbon dioxide can change the pH of water because of its slightly dissolution in water to form
carbonic acid, H2CO3 (a weak acid), according to Equation 9: (9)
CO2 + H 2O ® H 2CO3 (9)

Carbonic acid reacts slightly and reversibly in water to form a hydronium cation H3O+, and the
bicarbonate ion HCO3-, according to Equation 10:
Carbonic acid reacts slightly and reversibly in water to form a hydronium cation H3O+, and
the bicarbonate ion HCO3-, according to Equation 10:
(10)
H 2CO3 + H 2O ® HCO3- + H 3O + (10)
This chemical behaviour explains why water, which normally has a neutral pH of 7 has an acidic pH of
This chemical
approximately behaviour
5.5 when explains
it has been why
exposed to water,
air. which normally has a neutral pH of 7 has an
acidic pH of approximately 5.5 when it has been exposed to air.
At the moment, CO2 technology is widely introduced in treatments such as sewage water, industrial water
At the moment, CO2 technology is widely introduced in treatments such as sewage water,
or drinking water remineralisation.
industrial water or drinking water remineralisation.
The increased
The increased requirements
requirements of drinking
of drinking water
water in largein large
cities cities becomes
becomes necessary
necessary to use sources
to use sources of very soft
water of
andvery soft water
because and salinity
of its low becauseandof its
pHlow
aresalinity and pH are
very aggressive andvery
can aggressive and canphenomena
bring on corrosion bring on in
corrosion
the pipes phenomena
of the pipeline, withinthe
theappearance
pipes of theofpipeline, with
colour and the appearance
turbidity of colour
when these andmade
pipes are turbidity
of iron,
and by undermining these ones made with cement fibre by dissolving the calcium carbonate (CaCO3),
because of excessive aggressive CO2.
The introduction of carbon dioxide in the pipes regulates a state of equilibrium between dissolved
bicarbonates, calcium carbonate inlaid and the CO2 added.
Therefore, for the treatment of soft or aggressive waters, the use of CO2 in combination with lime or
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when these pipes are made of iron, and by undermining these ones made with cement fibre
by dissolving the calcium carbonate (CaCO3), because of excessive aggressive CO2.
The introduction of carbon dioxide in the pipes regulates a state of equilibrium between
dissolved bicarbonates, calcium carbonate inlaid and the CO2 added.
Therefore, for the treatment of soft or aggressive waters, the use of CO2 in combination with
lime or calcium hydroxide is advisable to increase water hardness. This process is called
remineralisation and is meaningful in water treatment plants, because soft water is indiges‐
tible.
The use of CO2 in wastewater neutralisation, Figure 15, offers great advantages in the operation
and the environment by preventing other chemicals:
• Better working conditions. Eliminate the risk of burns, toxic fumes and other injuries from
handling mineral acids
• Safe neutralisation. Avoiding risk of over-acidification with strong acids
• Low initial investment. Simple equipment, insurance and small dimensions
• Automated process. Automation avoids the handling of corrosive acids in the plant, pH
control is automatic
• Economy
Figure 15. Dosing system for sewage.
8.2.6. Carbonate mineralisation

The alkaline waste management presents significant problems, mainly because of its volume
and its geochemical properties that do not allow disposing in conventional landfills. Therefore,
the accelerated carbonation of this waste is another technological uses of CO2.
Carbonate mineralisation refers to the conversion of CO2 to solid inorganic carbonates.
Naturally occurring alkaline and alkaline-earth oxides react chemically with CO2 to produce
minerals, such as calcium carbonate (CaCO3) and magnesium carbonate (MgCO3). These
minerals are highly stable and can be used in construction or disposed of without concern that
the CO2 they contain will release into the atmosphere. One problem is that these reactions tend
to be slow, and unless the reactions are carried out in situ, there is a large volume of rocks to
move. Carbonates can also be used as filler materials in paper and plastic products.
8.2.7. Biological utilisation
Green plants convert carbon dioxide and water into food compounds, such as glucose and
oxygen. This process is called photosynthesis (Equation 11).
CO2 + 6 H 2O ¾¾
® C6 H12O6 + 6O2 (11)
The reaction of photosynthesis is as follows: Biological applications are based primarily on

the use of CO2 as food for plant growth. In a similar way as the plants take advantage of
sunlight and CO2 for biomass, or other products, ‘imitating’ nature, improving its results.
Therefore, this technology is also known as biomimetic transformation.
There are two main ways in the biological utilisation process: greenhouses carbonic fertilisa‐
tion and growth of microalgae.
8.2.7.1. Greenhouses carbonic fertilisation
CO2 is found naturally in the atmosphere and, therefore, in the greenhouse environment. It is
essential for plant growth, since it represents the carbon source for organic compounds they
need, in short, for compounds that constitute their biomass (leaves, stems, fruits, etc.).
CO2 is not the only factor involved in photosynthesis, so that for its use, other factors must be
at levels that do not limit the process. Light, temperature, amount of available nutrients and
the relative humidity are other environmental factors affecting photosynthetic activity.
During photosynthesis, plants capture light energy and CO2 through the leaves, and water
and nutrients through the roots. Thanks to these elements and chlorophyll leaves, plants get
synthesise sugars and various organic compounds required for their development. Photosyn‐
thesis is responsible for plant growth. Therefore, favouring photosynthesis we managed to
promote the development of the plants and agriculture in our case.
Yields of plant products grown in greenhouses can increase by 20% by enriching the air inside
the greenhouse with carbon dioxide. The target level for enrichment is typically a carbon
dioxide concentration of 800 ppm – or about two-and-a-half times the level present in the
atmosphere (Figure 16).
In the CENIT SOST-CO2 project that includes the entire life cycle of CO2, researching
technology uses as chemical and biological uses, the following results were confirmed, among
others [18]:
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growth. Therefore, favouring photosynthesis we managed to promote the development of the plants and
agriculture in our case.
Yields of plant products grown in greenhouses can increase by 20% by enriching the air inside the
Greenhouse
greenhouse with carbon dioxide. The target level Gas Emissions
for enrichment – Carbon
is typically Capture,dioxide
a carbon Storage and Utilisation 105
concentration of 800 ppm – or about two-and-a-half times the level present inhttp://dx.doi.org/10.5772/63154
the atmosphere (Figure 16).
Figure 16. Carbon

Figure 16. Carbon fertilisation
fertilisationin
inhydroponics
hydroponicsculture
culturegreenhouses
greenhouses.
.
In the CENIT SOST-CO2 project that includes the entire life cycle of CO2, researching technology uses as
• Rating combustion gases from combined cycle plants to use in vegetable crops in green‐
chemical and biological uses, the following results were confirmed, among others [18]:
houses, in applications in irrigation pipes to prevent clogging and to balance the pH in
 nutrient solutions.
Rating combustion gases from combined cycle plants to use in vegetable crops in greenhouses, in
applications in irrigation pipes to prevent clogging and to balance the pH in nutrient solutions.
• With regard to the quality of gas from CCGT, it can be recommended for direct use in
 greenhouses or other
With regard agricultural
to the quality uses.CCGT, it can be recommended for direct use in
of gas from
greenhouses or other agricultural uses.
• The carbonic fertilisation allows early crop production along with a greater amount of
 product
Thewith better
carbonic quality.allows early crop production along with a greater amount of product
fertilisation
with better quality.
8.2.7.2. Growth of microalgae
8.2.7.2. Growth of microalgae
Microalgae are photosynthetic microorganisms that can grow in diverse areas mainly in water
Microalgae are photosynthetic microorganisms that can grow in diverse areas mainly in water media
media where the forced culture can be carried out in diverse type of reactors in concordance
where the forced culture can be carried out in diverse type of reactors in concordance with its design and
with
operation.design
its and operation.
The advantage The advantage
of this process of thisare
is that microalgae process is that microalgae
a microorganism with a highare a microor‐
production
ganism with a high production rate (some species are able to duplicate their biomass
rate (some species are able to duplicate their biomass in 24 hours), and therefore with increased demand in 24
hours), and therefore
for CO2 conventional with increased
terrestrial plants. demand for CO2 conventional terrestrial plants.
The investigation
The investigation of microalgae
of microalgae cultureculture for different
for different purposes
purposes began in the began inlast
middle of thecentury,
middlewhen of last
century,
the Unitedwhen the United
States launched States launched
the ‘Aquatic the ‘Aquatic
Species Program’. At that Species
time, the Program’. At that
research focused time, the
on the
research
possibilityfocused on the
of obtaining possibility
biofuels of obtaining
from microalgae: biofuels
mainly from
methane andmicroalgae:
hydrogen, butmainly methane
after the oil crisis and
in
hydrogen,
the 1970s thebut after was
biodiesel the oil
alsocrisis in the 1970s the biodiesel was also considered.
considered.
Biofixation
Biofixation ofof
COCO
2 by by
2 microalgae,
microalgae, especially
especially as anfor
as an option option for the utilisation
the utilisation of flue gasesof fluepower
from gases from
power plants, has been the subject of extensive investigations in the United States,(IEA-GHG
plants, has been the subject of extensive investigations in the United States, Japan and Europe Japan and
Biofixation Network). However, none of the related projects have demonstrated the feasibility of the
Europe (IEA-GHG Biofixation Network). However, none of the related projects have demon‐
concept at a pre-industrial level. What is more, CO2 fixation efficiency is quite low because of the
strated the feasibility of the concept at a pre-industrial level. What is more, CO2 fixation
photobioreactors used in those pilot plants (raceway or open-ponds) (Figure 17).
efficiency is quite low because of the photobioreactors used in those pilot plants (raceway or
open-ponds) (Figure 17).
The current production of microalgae is mainly focused around a few species, such as Spirulina,
Chlorella, Dunaliella or Haematococcus for nutritional purposes (for humans) and animal feed
(especially aquaculture). Other sectors, such as cosmetics, effluent treatment and bioenergy,
have shown interest, incorporating these or other species of microalgae and cyanobacteria into
commercial products. Currently, 95% of the production of microalgae is based on open systems
Figure 17. Microalgae culture in open system (raceway) and close photobioreactor (Almeria University and Palmerillas
Figure 17.Center).
Research Microalgae culture in open system (raceway) and close photobioreactor (Almeria University and Palmerillas
Research Center).
The current production of microalgae is mainly focused around a few species, such as Spirulina, Chlorella,
Dunaliella or Haematococcus for nutritional purposes (for humans) and animal feed (especially
(raceways
aquaculture).orOther
circular open
sectors, suchponds). These
as cosmetics, systems
effluent have and
treatment a low rate ofhave
bioenergy, CO2shown
fixation and it is
interest,
estimated
incorporatingto these
be around
or other20–50% ofmicroalgae
species of the injectedandgas is effectively
cyanobacteria into set by microalgae
commercial [17].
products. Currently,
95% of the production of microalgae is based on open systems (raceways or circular open ponds). These
8.2.8.
systemsUse of CO
have a lowinrate
2 chemicals
of CO2 fixation and it is estimated to be around 20–50% of the injected gas is
effectively set by microalgae [17].
Carbon dioxide gas is used to make urea (used as a fertiliser and in automobile systems and
8.2.8. Use of
medicine), CO2 in inorganic
methanol, chemicalsand organic carbonates, polyurethanes and sodium salicylate.
Carbon dioxide
Carbon dioxide gasisiscombined with
used to make epoxides
urea (used as atofertiliser
create plastics and polymers.
and in automobile systems and medicine),
methanol, inorganic and organic carbonates, polyurethanes and sodium salicylate. Carbon dioxide is
Corn-to-ethanol plants
combined with epoxides have plastics
to create been the
and most rapidly growing source of feed gas for CO2
polymers.
recovery.
Corn-to-ethanol plants have been the most rapidly growing source of feed gas for CO2 recovery.
8.2.8.1. Artificial photosynthesis
8.2.8.1. Artificial photosynthesis
Because CO2 is a practically inert molecule, artificial photosynthesis of CO2 involves the use
Because CO2 is a practically inert molecule, artificial photosynthesis of CO2 involves the use of large
of large amounts of energy so it must use a clean source of energy (such as solar radia‐
amounts of energy so it must use a clean source of energy (such as solar radiation).Therefore, the use of
tion).Therefore, the usethe
catalytic agent to facilitate of process
catalytic agent even
allowing to facilitate the
take place at process allowing even
ambient temperature take place
and pressure is at
ambient temperature and pressure is necessary. In this case, it is
necessary. In this case, it is also called as photocatalysis or photoreduction. also called as photocatalysis
or photoreduction.
In photocatalysis two processes occur: CO2 reduction and oxidation of other compounds. Early works on
In
thephotocatalysis two processes
photocatalytic reduction occur:
of CO2 in COsolution
aqueous 2 reduction
wereand oxidation
published of other
between 1978 compounds. Early
and 1979 ([19, 20]),
works
and lateron the photocatalytic
numerous investigators reduction
have studiedofthe
CO 2 in aqueous
mechanism solution ofwere
and efficiency published
the process usingbetween
different
1978 and(oxides
catalysts 1979 of
([19, 20]), and
titanium, zinc later numerous
and cadmium, investigators
cadmium sulphide,have
siliconstudied
carbide),the
andmechanism and
reducing (water,
efficiency of theand
amines, alcohols) process using different
R light sources catalysts
(lamps xenon, mercury,(oxides of Thus,
halogen). titanium, zinc shown
it has been and cadmium,
that by
cadmium sulphide,
using specific silicon carbide),
semiconductors and reducingandagents,
reducing
can be(water, amines,
obtained a greatalcohols)
variety of and R light
products sources
(methane,
methanol, formaldehyde, formic acid, ethanol, ethane, etc.).
(lamps xenon, mercury, halogen). Thus, it has been shown that by using specific semiconduc‐
tors and reducing agents, can be obtained a great variety of products (methane, methanol,
Along with thermodynamics, catalysis is one of the core technologies for an economically interesting use
formaldehyde,
of CO2 as feedstockformic acid, processes.
in chemical ethanol, ethane, etc.).
This is one of the areas most sophisticated and complex of
modern chemical research. It is one of the major challenges for the scientific and technological
Along with thermodynamics, catalysis is one of the core technologies for an economically
developments related to the fields of energy and catalysis, as was highlighted in the report to officiate
interesting use of CObasic
Sciences US Department 2 as Energy:
feedstock
morein chemical
than 85% of allprocesses. This
products are is oneusing
produced of the areas most
chemical
catalysis [21].
Photocatalysis involve the production of reactions because of the incidence of light on a semiconductor
material. Unlike metals, these materials have a forbidden energy band, which extends from the top of the
so-called valence band to the bottom of the conduction band (Figure 18).
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sophisticated and complex of modern chemical research. It is one of the major challenges for
the scientific and technological developments related to the fields of energy and catalysis, as
was highlighted in the report to officiate Sciences US Department basic Energy: more than 85%
of all products are produced using chemical catalysis [21].
Photocatalysis involve the production of reactions because of the incidence of light on a

semiconductor material. Unlike metals, these materials have a forbidden energy band, which
extends from the top of the so-called valence band to the bottom of the conduction band
(Figure 18).
Figure 18. Diagram of behaviour of a semiconductor, TiO2, in light presence and participation in the photocatalytic
CO2 reduction organic products.
The main disadvantage in these cases remains in the low process efficiency.
In general, the process of photocatalytic reduction of CO2 requires a milder conditions and
lower energy consumption than chemical reduction [22].
8.3. Chemical conversion
Large quantities are used as a raw material in the chemical process industry, especially for
urea across CO2 reaction with NH3 and later dehydration of the formed carbamate. Urea is the
product most used as agricultural fertiliser. It is used in feed for ruminants, as carbon cellulose
explosives stabiliser in the manufacture of resins and also for thermosetting plastic products,
among others.
Methanol production, where CO is added as additive, is very a well-known reaction. The

production is carried out in two steps. The first step is to convert the feedstock natural gas into
a synthesis gas stream consisting of CO, CO2, H2O and hydrogen. This is usually accomplished
by the catalytic reforming of feed gas and steam. The second step is the catalytic synthesis of
methanol from the synthesis gas. If an external source of CO2 is available, the excess hydrogen
can be consumed and converted to additional methanol.
Methanol production, where CO is added as additive, is very a well-known reaction. The production is
carried out in two steps. The first step is to convert the feedstock natural gas into a synthesis gas stream
consisting of CO, Gases
108 Greenhouse CO2, H2O and hydrogen. This is usually accomplished by the catalytic reforming of feed
gas and steam. The second step is the catalytic synthesis of methanol from the synthesis gas. If an external
source of CO2 is available, the excess hydrogen can be consumed and converted to additional methanol.
CO2 is also used, to make inorganic and organic carbonates, carboxylic acids, polyurethanes
andused,
CO2 is also sodium salicylate.
to make Carbon
inorganic anddioxide
organiciscarbonates,
combined with epoxides
carboxylic to create
acids, plastics and
polyurethanes and sodium
polymers
salicylate. Carbon(Figure
dioxide 19).
is combined with epoxides to create plastics and polymers (Figure 19).
Figure 19. Different products made with CO2 derivatives.

Figure 19. Different products made with CO2 derivatives.
9. New ways for CO2 uses
In general, the area of CO2 utilisation for carbon storage is relatively new and less well known compared
to other9. New approaches,
storage ways for CO suchuses
as geologic storage. Thus, more exploratory technological investigations
2
are needed to discover new applications and new reactions.
In general, the area of CO utilisation for carbon storage is relatively new and less well known
2
Many challenges exist for achieving successful CO2 utilisation, including the development of technologies
compared to other storage approaches, such as geologic storage. Thus, more exploratory
capable of economically fixing CO2 in stable products for indirect storage.
technological investigations are needed to discover new applications and new reactions.
Many
Significant challengesand
innovation exist for achieving
technical successful
progress CO2made
are being utilisation,
acrossincluding
a number theofdevelopment of
utilisation technologies.
technologies capable
The electrochemical of economically
reduction fixing
could be really CO2 in stable
attractive becauseproducts
it is anfor indirect way
excellent storage.
for renewable
energy storage.
Significant innovation and technical progress are being made across a number of utilisation
technologies. The electrochemical reduction could be really attractive because it is an excellent
9.1. Power torenewable
way for gas technology (P2G)
energy storage.
In the 3rd Carbon Dioxide Utilisation Summit, October 2014 in Bremen, Germany, ETOGAS GmbH
9.1.its
presented Power to gasplan
turn-Key technology (P2G) Power-to-Gas for SNG through electrolysis processes [18].
and technology
In the 3rd Carbon Dioxide Utilisation Summit, October 2014 in Bremen, Germany, ETOGAS
This technology uses COits
GmbH presented 2 as a feed gas for the production of carbon products with Etogas methanation
turn-Key plan and technology Power-to-Gas for SNG through electrolysis
plant (Figure 20), which
processes [18]. are reactor systems for conversion of H2 and CO2 to methane (synthetic natural
gas). The produced gas is DVGW- and DIN-compliant synthetic natural gas and can be used directly, e.g.,
as a fuelThis
for atechnology uses CO2 as a feed gas for the production of carbon products with Etogas
CNG vehicle.
methanation plant (Figure 20), which are reactor systems for conversion of H2 and CO2 to
methane (synthetic natural gas). The produced gas is DVGW- and DIN-compliant synthetic
natural gas and can be used directly, e.g., as a fuel for a CNG vehicle.
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Figure 20. SNG schematic process. Source: ETOGAS Project.
9.2. Electrochemical CO2 utilisation
According to DNV GL, electrochemical CO2 utilisation presents some advantages as follows:
Production de-coupled from the sun (flexibility in renewable energy source); land use is
minimised and no limitation with respect to geography; no competition with food (corn,
sugar); flexibility in end fuel – ethanol, butanol or diesel (depending on the organism used);
flexibility in electrochemical process (matching to supply/demand of renewable energy); and
significant net reduction in CO2 emission (Figure 21).
Figure 21. Electrochemical production of formic acid (HCOOH) and CO. Source: third Carbon Dioxide Utilisation
Summit. DNV GL.
9.3. Polymers production
Bayer MaterialScience (Germany) in the Project “Dream Production” combines part of waste
streams of coal-fired power plants, CO2, with the production of polymers. The target is the
design and development of a technical process able to produce CO2-based polyether polycar‐
bonate polyols on a large scale. The first step was to convert the CO2 in new polyols, and these
polyols showed similar properties such as products already on the market and can be proc‐
essed in conventional plans as well (Figure 22).
Figure 22. Target product polyurethanes – All rounder among plastics. Source: 3rd Carbon Dioxide Utilisation Sum‐
mit. Courtesy: Bayer.
The CO2 thus acts as a substitute for the petroleum production of plastics. Polyurethanes are
used to produce a wide range of everyday applications. When they are used for the insulation
of buildings, the polyurethane saves about 80% more energy than it consumes during
production. Light weight polymers are used in the automotive industry, upholstered furniture
and mattress manufacturing.
9.4. Macrofouling control in industrial facilities
In the past years, several projects have been focused in the direct use of flue gases from
Combined Cycle Power Plants for developing different applications. In this way, the project
CENIT SOST-CO2 has demonstrated the use of flue gases from CCPP in a direct way to control
the pH in the cooling water systems with refrigeration tower and Iberdrola has developed an
application for power plants.
Another application for the future will be “CO2 for Zebra Mussel Control”. A project developed
by Iberdrola and the University of Salamanca shows that carbonic acidification just in the
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moment when the larva of zebra mussel are in the adequate phase (pediveliger) causes a much
greater lethality than inorganic acids because of the synergistic effect of the lethal hypercapnia
by physiological changes in cell metabolism of the larvae. (CDTI Project: Seguimiento de la
incidencia del mejillón cebra (Dreissena polymorpha) en el Ciclo Combinado de Castejón 2009-2011.
Iberdrola – Universidad de Salamanca).
The project LIFE13 ENV/ES/000426. CO2FORMARE [23], "Use of CO2 as a substitute of

chlorine-based chemicals used in O&M Industrial processes for macrofouling remediation”,
led by Iberdrola Generación, seeks to demonstrate the viability of using CO2 from combustion
gases to control macrofouling (fouling caused by larger organisms, such as oysters, mussels, clams
and barnacles) in a thermal power plant (Castellon CCPP), cooled by sea water. First estimates
indicate that a 400 MW CCPP (Figure 23) may be necessary to use up to 50,000 t CO2 yr–1, [23].
Figure 23. Castellon Power Plant. Courtesy: Iberdrola.
10. Others
The Carbon Storage Program of the NETL (National Energy Technology Laboratory) of US
Department of Energy supports four main CO2 utilisation research areas: cement, polycar‐
bonate plastic, mineralisation and enhanced hydrocarbon recovery. Several projects on
active CO2 utilisation focused in these areas receive Department of Energy (DOE) funds that
aim to obtain the goals for the Carbon Storage Program.
Author details
Bernardo Llamas1,2*, Benito Navarrete3, Fernando Vega2, Elías Rodriguez4,5,

Luis F. Mazadiego1, Ángel Cámara1 and Pedro Otero6
*Address all correspondence to: bernardo.llamas@upm.es
1 Escuela de Ingenieros de Minas y Energía, Universidad Politécnica de Madrid (UPM),

Madrid, Spain
2 INERGYCLEAN Technology, Almería, Spain
3 Escuela Técnica Superior de Ingeniería de Sevilla, Sevilla, Spain
4 IBERDROLA Generación, Madrid, Spain
5 Westec Environmental Solutions, llc, Chicago, USA
6 Es.CO2. Centro de Desarrollo de Tecnologías de Captura de CO2, CIUDEN, León, France
Authors, Elías Rodriguez and Pedro Otero, retired from their affiliations.
References
[1] http://www.esrl.noaa.gov/gmd/ccgg/trends/ [Accessed on 1 February 2016].
[2] Intergovernmental Panel on Climate Change: Climate Change 2013: The Physical Sci‐
ence Basis. Cambridge University Press. UK, 2013.
[3] International Energy Agency. (ed.): Key World Energy Statistics 2015. International En‐
ergy Agency publication. 2013, 82 pp.
[4] Global CCS Institute: The Global Status of CCS. Global CCS Institute. 2015. 24 pp.
[5] E. Rubin, H. Mantripragada, A. Marks, P. Versteeg, J. Kitchin: The outlook for improved
carbon capture technology. Progress in Energy and Combustion Science, 38(5). 2012.
[6] L. Kohl, R.B. Nielsen: Gas purification. ELSEVIER. 1997.
[7] Toftegaard, Maja Bøg et al. Oxy-fuel combustion of solid fuels. Progress in Energy and
Combustion Science. 2010, 36(5). 581-622.
[8] P. Noothout, F. Wiersma, O. Hurtado, P. Roelofsen, D. Macdonald: CO2 pipeline in‐

frastructure, report 2013/18. IEA GHG. 2014. United Kingdom.
[9] O. Skovholt: CO2 Transportation System. Energy Conversion & Management. 1993.
Vol. 34, 9–11, 1095–1103.
www.ebook3000.com
http://dx.doi.org/10.5772/63154
[10] B. Llamas, P. Cienfuegos: Multicriteria Decision Methodology to Select Suitable Areas for
Storing CO2. Energy & Environment. 2012. Vol. 23, 2–3, 249–264.
[11] R.W. Klusman: Baseline Studies of Surface Gas Exchange and Soil-Gas Composition
in Preparation for CO2 Sequestration Research: Teapot Dome, Wyoming. The Ameri‐
can Association of Petroleum Geologists. AAPG Bulletin. 2005. 89, 981–1003.
[12] M. Ortega, M.A. Rincones, J. Elío, J. Gutiérrez, B. Nisi, L.F. Mazadiego, L. Iglesias, O.
Vaselli, F. Grandia, R. de la Vega, B. Llamas: Gas Monitoring Methodology and Applica‐
tion to CCS Projects as Defined by Atmospheric and Remote Sensing Survey in the Natural
Analogue of Campo de Calatrava. Global Nest Journal. 2014. 16(2), 269–279.
[13] J. Elío, M. Ortega, B. Nisi, L.F. Mazadiego, O. Vaselli, J. Caballero, L. Quindós-Ponce‐

la, C. Sainz-Fernández, J. Pous: Evaluation of the Applicability of Four Different Radon
Measurement Techniques for Monitoring CO2 Storage Sites. International Journal of
Greenhouse Gas Control. 2015a. 41, 1–10.
[14] Llamas, B.; Mazadiego, L.F.; Elío, J.; Ortega, M.; Grandia, F.; Rincones, M.A. System‐
atic Approach for the Selection of Monitoring Technologies in CO2 Geological Storage
Projects. Application of Multicriteria Decision Making. Global Nest Journal. 2014.
(16-1), pp. 36 - 42.
[15] R.W. Klusman: Comparison of Surface and Near-Surface Geochemical Methods for
Detection of Gas Microseepage from Carbon Dioxide Sequestration. International
Journal of Greenhouse Gas Control. 2011. 5, 1369–1392.
[16] L. Vega: El CO2 como recurso. De la naturaleza a los usos industriales. Gas Natural
Fenosa Foundation. 2010.
[17] Technology Platform Spanish CO2.Usos del CO2: un camino hacia la sostenibilidad.
2013.
[18] http://www.cenit-sostco2.es/ [Accessed on 1 December 2015].
[19] M. Halmann. Photoelectrochemical reduction of aqueous carbon dioxide on p-type

gallium phosphide in liquid junction solar cells. Nature. 1978, 275(5676): 115-116.
[20] Inoue, T., Fujishima, A., Konishi, S. and Honda, K. Photoelectrocatalytic Reduction of
Carbon Dioxide in Aquesous Suspensions of Semiconductor Powders. Nature. 1979,
277: 637.
[21] US Department of Energy, DOE: Basic research needs, Catalysis for Energy. 2007. Basic
Energy Sciences Workshop.
[22] Kohno, Y., Hayashi, H., Takenaka, S., Tanaka, T., Funabiki, T. and Yoshida, S. Photo-
enhanced reduction of carbon dioxide with hydrogen over Rh/TiO2. Journal of Photochem‐
istry and Photobiology. 1999. A 126, 117-123.
[23] http://www.etogas.com/ [Accessed on 1 December 2015].

[24] http://www.co2formare.eu/ [Accessed on 12 December 2015].
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Chapter 6
Review of Recent Developments in CO2 Capture Using

Solid Materials: Metal Organic Frameworks (MOFs)
Mohanned Mohamedali, Devjyoti Nath, Hussameldin Ibrahim and

Amr Henni
http://dx.doi.org/10.5772/62275
Abstract
In this report, the adsorption of CO2 on metal organic frameworks (MOFs) is comprehen‐
sively reviewed. In Section 1, the problems caused by greenhouse gas emissions are ad‐
dressed, and different technologies used in CO2 capture are briefly introduced. The aim
of this chapter is to provide a comprehensive overview of CO2 adsorption on solid mate‐
rials with special focus on an emerging class of materials called metal organic frame‐
works owing to their unique characteristics comprising extraordinary surface areas, high
porosity, and the readiness for systematic tailoring of their porous structure. Recent liter‐
ature on CO2 capture using MOFs is reviewed, and the assessment of CO2 uptake, selec‐
tivity, and heat of adsorption of different MOFs is summarized, particularly the
performance at low pressures which is relevant to post-combustion capture applications.
Different strategies employed to improve the performance of MOFs are summarized
along with major challenges facing the application of MOFs in CO2 capture. The last part
of this chapter is dedicated to current trends and issues, and new technologies needed to
be addressed before MOFs can be used in commercial scales.
Keywords: CO2 capture, solid sorbent, MOFs, ZIFs
1. Introduction
1.1. Environmental problem and CO2 emissions
The increasing level of CO2 emission is considered one of the major environmental challenges
that our planet is facing today. The concentration of greenhouse gases in the atmosphere
reached a new record in 2013, with CO2 at 396 ppm which represents 142% of the concentration
of the pre-industrial era [1]. Findings of a recent global atmosphere watch reported in a
greenhouse gas bulletin [1] revealed that CO2 concentration has increased between 2012 and
2013, more than any other year since 1984, which was attributed to the reduced uptake by the
earth’s biosphere. This alarming level of CO2 shows the urgency for taking immediate actions
to prevent serious repercussions of climate change. On December 2015, at the Paris Climate
Conference (COP21), 195 countries adopted a historical and the first legally binding global
climate agreement to keep the increase in global average temperature to well below 2oC above
pre-industrial levels. The discovery of new fossil fuel reserves, combined with rising energy
demand, led to an increase in the number and capacities of power plants worldwide. This
situation is expected to extend into the future due to various factors such as industrial
development and economic growth, especially in developing nations, which in turn is expected
to further contribute to increasing levels of greenhouse gas emissions in years to come.
According to a recent report by the Energy Information Administration, energy consumption
is projected to rise by 56% between 2010 and 2040. Fossil fuels will continue to supply about
80% of the world energy through 2040. Industrial energy consumption represents the greatest
share of emissions and is projected to consume more than 50% of the energy delivered in 2040.
According to currently implemented regulations regarding fossil fuels, CO2 emissions from
power plants is projected to increase by 46% compared to emission level in 2010 [2].
Among several approaches that could be used to overcome the greenhouse gas effect is the
utilization of clean energy alternatives which could be the ultimate solution to the climate
change problem in terms of reducing CO2 emissions. However, these green technologies still
require significant modifications to the current energy framework. The great challenges facing
these green technologies lie in the difficulty for implementation at industrial scale, which
makes it economically infeasible when compared to fossil fuel-based power plants. This
implies that unless green energy alternatives and energy infrastructure for the commerciali‐
zation and the implementation of these new technologies are attained, the pursuit of new
CO2 emission reduction technologies will continue to be the most practical method to address
greenhouse gas effects until the advancement in clean energy technologies reaches commercial
stages.
There are three different strategies to reduce emissions of CO2 from fossil fuel-based power
plants. These include post-combustion capture in which CO2 is separated from the combustion
flue gas stream that is mainly composed of nitrogen and some other minor components such
as water vapor and oxygen. The separation process in this scheme is a downstream unit which
allows for an easy retrofit of a post-combustion capture unit to an existing power plant.
However, the limitations of this technique include a low CO2 partial pressure, relatively high
flue gas temperature and large quantities of CO2 in the flue gas stream [3, 4]. In the pre-
combustion capture scenario, the fossil fuel is treated under certain temperature and pressure
to gasify the fuel and produce hydrogen. This method offers streams with high CO2 partial
pressure and thus easy separation by utilizing variety of solvents; however, it requires
significant modifications to the power generation plant. The last scenario is called the oxy-fuel
capture in which the fuel is burned under a pure oxygen environment which requires the
separation of oxygen/nitrogen from an air stream. The process produces pure CO2 and water
vapor which can be easily recovered through a simple condensation unit. Each separation
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scenario requires a different capture technology, and therefore the properties, characteristics,
and operation of the separation process are also entirely different among the three strategies.
The most advanced process for implementation in the field is post-combustion. We will
therefore, in this chapter, focus on the post-combustion separation applications.
1.2. Existing technologies for CO2 capture

In order to locate metal organic frameworks (MOFs) on the map of the technologies used for
CO2 capture applications, we will briefly describe the major technologies that have been
employed and discuss their advantages and limitations. Figure 1 shows the different technol‐
ogies used for CO2 capture, whereas MOFs are used under the category of membranes and
adsorbents.
The most widely investigated technology for CO2 capture from flue gas is absorption using
aqueous amine solutions such as monoethanolamine (MEA), diethanolamine (DEA), and
methyldiethanolamine (MDEA), as well as blends of different amines [5–7]. Amine scrubbers
are considered a well-developed technology and is available in commercial scale for post-
combustion capture applications [8]. The major limitations of this technology include the high
energy required for solvent regeneration, stability of the amine system at the regeneration
conditions, and the negative influence of impurities present in the flue gas that might signifi‐
cantly affect the stability and performance of the solvent [9, 10].
Under the category of absorption technology and in order to overcome the limitations of
amine-based technologies, aqueous ammonia as a solvent for CO2 separation has also been
widely used to benefit from the low heat of absorption of ammonia-based solvents as compared
to amine systems. Besides, the ammonia can also absorb other impurities existing in the gas
stream such as NO and SOx. The major drawback of ammonia-based solvents lies in the need
to cool the flue gas prior to introducing it to the absorption column to prevent ammonia losses
to the gas stream. This adds a huge energy requirement considering the large volume of flue
gas stream that typically needs to be treated [11]. The chilled ammonia process faces similar
issues in addition to fouling of the heat exchanger by ammonium bicarbonate deposition from
saturated solutions [4].
Great efforts have been made to find new and efficient materials for absorptive CO2 separation.
Ionic liquids (ILs) are liquid salts composed of cations and anions, have been proposed as
promising solvents to replace the existing amine-based solvents. ILs possess several remark‐
able properties that make their application in CO2 separation one of the hottest research topics
in the last few years [12–14]. These properties include low volatility, high CO2 solubility, good
thermal stability, and the possibility of systematically tuning the structure toward certain
properties [15–17]. Several review papers reporting experimental data related to CO2 solubil‐
ity, selectivity, effect of ILs structure on performance, and the stability of ILs are available [12,
18]. Recent developments on the application of the amine-modified ILs, known as task-specific
ILs (TSILs), are also widely discussed in the literature [19, 20], including both physical and
chemical interactions with CO2. Unfortunately, many ILs and TSILs suffer from a common
problem of high viscosity after CO2 absorption. Even though some recent reports mentioned
the availability of ILs with low viscosities, it is still evident that much work has to be done to
overcome this limitation. Finding cheap routes for the synthesis of these materials is one of the
greatest challenges facing researchers working in this area [21]. In this chapter, a great portion
will be dedicated to the incorporation of ILs into the pores of MOFs to improve their CO2
capture capabilities.
Figure 1. Different technologies used for CO2 capture [22].
2. CO2 capture using solid sorbents
2.1. Criteria for the evaluation of solid sorbents
In order to evaluate solid materials for their performance in CO2 separation from flue gases,
some important performance criteria must be met. These include:
• Adsorption capacity: it is a key criteria in evaluating solid sorbent performance. It provides

information on the amount of CO2 that could be adsorbed by a given solid material. It can
be represented in terms of gravimetric uptake which is the amount of CO2 adsorbed per unit
mass sorbent (gram CO2/gram sorbent, or cm3 CO2/gram sorbent). The volumetric uptake
is another measure for capacity, and it reports the CO2 uptake per volume of sorbent material
(gram CO2/cm3 sorbent, or cm3 CO2/cm3 sorbent). This criterion is of great importance
because it represents the amount of sorbent needed for a particular duty and therefore the
size of the adsorption bed. It is also considered a crucial factor in determining the energy
requirement during the regeneration step.
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• Selectivity for CO2: it represents the CO2 uptake ratio to the adsorption of any other gas
(typically nitrogen for post-combustion capture, and methane for natural gas). It is an
essential evaluation criterion, and affects the purity of the adsorbed gas, which will
significantly influence the sequestration of CO2. The simplest method to estimate the
selectivity factor is to use single-component adsorption isotherms of CO2 and nitrogen.
• Enthalpy of adsorption: it represents another critical parameter in the evaluation of the
performance of solid sorbents. It is a measure of the energy required to regenerate the solid
sorbent, and it therefore significantly influences the cost of the regeneration process. It
represents the affinity of the material toward CO2 and measures the strength of the adsor‐
bate–adsorbent interaction.
• Physical, thermal, and chemical stability: in order to reduce operating costs, solid sorbents
must demonstrate stability under flue gas conditions, adsorption operation conditions, and
during the multi-cycle adsorption–regeneration process. In particular, stability in the
presence of water vapor is essential for the sustainable performance of the solid sorbent. In
addition to thermal properties of the solid sorbent, heat capacity and thermal conductivity
are also important in heat transfer operations.
• Adsorption/desorption kinetics: the time of the adsorption–regeneration cycle greatly
depends on the kinetics of the CO2 adsorption–desorption profile, which is measured in
breakthrough experiments. Sorbents that adsorb and desorb CO2 in a shorter time are
preferred as these reduce the cycle time as well as the amount of sorbent required, and
ultimately the cost of CO2 separation.
• Cost of the sorbent material: it is an important factor in the selection of the sorbent material.
Materials that exhibit excellent adsorption attributes, and are readily available at low cost,
are considered the main targets for researchers working in the field of CO2 capture. Besides,
the environmental impact of synthesizing these materials is considered one of the greatest
challenges to overcome.
In the following sections, we describe the main solid sorbents used for CO2 capture, their
applications, major attributes, and limitations.
2.2. Zeolites
Zeolites are porous crystalline aluminosilicate materials available naturally, but can also be
prepared synthetically. The zeolite framework is composed of tetrahedral T atoms where T
could be Si or Al, connected by oxygen atoms to form rings of different pore structures and
sizes. The pore size of the zeolite framework varies between 5 and 12 Å [23]. They are widely
used as catalysts in the refining industry [24, 25], fine chemicals synthesis [26, 27], and in gas
separation applications [28, 29]. Zeolites are considered promising candidates in CO2 capture
application as has been widely reported in the literature [30–32]. CO2 can be adsorbed on
zeolites through different mechanisms, such as molecular sieving effect based on the difference
in size [33, 34]. Separation can also take place based on polarization interactions between the
gas molecule and the electric field on the charged cations in the zeolite framework [33].
Accordingly, CO2 removal with zeolites can be controlled by changing the pore size, polarity,
and the nature of the extra framework cation. Among the different zeolites investigated for
CO2 capture applications, zeolite 13X is the most widely studied sorbent, and is considered
the benchmark technology for solid sorbents [35, 36]. Research on the use of zeolites as sorbents
for CO2 capture can be categorized into different areas depending on the approach and the
techniques adopted to address the improvement in capture performance. These categories
comprise tuning the pore size, designing zeolites with controlled polarities, investigating novel
zeolites, optimizing the cation exchange, and most recently incorporating amine moieties and
other chemical functions into the zeolite frameworks. Ocean et al. [37] have studied the
selectivity to adsorb CO2 by controlling the pore size of an NaKA zeolite through the synthesis
of nanosized NaKA zeolites. Overall, the adsorption kinetics on the nanosized crystals was
fast enough for CO2 capture applications; however, the formation of a thin layer on the
nanosized NaKA zeolite, due to intergrowth on the surface, did not considerably improve the
adsorption kinetics. In contrast, Goj et al. [38] performed atomistic simulations for silicalite,
ITQ-3, and ITQ-7, and reported a positive effect on CO2 uptake and selectivity by tuning the
pore apertures. Sravanthi et al. [39] provided a novel approach to control the pore size and
volume by utilizing pore expansion agents and obtained average pore size around 30 nm. The
application of the pore-expanded MCM-41 in CO2 separation resulted in the uptake of about
1.2 mmol/g.
Several studies have been conducted to control zeolite affinity toward CO2, which can be
realized by tuning the polarity of the zeolite through alteration of the Si/Al ratio and the
nature of the cation. Remy et al. [33] studied the selective separation of CO2 on low-silica KFI
zeolite (Si/Al = 1.67) by employing ion exchange with Na, Li, and K. Li-exchanged KFI has
shown the highest CO2 uptake which was attributed to the large pore volume as compared
to Na and K cations. In comparison with high-silica KFI sample (Si/Al = 3.57–3.67), Li–KFI
had the highest capacity at low pressure due to the strong electrostatic field. The overlap
between pore size and polarity effects is also strongly observed for amine-supported zeolites,
which have gained considerable attention in the last few years [40–45]. For instance, Ahmad
et al. [46] have impregnated melamine into β-zeolite and obtained dynamic CO2 uptake of
3.7 mmol/g at atmospheric pressure and temperature of 25 °C. The major challenge facing
amine-modified zeolites is the tradeoff between the increased affinity toward CO2 (strong
interaction with the sorbent) and the reduction in pore volume, and consequently the uptake,
especially, at low pressures. Factors such as amines loading, distribution, and the nature of
the cation can play a vital role to avoid the blockage of the porous structures with the bulky
amine moieties [42, 47]. Kim et al. [48] have performed a rigorous investigation through the
simulation of thousands of zeolites to evaluate the adsorption properties of these materials
and identify the optimum structures for improved CO2 separation attributes. This study
provides a systematic approach to rank and select appropriate zeolites for the required
capture objectives. However, important factors such as stability under humid environment,
adsorbent and process cost, and the availability of zeolite structures were not taken into
consideration.
The hydrophilic nature of most zeolite structures is considered a major drawback of zeolites
especially for post-combustion CO2 applications [49, 50]. Water competes with CO2 on the
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available sorption sites and might influence the zeolite structure and framework [51]. As
explained earlier, the presence of the exposed cation sites increases CO2 uptake. In a recent
study by Serena et al. [52], the relationship between the water content of the zeolite and the
density of the cations was investigated, and a linear relationship was found to describe the
decrease of the cation population with increasing water content. This observation highlights
the detrimental effect of the presence of water vapor on the adsorption of CO2 on zeolites.
2.3. Carbon-based CO2 capture
Carbon-based adsorbents have been used for CO2 separation in different forms including
activated carbons (ACs), carbon nanotubes (CNTs), and graphenes. Activated carbons have
an amorphous porous structure with high surface areas that are readily available for CO2
uptake. They have been widely investigated as sorbents for CO2 removal due to their low cost
and the availability of raw materials [53–55]. However, there are no active sites to bond with
the adsorbed CO2 as cations in zeolite sorbents. This weak interaction results in lower enthalpy
and therefore lower energy requirement for regeneration. On the contrary, ACs have very low
CO2 uptake at low pressures due to the absence of the electric field on the surface. Kacem et
al. [56] performed a comparison between the performance of ACs and zeolite for CO2/N2 and
CO2/CH4 separation based on their capacity, regeneration capacity, and reusability. It was
concluded that at higher pressures (above 4 bars), the CO2 uptake for ACs was much higher
than zeolites. Also, the recovered CO2 after the regeneration of ACs had higher purity than in
the case of zeolites. When compared to zeolites, ACs maintain their adsorption stability even
in the presence of water vapor which does not cause any framework failure [57].
In order to enhance the adsorption capacity on ACs, several studies have been conducted in
order to improve the affinity toward CO2 by introducing amine-based functional groups [58–
61]. In a recent study, Maria et al. [62] described a systematic surface modification of micro‐
porous ACs through a stepwise chemical treatment. They were successful in grafting amine
and amide functional groups on the surface of ACs with only 20% loss of surface area. Gibson
et al. [63] studied the polyamine-impregnated porous carbons and achieved 12 times higher
CO2 capacity than bare porous carbon. Chitosan and triethylenetetramine have been success‐
fully impregnated onto the surface of ACs and have shown 60 and 90% increased CO2 uptake
at 298 K and 40 bars. In addition to amine functional groups, ammonia-modified ACs, at
atmospheric pressure and a temperature range from (303 to 333) K, have been studied [64].
Authors report that an enthalpy of 70.5 kJ/mol was obtained compared to 25.5 kJ/mol for the
pristine ACs, suggesting the possibility of chemisorption. Another report has also supported
the improved adsorption capacity and selectivity by employing NH3 at high temperature and
has considerably improved CO2 uptake from 2.9 mmol/g for the bare AC to 3.22 mmol/g for
the modified one at 303 K and 1 bar.
Several studies have been dedicated to the application of amine-modified carbon nano tubes
(CNTs) as solid sorbents for CO2 separation [65–69]. Industrial grade CNTs have been
functionalized with tetraethylenepentamine (TEPA) by Liu et al. [65], and the effects of amine
loadings on the CO2 uptake, heat of adsorption, and adsorbent regenerability were investi‐
gated. TEPA-impregnated CNTs have shown an enhanced capacity of 3.09 mmol/g at 343 K.
Similar studies were also reported using different amines such as (3-aminopropyl)triethoxy‐
silane (APTES) [70], polyethyleneimine (PEI) [67], and other amines (primary, secondary,
tertiary, diamines, and tri-amines) [71].
Graphene is a planar sheet of carbon atoms extended in two dimensions, and was discovered
in 2004 [72]. Graphite-based capture was recently introduced (after 2011) as a promising
candidate for CO2 capture applications, and research is growing rapidly in this area [73–77].
A recent review by Najafabadi is available on the current status and research trends of using
graphene and its derivatives as solid sorbents for CO2 capture [78]. Research in this area
involves grafting various functional groups on graphene such as N-doped graphene compo‐
sites (surface area = 1336 m2/g), as reported by Kemp et al. [79], which showed a reversible
CO2 capacity of 2.7 mmol/g at 298 K and 1 atm as well as enhanced stability for repeated
adsorption cycles. Borane-modified graphene was also reported by Oh et al. [80], obtaining a
CO2 uptake of 1.82 mmol/g at 298 K and 1 atm. Some novel hybrid materials have also been
introduced to obtain better improvements in the adsorption properties, including mesoporous
graphene oxide (GO)-ZnO nanocomposite [81], mesoporous TiO2/graphene oxide nanocom‐
posites [82], Mg–Al layered double hydroxide (LDH), graphene oxide [83], MOF-5 and
aminated graphite oxide (AGO) [84], UiO-66/graphene oxide composites [85], and MIL-53(Al)
and its hybrid composite with graphene nanoplates (GNP) [86].
2.4. Metal organic frameworks
A more recent class of porous materials was manufactured and named metal organic frame‐
works. They represent one of the promising adsorbents and have gained significant attention
during recent years for gas separation applications [87, 88]. MOFs are composed of metal ions
or clusters (nodes) bridged by organic ligands (connecters) to form various structures and
networks. MOFs are well recognized for their extraordinary surface areas, ultrahigh porosity,
and most importantly the flexibility to tune the porous structure as well as the surface
functionality due to the presence of organic ligands that can easily be chemically modified [89,
90]. One main advantage of MOFs over other solid materials is the possibility to tailor the pore
size and functionality by rational selection of the organic ligand, functional group, metal ion,
and activation method.
Several review papers are available in the literature for gas separation using MOFs [91–96];
however, great progress has been achieved during the past four years (2012 onward). In order
to address the limitations of MOFs and investigate new structures, novel functional groups,
in addition to hybrid systems and technologies, more studies are needed to explore the
mechanisms involved and to improve the uptake capacity in a humid environment. For these
reasons, considerable effort has been observed during the past decade to address gas separa‐
tion and adsorption using MOFs. Figure 2 shows the number of publications on CO2 capture
and separation using MOFs during the past 15 years, which reflects the growing interest of
MOFs as efficient solid sorbents.
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4500
4000
Number of Publications
3500
3000
2500
2000
1500
1000
500
0
2000 2002 2004 2006 2008 2010 2012 2014
Year
25000
Number of Publications
20000
15000
10000
5000
0
2000‐2004 2005‐2009 2010‐2015
Period
Figure 2. Number of publications on CO2 capture using MOFs (based on Web of Science database)
Figure 2. Number of publications on CO2 capture using MOFs (based on Web of Science database)
4. Adsorption of CO2 on metal organic frameworks

3. Adsorption of CO on metal organic frameworks
CO2 capture performance of different 2 MOFs will be comprehensively reviewed in terms of their capacity, selectivity,
heat of reaction, and major challenges facing researchers, and some ideas to approach these challenges will also be
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adsorption are considered the main criteria for the evaluation
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3.1.corresponds
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post-combustion 2 Capture The gravimetric uptake of CO2 is indicative of the ability of
MOFs to adsorb CO2 and, therefore, we have reported CO2 uptake along with MOF surface area, and other properties
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for MOFs published after 2012 which could be added to the published reviews that have listed these data in a table
format. Table 1 for
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represents of MOFs
the properties for CO
of MOFs 2 separation.applications,
at high-pressure CO2 uptakewhile
is a proportional function
Table 2 presents the low-
pressure data.
Table 1. Adsorption capacities at high pressure

of pressure in the gas phase, where the low pressure corresponds to post-combustion appli‐
cations. The gravimetric uptake of CO2 is indicative of the ability of MOFs to adsorb CO2 and,
therefore, we have reported CO2 uptake along with MOF surface area, and other properties
for MOFs published after 2012 which could be added to the published reviews that have listed
these data in a table format. Table 1 represents the properties of MOFs at high-pressure
applications, while Table 2 presents the low-pressure data.
Surface Area (m2/g)
Capacity Pressure Temp. Qst

Common name BET Langmuir Selectivity Ref.
(wt%) (bar) (K) (kJ/mol)
UiO(bpdc) 2646 2965 72.5 20 303 [97]
ZJU-32 3831 49 40 300 [98]
UPG-1 410 514 11.9 9.8 298 24 24 [99]
Cu3(H2L )(bipy)2.11H2O
2
6.4 8.5 298 [100]
Cu3(H2L )(etbipy)2.24H2O
2
4.7 9.6 298 [100]
NU-111 4932 61.8 30 298 23 [101]
HTS-MIL-101 3482 52.8 40 298 [102]
DGC-MIL-101 4198 59.8 40 298 [102]
UTSA-62a 2190 43.7 55 298 16 [103]
ZIF-7 312 355 20.9 10 298 33 [104]
{Ag3[Ag5(l3-3,5-Ph2tz)6]
12.3 10 298 10.5 19.1 [105]
(NO3)2}n
{Ag3[Ag5(l3-3,5-tBu2tz)6]
5.4 10 298 14 15 [105]
(BF4)2}n
Basolite® C 300 1706.42 41.9 224.99 318 18 [106]
Basolite® F300 1716.46 24.1 224.99 318 19 [106]
Basolite® A100 1524.8 26.9 224.99 318 9 [106]
IRMOF-8 1599 1801 7.8 1 298 21.1 [107]
IRMOF-8-NO2 832 926 3.8 1 298 35.4 [107]
MIL-101(Cr) 2549 24.2 30 303 [108]
HKUST-1 1326 26.3 30 303 [108]
DMOF 1980 38.1 20 298 12a 20 [109]
DMOF-DM1/2 1500 27.5 20 298 [109]
DMOF-Br 1320 24.3 20 298 [109]
DMOF-NO2 1310 32 20 298 [109]
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Surface Area (m2/g)
Capacity Pressure Temp. Qst

(wt%) (bar) (K) (kJ/mol)
DMOF-TM1/2 1210 23.9 20 298 [109]
DMOF-TF 1210 16.2 20 298 9a 18 [109]
DMOF-Cl2 1180 26.4 20 298 17 21 [109]
DMOF-OH 1130 24.8 20 298 [109]
DMOF-DM 1120 25.4 20 298 23 a

23 [109]
DMOF-TM 1050 23.6 20 298 28 a

29 [109]
DMOF-A 760 17.1 20 298 [109]

a
IAST selectivity
Table 1. Adsorption capacities at high pressure
Surface Area (m2/g)
Capacity Pressure Temp. Qst (kJ/

(wt%) (bar) (K) mol)
rht-MOF-pyr 2100 12.7 1 298 28 [110]
rht-MOF-1 2100 11 1 298 29 [110]
JLU-Liu22 1487 15.6 1 298 30 [111]
SIFSIX-3-Zn 8.9 1 298 [112]
SIFSIX-3-Cu 9.6 1 298 [112]
SIFSIX-3-Co 223 10 1 298 47 [112]
SIFSIX-3-Ni 368 10.3 1 298 51 [112]
{[H2N(CH3)2]4[Zn9O2(BTC
844 1132 10.9 0.91 298 29 [113]
)6(H2O)3].3DMA}cn
{[NH2(CH3)2,
406 539 6.4 0.91 298 30 34.7 [113]
Cd(BTC)].DMA}n
Ni-DOBDC 798 18.2 1 298 [114]
Py-Ni-DOBDC 409 12 1 298 [114]
UiO(bpdc) 2646 2965 8 1 303 [97]
ZJU-32 3831 4.8 1 300 [98]
Cu-TDPAH 1762 18.4 1 298 200a 33.8 [115]
Zn/Ni-ZIF-8-1000 750 9.9 1 298 30a 61.2 [116]
ZIF-8-1000 9.6 1 298 23.5 a

49.7 [116]
Surface Area (m2/g)

Zn(5-mtz)(2-eim).(guest)
1430 1981 8.2 1 295 81 22.5 [117]
[ZTIF-1]
Zn(5-mtz)(2-pim).(guest)
1287 1461 3.8 1 295 20 [117]
[ZTIF-2]
UTSA-49 710.5 1046.6 13.6 1 298 95.8 [118]
ZJNU-40 2209 16.4 1.01 296 18.4 [119]
UPG-1 410 514 2.1 1 298 24 24 [99]
InOF-8 6.9 1 295 45.2 [120]
Cu3(H2L )(bipy)2.9H2O
1
2.5 1 195 [100]
Cu3(H2L2)(bipy)2.11H2O 2.3 1 298 [100]
Cu3(H2L2)(etbipy)2.24H2O 0.5 1 298 [100]
UiO-66(Zr100) 1390 1644 6.2 1 298 26 [121]
UiO-66(Ti32) 1418 1703 6.4 1 298 28 [121]
UiO-66(Ti44) 1749 2088 7.2 1 298 34 [121]
UiO-66(Ti56) 1844 2200 8.8 1 298 37 [121]
NU-111 4932 4.8 1 298 23 [101]
JLU-Liu1 145 221 5.9 1 298 47.7 [122]
HTS-MIL-101 3482 12.3 1 298 [102]
DGC-MIL-101 4164 14.5 1 298 [102]
UNLPF-1 13.9 1 273 [123]
UTSA-62a 2190 8.1 1 298 16 [103]
[Zn2(BME-bdc)x(DB-
21.7 0.91 195 [124]
bdc)2_xdabco]n
Zn-DABCO 1870 1902 7.2 1 298 22.4 [125]
Ni-DABCO 2120 2219 8.1 1 298 25.8 [125]
Cu-DABCO 1616 1678 6.2 1 298 22.4 [125]
Co-DABCO 2022 2095 4.1 1 298 29.8 [125]
ZnAcBPDC 920 11.7 0.9 293 [126]
ZnBuBPDC 850 7.6 0.89 293 [126]
Mg/DOBDC 1415.1 25 1 298 47 [127]
Co/DOBDC 1089.3 21.6 1 298 37 [127]
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Surface Area (m2/g)

Ni/DOBDC 1017.5 20.5 1 298 42 [127]
MIL-100(Cr) 1528.7 9.5 1 298 [127]
ZIF-7 312 355 9.1 1 298 [104]
{Ag3[Ag5(l3-3,5-Ph2tz)6]
1.6 1 298 10.5 19.1 [105]
(NO3)2}n
{Ag3[Ag5(l3-3,5-
1.6 1 298 14 15 [105]
tBu2tz)6](BF4)2}n
CuBTTri 1700 10.8 1 293 [128]
pip-CuBTTri 380 7.1 1 293 130 a

96.5 [128]
Basolite® C 300 1706.42 9.4 0.95 318 18 [106]
Basolite® F300 1716.46 2.4 0.95 318 19 [106]
Basolite® A100 1524.8 4.4 0.95 318 9 [106]
IRMOF-8 1599 1801 51.2 30 298 21.1 [107]
IRMOF-8-NO2 832 926 31.3 30 298 35.4 [107]
CPM-5 2187 8.8 1 298 16.1 36.1 [129]
Ni-MOF-74 1252 1841 19.4 1 298 [130]
Mg-MOF-74 1416 2085 30.1 1 298 [130]
MIL-101(Cr) 2549 6.8 1 303 [108]
HKUST-1 1326 13.2 1 303 [108]
[Cu(tba)2]n 7.3 1 293 25 a

36.0 [131]
IRMOF-74-III-CH3 2640 10 1 298 [132]
IRMOF-74-III -NH2 2720 10.4 1 298 [132]
IRMOF-74-III-
2170 7 1 298 [132]
CH2NHBoc
IRMOF-74-III-
2220 6.6 1 298 [132]
CH2NMeBoc
IRMOF-74-III-CH2NH2 2310 10.8 1 298 [132]
IRMOF-74-III-
2250 9.6 1 298 [132]
CH2NHMe
DMOF 1980 1 298 12a 20 [109]
DMOF-DM1/2 1500 8.1 1 298 [109]
DMOF-Br 1320 6.4 1 298 [109]

Surface Area (m2/g)

DMOF-NO2 1310 9.9 1 298 [109]
DMOF-TM1/2 1210 8.1 1 298 [109]
DMOF-TF 1210 3.3 1 298 9a 18 [109]
DMOF-Cl2 1180 8.8 1 298 17 a

21 [109]
DMOF-OH 1130 9.6 1 298 [109]
DMOF-DM 1120 1 298 23 a

23 [109]
DMOF-TM 1050 13.3 1 298 28 a

29 [109]
DMOF-A 760 10.6 1 298 [109]
CPM-33a 966 1257 12.6 1 298 22.5 [133]
CPM-33b 808 1119 19.9 1 298 25 [133]
Ni3OH(NH2bdc)3tpt 805 1115 14.8 1 298 21.5 [133]
Ni3OH(1,4-ndc)3tpt 222 310 4.6 1 298 25.3 [133]
Ni3OH(2,6-ndc)3tpt 1002 1392 7.9 1 298 24.7 [133]
Ni3OH(bpdc)3tpt 724 1009 5.5 1 298 18.7 [133]
ZIF-7-S 150 3.7 1 303 [134]
ZIF-7-D 25 9 1 303 [134]
ZIF-7-R 5 8.7 1 303 34 [134]
HKUST-1 2203 12.8 1 313 [135]
Fe-MIL-100 2990 6.6 1 313 [135]
Zn(pyrz)2(SiF6) 10.8 1 313 [135]
Mg2(dobpdc) 1940 23.8 1 313 [135]
Ni2(dobpdc) 1593 21.2 1 313 [135]
mmen-Mg2(dobpdc) 15.8 1 313 [135]
mmen-Ni2(dobpdc) 7.3 1 313 [135]
mmen-CuBTTri 11.3 1 313 [135]

a
IAST selectivity
Table 2. Adsorption capacities at low pressure
3.2. Strategies to Improve the CO2 Capture Performance on MOFs
Several strategies have been adopted to improve the performance of MOFs in CO2 capture
applications. The ability to precisely tune the MOF structures has led to versatile approaches
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that can be utilized to enhance CO2 uptake, selectivity, and the affinity toward CO2. These
methods could be classified into effects of open metal sites, pre-synthetic modifications of the
organic ligand, and post-synthetic functionalization schemes.
3.2.1. Open Metal Sites
Open metal sites in MOFs are formed by the removal of a solvent molecule coordinated to the
metal nodes by applying vacuum and/or heat after the synthesis of framework in a process
called “activation.” The presence of open metal sites on the MOF framework has a great impact
on the selectivity toward CO2 as well as on the binding energy between the adsorbed CO2
molecules and the surface of MOF sorbents. These coordinately open metal centers act as
binding sites where CO2 molecules can attach and bind to the pore surface by the induction of
dipole–quadrupole interactions. Allison et al. [136] have developed a systematic procedure to
precisely understand the interactions between the CO2 molecule and the force field generated
by the open metal sites in MOF-74. The developed method allows for accurate estimation of
adsorption isotherms using computational approach which enables the evaluation of different
hypothetical open metal sites. These observations confirm previous findings of Kong et al. on
understanding CO2 dynamics in MOFs with open metal centers [137]. Among the MOF family,
HKUST-1, M-MIL-100, M-MIL-101, and M-MOF-74 are the most widely studied frameworks
with open metal sites (M represents the metal site). However, to precisely investigate the
influence of the open metal sites, we need to isolate the effects of the nature of organic ligands,
the synthesis route, and functional groups present in the framework. It was observed that
utilizing light metal sites provides higher surface areas, and therefore improve CO2 uptake at
low pressures for MOF-74 [138]. Several studies have reported the effects of metal centers using
computational approach as reported for M-MOF-74 [138–140] where noble metals such as Rh,
Pd, Os, Ir, and Pt are considered promising candidates for CO2 capture (see Figure 3).
Casey et al. [141] studied the isostructural series of HKUST-1 for various metal centers (Mo,
Ni, Zn, Fe, Cu, and Cr) to get insights into the adsorption mechanism and the force field created
by different metal types. It was found that the presence of divalent metals such as Mg2+
significantly increased CO2 binding strength and resulted in higher selectivity toward CO2. In
addition to the nature of the metal nodes, it was found that the activation method plays a vital
role in determining CO2 uptake and affinity toward CO2 which was in agreement with
Llewellyn et al. [142] for MIL-100 and MIL-101, where various activation methods resulted in
different CO2 loadings and heat of adsorption.
In a recent study, Cabelo and coworkers [143] investigated the interaction between CO2 and
the unsaturated Cr(III), V(III), and Sc(III) metal sites in MIL-100 framework using variable
temperature infrared spectroscopy. The enthalpy of adsorption for Cr(III), V(III), and Sc(III)
were amounted to be (−63, −54, and −48) kJ/mol, respectively, which are considered among the
highest values for CO2 adsorption on MOFs with open metal centers to date. The synthesis
and characterization of an M-DABCO series (M = Ni, Co, Cu, Zn) were described by Sumboon
et al. [125] to systematically evaluate the effect of the metal identity on surface area, pore
volume, and CO2 uptake. It was concluded that Ni-DABCO has shown the highest pore volume
and specific surface area due to the high charge density present at the metal center. Comparison
Figure 3. Top: ΔE for CO2 adsorption (in kJ/mol) in M-MOF-74. Bottom: Magnitude of the adsorption energy of CO2
relative to H2O. A positive value in this plot means that CO2 binds more strongly than H2O (Adapted from [139]).
of the M-DABCO with activated carbons and MIL-100(Cr) revealed that the unsaturated
cations possess exceptional CO2 uptake of 180 cm3/g at 1 bar and 298 K [as compared to 30
cm3/g for ACs and 60 cm3/g for MIL-100(Cr),144].
3.2.2. Pre-synthetic Modifications of MOFs
Organic ligands are the linkers that connect the metal nodes together and therefore determine
the framework structure, pore volume, pore window, and surface area which are very crucial
characteristics in CO2 separation process. Ligand functionalization is considered to be a
powerful tool to improve the adsorption of CO2 on MOFs due to the wide range of functional
groups and the ease of modifying the organic ligand through strong covalent interactions. In
a recent computational work by Torrissi et al., the impacts of various functional groups
attached to the ligand part were investigated by density functional theory (DFT) [145]. The
incorporation of amine functional moieties to the organic ligands has witnessed much attention
in recent years, due to the proven positive effect of the presence of open nitrogen sites on the
MOF frameworks [146]. Keceli et al. [147] studied four biphenyl ligands modified with amide
groups of different chain lengths. Varying the length of the alkylamide group has shown a
great impact on the porosity, surface area, and CO2 capacity. It was also evident that the
activation procedure has great influence on the surface area of the resulting material which is
attributed to the different mechanisms of solvent removal from the MOF framework. Three
amino-functionalized MOFs have been prepared from 2-aminoterephthalate (ABDC) and
three different metals (Mg, Co, and Sr). Despite a low surface area (63, 71, and 2.5 for Mg, Co,
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and Sr, respectively) and a relatively low CO2 uptake (1.4 mmol/g at 1 bar and 298 K), the
prepared MOFs had exceptional selectivity toward CO2 (396 was recorded for Mg-ABDC) and
exhibited high heat of adsorption [148]. Shimizu and coworkers [149] used 3-amino-1,2,4-
triazole ligands to design a 3D structure MOF with 782 m2/g surface area and 0.19 cm3/g pore
volume that is capable to achieve CO2 uptake of 4.35 mmol/g at 1.2 bar and 273 K. Moreover,
the as-synthesized MOF has shown enthalpy of adsorption of 40.8 kJ/mol at zero coverage
which was comparable to the commercial zeolite NaX (48.2 kJ/mol). In a similar study, Xiong
et al. [118] used triazole ligands to prepare a new framework called UTSA-49 by incorporating
nitrogen atoms and methyl functional groups on 5-methyl-1H-tetrazole ligands which
recorded 13.6 wt% CO2 uptake at 1 bar and 298 K and 27 kJ/mol enthalpy (Figure 4). These
observations were in agreement with work reported by Gao et al. for the influence of triazolate
linkers [150]. It is essential to understand the synergistic effect between the multiple functional
groups on the pore surface and their size exclusion effects which are considered potential
approaches to optimize the performance of functionalized MOFs. Table 3 summarizes CO2
capture properties of MOFs modified with different amino functional groups.
Figure 4. (a) Adsorption (solid) and desorption (open) isotherms of carbon dioxide (red circles), methane (blue
squares), and nitrogen (green triangles) on UTSA-49a at 298 K. (b) Mixture adsorption isotherms and adsorption selec‐
tivity predicted by IAST of UTSA-49a for CO2 (50%) and CH 4 (50%) at 298 K. (c) Mixture adsorption isotherms predict‐
ed by IAST of UTSA-49a for CO2 and N 2 (10:90, 15:85, and 20:80) at 298 K. (d) Mixture selectivity predicted by IAST of
UTSA-49a for CO2 and N2 (10:90, 15:85, and 20:80) at 298 K. Adapted from [118].
CO2 Enthalpy of Surface

Type of functional
MOF name uptake adsorption Pressure Temperature area Ref.
group
(wt. %) (kJ/mol) (m2/g)
ZIF-10 IM 20.9 14.9 0.9 298 - [151]
ZIF-68 (bIM)(nIM) 41.3 33.3 0.9 298 1220 [151]
ZIF-69 (cbIM)(nIM) 38.1 25.9 0.9 298 1070 [151]
ZIF-71 dcIM 18.0 19.4 0.9 298 - [151]
Cu2(L)(H2O)2 Pyrazol 32 - 1 195 844.5 [152]
[Zn2(L)] Pyrazol 37.4 - 1 195 1075.4 [152]
[Cd2(L)] Pyrazol 24.6 - 1 195 571.7 [152]
[Co2(L)(H2O)6] Pyrazol 31.6 - 1 195 734.6 [152]
Zn4(bpta)2-1 Bipyridine pillar ligands 8.2 34.82 1.2 298 413 [153]
Zn4(bpta)2-1 Bipyridine pillar ligands 3.1 27.69 1.2 298 51 [153]
Cu2L (DMA)4 Acrylamide 22.2 35 1 296 1433 [154]
2-Aminoisonicotinate and
Zn(ad)(ain) 9.2 40 1 298 399 [155]
adeninate
bio-MOF-11 Adenine 22.2 33.1 1 273 1148 [156]
bio-MOF-12 Adenine 16.2 38.4 1 273 - [156]
bio-MOF-13 Adenine 10.4 40.5 1 273 - [156]
bio-MOF-14 Adenine 8 - 1 273 17 [156]
Cu(tba)2 Triazol 7.3 36 1 293 - [131]
Table 3. CO2 uptake for MOFs modified with amine containing ligands
Apart from amine groups, there are other functional moieties that are proven to be effective
in enhancing the performance of MOFs in CO2 capture. Phosphonate and sulfonate organic
ligands have gained tremendous attention recently due to their significant improvements in
MOF stability toward water [157]. Several studies are reported based on the use of phosphonate
and sulfonate ligands, for instance, the selective CO2/N2 separation over nitrogen-containing
phosphonate MOFs was studied by Marco et al. [100], and the synthesis, stability, porosity of
the phosphonate MOFs [158], and their major applications were reported for water stability
studies [159–161]. The shielding effect exhibited by phosphonate groups were responsible for
the improved stability under humid conditions up to 90% relative humidity at 353 K as
observed for CALF-30 [161]. The enhanced water stability of these MOFs was attributed to the
kinetic blocking effect which makes the framework completely hydrophobic [159].
MOFs containing nitrogen-donor building blocks were also widely investigated, particularly
adenine group which was extensively used due to framework robustness, richness in nitrogen
sites, and framework diversity [162]. Song et al. [163] reported the preparation of three new
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adenine-based MOFs by controlling the adenine coordination with Cd metal sites. This study
has provided insight into the controlled synthesis of MOFs by controlling the structure
building units (SBU) which can be utilized to extend the idea to include multiple building units
within the same framework. Similar studies are also available based on adenine groups as
building units, where the effect of the adenine functionalization on framework topology,
porosity, and adsorption behavior was investigated [164]. The use of Zn-adeninate SBU led to
the discovery of highly porous Bio-MOF-11 to 14 series [165] and Bio-MOF-100 [166] with
exceptional surface area (4300 m2/g) and very large pore volume (4.3cm3/g); however, the
framework stability of these materials still needs to be addressed as the material tends to lose
its porosity under harsh activation environment. This issue has been tackled by Zhang et al.
[167] to prepare more stable adenine-based PCN-530 structure. Lin et al. have observed high
density of open nitrogen-donor sites on 1,3,5-tris(2H-tetrazol-5-yl)benzene (H3BTT) which
was responsible for the enhanced CO2 capacity [146] through the improvement of the frame‐
work porosity and the utilization of nitrogen sites readily available to adsorb CO2. However,
the richness of nitrogen atoms in the framework does not necessarily favor CO2 adsorption, as
reported by Gao et al. [110] for the case of tetrazolate-based rth-MOF that has more exposed
nitrogen sites as compared to pyrazolate-based rht-MOF and yet was showing less CO2 uptake
attributed to the strong electric field observed on the pyrazolate-based rht-MOF.
Other ligand modifications are also reported in literature by deploying several types of
functional groups such as hydroxyl groups (OH) on Zn(BDC) [168], (CH3)2, (OH), and (COOH)
on MIL-53(Al) [145], NO2 on IRMOF-8 [107] as well as alkyl and nitro groups grafted on DUT-5
[169]. Based on the contribution by Yaghi’s group [170], several studies were dedicated to
understand the effects of ligand extension on the pore size, surface area, and the sorption
behavior of MOFs [98, 109, 133, 171–173]. Recently, zeolite-like MOFs denoted as ZTIFs have
attracted great interest due to their unique characteristics for tuning the structure toward
various applications [174, 175]. New frameworks (ZTIF-1 and ZTIF-2) were recently reported
based on the incorporation of tetrazolates into Zn-Imidazolate structures [176], with similar
structures. UTSA-49 was also reported by Chen and coworkers for the selective separation of
CO2/N2 mixture [117].
Lately, the idea of mixed ligand approach for the synthesis of MOFs with tunable properties
has gained much attention which allows for incorporating several functionalities within each
ligand to target certain properties such as improving the stability and the capacity for CO2
simultaneously [177]. For instance, the water stability issue was tackled by Marco and
coworkers [178] by utilizing two heterocyclic N-donor-mixed phosphonate-based organic
ligands. The designed MOF has shown great water stability and achieved CO2 uptake of 77
cm3/g at low pressure and 195 K. By deploying the mixed-ligand approach, Liu et al. [179] have
successfully prepared Co-based MOFs containing both benzenetricarboxylic- and triazole-
based ligands by using a solvo-thermal synthesis technique. The synthesized MOFs displayed
CO2 uptake of up to 15.2 wt. % at 1 bar and 295 K as well as remarkable selectivity toward
nitrogen. A detailed investigation of mixed ligand approach in the design of MOFs is available
in literature [180, 181]; however, further work is still needed to optimize the synthesis condi‐
tions and correlate the observed performance to the appropriate constituents on the organic
ligands. Recent work by Yaghi et al. provided tools to quantitatively map different functional
groups incorporated into the same MOF structure [182].
3.2.3. Post-synthetic Functionalization of MOFs

As mentioned previously, tuning the affinity of the framework functionalities toward CO2 is
crucial for improving adsorptive capacities. The aim is to decorate the pore surface in order
to have high adsorption selectivity and capacity and yet minimize the regeneration energy.
In addition to the pre-synthetic modification of the organic linker, post-synthetic functional‐
ization of MOFs (PSM) is considered a viable route to insert functionalities into the MOF
structure after the formation of the basic framework. This approach can overcome the
limitations observed in pre-synthetic functionalization, for instance precise control of the
synthesis conditions is needed to preserve the functional groups during the solvo-thermal
synthesis conditions. Note that some functional groups are not stable under synthesis
conditions which require a narrow range of conditions to prepare the MOFs. Others, however,
cannot be introduced to the synthesis mixture due to solubility issues, hindrance effects, and
they might participate in the crystallization process and yield unwanted materials. Besides,
inserting functional groups on the metal sites prior to the synthesis of the framework might
intervene in the formation of the building units which can result in the deterioration of the
crystal structure [183–185]. PSM is therefore considered an attractive pathway to tailor the
properties of MOFs toward better CO2 capture performance.
In order to make use of high amine affinity toward CO2, several amine moieties were selected
for the modification of various solid sorbents [186–189] including MOFs [190, 191]. Ethyl‐
ene diamine (en) is considered the most commonly used type of amine for PSM of MOFs for
CO2 capture application. In 2014, Lee et al. [192] reported grafting the diamine into the
expanded MOF-74 or Mg(dopbdc) structure at amine loadings of 16.7 wt. % at room
temperature which exhibited very high CO2 uptake of 13.7 wt% at 0.15 bar higher than the
12.1 wt. % capacity reported by McDonald et al. for N,N'-dimethylethylenediamine (mmen)
grafted on Mg(dopbdc) [173]. The isosteric heat of adsorption was recorded to be 49 to 51 kJ/
mol indicating chemisorption of CO2 molecules which was further confirmed by the
formation of carbamic acid probed by the in situ Fourier transform infrared spectroscopy
(FTIR) experiments. The en grafted Mg(dopbdc) was further evaluated for the multicycle
adsorption, and it has only lost 3% of its CO2 uptake after five cycles. Moreover, en-
Mg(dopbdc) has also shown stable structure and capacity after exposure to different moisture
contents, and therefore this material has a potential for large-scale CO2 capture (see Figure
5). NH2, CH2NH2, CH2NHMe along with other functional groups were recently grafted on
IRMOF-74, and it was found that IRMOF-74-III-CH2NH2 displayed CO2 capacity of 3.2 mmol/
g at 1 bar [132]. The sodalite-type structure Cu-BTTri was also grafted by en functional group
[193] which showed chemisorption interaction with the adsorbed CO2 molecule as can be
observed from the high isosteric heat of adsorption (90 kJ/mol). However, the en-Cu-BTTri
has only shown improved capacity at low pressure while the unmodified MOF shows higher
uptakes at high pressure which is attributed to the significant reduction in Brunauer–Emmett–
Teller (BET) surface area from 1770 to 345 m2/g due to the pore blocking effect of the en
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group. In an attempt to address this issue, McDonald at al. functionalized mmen group on
Cu-BTTri and preserved a BET surface area of 870 m2/g with 96 kJ/mol isosteric heat of
adsorption, nitrogen selectivity of 327, and CO2 uptake of 9.5 wt.% under 0.15 bar CO2/0.75
bar N2 mixture at 25 °C. The negative impact of alkylamine functional groups on reducing
the surface area was evident, and one approach to overcome this issue is to introduce ligand
extension prior to the introduction of the amine group so as to increase the MOF porosity
and avoid the pore-blocking problem during PSMs [132]. Also, a deep insight into the
mechanism of CO2 adsorption on alkylamine-grafted MOFs is crucial to further under‐
stand the interactions for improved structural design and amine loadings [194]. Other amine
functionalities such as piperazine were also grafted into Cu-BTTri [128] and exhibited 2.5
times higher CO2 uptake as compared to bare Cu-BTTri, while the heat of adsorption confirms
the chemisorption interactions. The area reduction was also evident as it was reduced from
1700 m2/g to 380 m2/g (similar to ethylendiamin, (en)- Cu-BTTri [195]). Pyridine was also
grafted on Ni-DOBDC to improve the water stability and increase the hydrophobicity of the
material [196]. Experimental observations supported by simulations results confirmed the
enhanced water stability for the Pyridine-Ni-DOBDC samples while maintaining the CO2
uptake at atmospheric conditions and low pressures. It was also concluded that the amine
moiety was grafted on the unsaturated metal sites of the framework, which makes this
approach desirable for amine functionalization. From a combined experimental and simula‐
tion study, it was found that pyridine modification of an MOF can reduce H2O adsorption
while retaining considerable CO2 capacity at conditions of interest for flue gas separation.
This indicates that post-synthesis modification of MOFs by coordinating hydrophobic ligands
to unsaturated metal sites may be a powerful method to generate new sorbents for gas
separation under humid conditions. Amine functionalization to target the water stability of
MOFs will be further discussed in the next section.
It is evident from the previous discussion that amine impregnation into MOFs always
sacrifices the surface area of the final product. Therefore, the choice of the amine that can
improve the affinity toward CO2 and attain high surface area simultaneously is a trade-off
issue. MIL-101 materials were reported to have the highest pore volume and surface area
among MOFs to date (BET = 3125 m2/g and 1.63 cm3/g). Hence they allow the incorpora‐
tion of amines with longer alkyl chains such as polyethyleneimine while at the same time
maintaining relatively high surface area (1112.6 m2/g after 75 wt% amine loading). PEI-
loaded MIL-101 prepared by Lin et al. [197] exhibited remarkably high CO2 uptake of 4.2
mmol/g at 0.15 bar and 298 K with exceptional CO2/N2 selectivity of 770 at 25 °C.
Optimization of amine loadings and distribution within the MOF structure is a detrimental
factor for the impact of these functionalities on the performance in CO2 capture process. Precise
control of the different factors during the grafting process is crucial to append these groups
exactly on the unsaturated metal centers, while avoid blocking the pores and hindering access
to the interior volume. Improving the PSM methods is considered one of the means to achieve
the ideal grafting and amine distribution [191].
combined experimental and simulation study, it was found that pyridine modification of an MOF can reduce H2O
adsorption while retaining considerable CO2 capacity at conditions of interest for flue gas separation. This indicates
that post-synthesis modification of MOFs by coordinating hydrophobic ligands to unsaturated metal sites may be a
powerful method to generate new sorbents for gas separation under humid conditions. Amine functionalization to
target the water stability of MOFs will be further discussed in the next section.
Figure 5. Top: Adsorption isotherms of CO2 for 1-en at the indicated temperatures. Bottom: Adsorption–desorption cy‐
cling of CO2 for 1-en showing reversible uptake from (a) simulated air (0.39 mbar CO2 and 21% O2 balanced with N2)
and from (b) simulated flue gas (0.15 bar CO 2 balanced with N2). (c) time-dependent CO2 adsorption for porous materi‐
als (A = 1-en, B = mmen-Mg2(dobpdc), C = 1, D = Mg-MOF-74, E = Zeolite 13X, F = MOF-5). (d) CO2 adsorption ratio of
1-en in flue gas (after 6 min exposure to 100% RH at 21 °C) to 1-en in flue gas (Adapted from [192]).
4. Recent Advances and Current Trends
4.1. Hybrid Systems Based on MOFs
For more efficient utilization of MOFs sorbents, several hybrid systems based on MOFs with
other solid sorbents have been investigated in the literature. The objective of having hybrid
materials is to utilize the synergism between the two sorbents and therefore ultimately
improve the overall performance in CO2 separation. Moreover, sorbents such as activated
carbons, graphenes, and CNTs provide the added feature of high surface area and easily
functionalized sites which contribute to the tuning of the final properties of the composite
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material. CNTs represent one of the effective candidates that can improve the properties of
MOFs for gas adsorption applications. Zhu et al. [198] incorporated HKUST-1 in the interspace
of CNTs. The designed composite exhibited superior selectivity and a CO2 saturation capacity
of 7.83 mmol/g at 298 K, which was attributed to the high porosity and surface area. In a similar
study, multiwall CNTs, well dispersed in MIL-101 (Cr), were successfully prepared and
maintained the same framework and crystal structure as MIL-101. An increase of 60% in
CO2 uptake was observed for the MWCNT-MIL-101 composite which was attributed to the
increased porosity as a result of incorporating CNTs [199], as was confirmed by similar work
on MWCNT-MIL-53(Cu) composite [200].
Graphene oxide composites with different MOFs are extensively reported in the literature such
as HKUST-1 [201], MOF-5 [202], and Cu-BTC [203]. Graphite oxide (GO) is considered a
stabilizing agent for MOFs under humid environment, and it has shown remarkable CO2
capacity of 3.3 mmol/g and great stability under simulated flue gas conditions for GO/Cu-BTC
composite [203]. The synthesis of Cu-based MOFs composite with aminated graphite oxides
(GO) was carried out and fully characterized by Zhao et al. [204]. The composite exhibited 50%
enhanced porosity as compared to the parent MOF and displayed unique structure and pore
sizes effective for size exclusion separation of CO2 from the flue gas. Silica aerogel (SA) was
also investigated as a promising candidate for hybrid systems with ZIF-8 [205]. The detailed
characterizations of the SA/ZIF-8 confirmed the presence of the two phases in the composite
after sol–gel synthesis procedure with different ZIF-8 loadings and mild BET surface area [205].
Several composite materials have been reported for various applications; however, utilizing
these hybrid systems in CO2 adsorption might be a promising route for improving the CO2
capture process. Ahmed et al. [206] published a review of information related to the synthesis
and adsorption applications of MOF composite materials.
4.2. Ionic Liquids/MOF Composites
Ionic liquids as solvents for the absorption separation of CO2 from flue gas are discussed in
Section 1.2 in order to overcome the limitations related to the poor dynamics of CO2 separation
in ILs due to their high viscosity. MOFs can act as an ideal support material for the incorpo‐
ration of ILs into their porous structure while preserving their unique properties. The concept
of immobilization of ILs into solid sorbents has been reported for various applications. For
instance, ILs immobilization on mesoporous silica was reported for the catalytic esterification
reaction [207], ILs addition into polymer gels for ionic conductivity applications [208], ILs/
Zeolite composites [209], in addition to several review papers available on this topic indicating
the widespread use of this new approach over the past years [210, 211]. Computational
investigation of the theoretical possibility of incorporating ILs into MOFs was studied by
Jiang’s group for (BMIM)PF6 IL supported on IRMOF-1 for CO2 capture applications [212].
The confinement effects of the narrow pore on the ILs and the ionic interactions between
[BMIM]+ favor the open pore while the anion, [PF6]−, was attached to the open metal sites, was
observed in a simulation study. It was ascertained that CO2 was favorably attached to the
[PF6]− anions sites. The study demonstrated that IL/MOF composites are a potential candidate
for CO2 adsorption and have displayed significantly high CO2/N2 selectivity. To the best of our
knowledge, the first report on an experimental attempt to immobilize ILs into MOF structures
was published by Liu et al. [213] for the insertion of Bronsted acidic ILs (BAIL) into the pores
of MIL-101 using post-synthetic approach with triethylene diamine (TEDA) or imidazole
(IMIZ) as a solvent assisting during the functionalization process. Nitrogen adsorption
isotherms of bare MIL-101, TEDA-BAIL/MIL-101, and all (IMIZ-BAIL/MIL-101) samples
showed type-I isotherm indicating the microporous nature of the composite. BET surface area
was 1873 m2/g for the bare MIL-101 which was slightly decreased to 1728 m2/g and 1148 m2/g
for IMIZ-BAIL/MIL-101 and TEDA-BAIL/MIL-101, respectively. Following this leading report,
Jhung’s group [214] successfully grafted up to 50 wt.% acidic chloroaluminate IL on MIL-101
which reduced the BET surface area of the bare MIL-101 by around 60%. The incorporation of
ILs with basic nature which is favorable for CO2 adsorption was for the first time reported by
Kitagawa et al. [215]. A detailed characterization and investigation of the phase behavior of
the immobilized 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylamide) denoted as
EMI-TFSA ILs into ZIF-8 was presented in this study. A reduction of 29% in pore volume was
measured in N2 adsorption isotherm experiments and computational calculations. The EMI-
TFSA/ZIF-8 composite has shown distinctive ion conductivity at low temperature as reported
in a second paper by the same group [216]. The prospect of IL/MOF composite for gas
separation is still under computational investigation with no reported experimental studies of
CO2 adsorption on these composites. Recently, Vincent-Luna et al. [15] investigated the effects
of adding room temperature ILs (RTILs) into the pores of Cu-BTC structures. The adsorption
of CO2, N2, CH4, and their mixtures were studied by utilizing various RTILs having the same
cation 1-ethyl-3-methylimidazolium [EMIM]+ and different anions such as bis[(trifluorometh‐
yl)-sulfonyl]imide [Tf2N]−, thiocyanate [SCN]−, nitrate [NO3]−, tetrafluoroborate [BF4]−, and
hexafluorophosphate [PF6]−. The RTIL/Cu-BTC composite has shown enhanced CO2 uptakes
at low pressures with high CO2/N2 selectivity due to the polarization driving force rendering
these materials as a promising system for post-combustion CO2 capture. Another application
of IL/MOF composite as a precursor for the preparation of nitrogen and boron–nitrogen (N-
and BN-)-decorated porous carbons was recently reported by Aijaz et al. [217] as a novel
synthesis strategy.
4.3. Ab/Adsorption in Ionic Liquids/MOF Slurry System
Another approach to utilize the combined synergistic advantages of MOF and IL composites
is through a novel hybrid adsorption–absorption technology. This novel technology can
provide an efficient approach to utilize the high capacity, selectivity, and low heat of adsorp‐
tion of the solid sorbents along with the advantages of having a continuous flow process that
allows for better heat integration and separation rates in contrast to the conventional batch
process used in adsorption-only process. Mass transfer enhancement due to the dispersion of
fine solids in liquid solvents was studied and insight into the mechanism and the analysis of
different mass transfer resistances were described by Zhang and coworkers [218] which was
in agreement with previous findings [219–221]. As far as enhancement of CO2 capture in slurry
systems is concerned, a study dealing with AC particles dispersed in K2CO3 aqueous solution
was reported by Sumin et al. [222] to investigate the influence of the hydrodynamics on the
mass transfer improvements. In a similar work by Rosu et al. [223], AC particles were also
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Figure 6. Top left: schematic of the slurry system. (a) Comparison of selectivity toward N2. (b) ab/adsorption enthalpy.
(c) CO2 uptake at 303.15 K (Adapted from [225]).
found to improve the absorptive CO2 capture process. The unique characteristics of MOFs in
CO2 adsorption and their recent applications in aqueous solution environment [224] have
opened the door toward the possibility of immersing MOF particles in various physical and
chemical solvents for CO2 separation application. This novel unit operation process can
overcome the limitations reported for conventional adsorption on MOFs such as high pressure
drop and the necessity for formulating the powders into different shapes and sizes which
affects their structural stability and reduces the active surface area. Liu et al. [225] reported,
for the first time, the preparation of ZIF-8/glycol and ZIF-8/glycol/2-methylimidazole slurries
(Figure 6). CO2 uptake of 1.25 mmol/L was recorded for the slurry system with CO2/N2
selectivity of 394 at 1 bar, and most importantly a very low enthalpy of 29 kJ/mol. In a similar
work by Lei et al. [226], ILs [EMIM, TF2N] and [OMIM, PF6] were used to prepare slurry
systems with ZIF-8 and ZIF-7. CO2 adsorption in the slurry system has shown a promising
performance with isosteric heat of adsorption less than 26 kJ/mol. Following these two studies,
the solubility of CO2 in physical solvents such as methanol mixed with ZIF-8 was also
investigated [227]. The study revealed that ZIF-8 can significantly improve the low pressure-
CO2 uptake in physical solvents and can dramatically reduce the solvent losses by evaporation
to the gas phase at the top of the absorber. Increasing ZIF-8 loadings has shown further
enhancement of the CO2 capacity, as observed previously [225]; however, it is worth noting
that a high solid loading in the slurry system was not recommended from process engineering
point of view as it might cause some problems during the pumping of the slurry mixture and
increases the solid losses in the multicycle separation process [225].
For future studies on MOF-based slurry systems, there is basic selection of criteria that needs
to be satisfied by both MOF and the liquid solution. The selection of the MOF possessing the
appropriate pore size for the preparation of the slurry system is very important to guarantee
that the size of the liquid is large enough and does not occupy the pores which leaves no space
for CO2 to adsorb. Moreover, the structural stability of the MOF in the aqueous solution is
essential so that it does not lose its porous framework nor its surface area. The selection of the
liquid candidate is crucial, as it should not provide any extra mass transfer resistance for
CO2 molecules. Further, experimental and computational investigations are still required to
understand the separation mechanism in slurry mixtures and to have insight into the different
types of interactions between the gas, liquid, and solid materials.
5. Challenges and Outlook
In conclusion, MOFs are considered the largest growing research area in CO2 capture, with
great achievements and developments. Due to their versatile structures and possibilities for
various functionalization approaches, the door is still open for further improvements and
advancements of their performance under real flue gas conditions, and in large-scale applica‐
tions. Although we have reported MOFs with distinguished properties and exceptional CO2
capacity, selectivity, and stability, there are still some concerns that need to be addressed before
reaching commercial scale level. The lack of information about the performance of MOFs under
real gas mixture conditions is one of the key issues to understand the actual working uptakes
and identify any possible limitations. Further experimental testing of MOFs using, for example,
a gas mixture containing all the impurities that might be present in an actual flue gas is needed
high-throughput technique. Computational gas mixture studies can provide essential infor‐
mation in this regard; however, experimental investigation is still considered the most reliable
approach. MOF stabilities in humid conditions, high temperature, and harsh mechanical stress
situations must be given much attention. Several studies were performed to target MOF
stability, and great achievements were recorded in this field [228, 229], as reviewed in refer‐
ences [160, 230]. Finally, in the following section, we focus on water stability studies as it is
one of the main drawbacks of MOFs.
5.1. Water Stability of MOFs
Water stability is a major challenge that has to be overcome before metal organic framework
can be used in removing carbon dioxide from flue gas. The core structure of MOF reacts with
water vapor content in the flue gas leading to severe distortion of the structure and even failure.
As a consequence, the physical structure of MOF is changed, e.g., reduction of porosity and
surface area, etc. that decreases the capacity and selectivity for CO2. Complete dehydration of
flue gas increases the cost of separation. It is therefore essential for MOFs to exhibit stability
in the presence of water up to certain extent [91].
Metal–ligand coordination bond, which is the most significant part of MOF, is hydrolyzed with
water, resulting in the displacement of ligand bond; and as a consequence, the whole structure
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usually collapses [91]. The stability of MOF in the presence of water depends on the strength
of metal ligand bond. pKa values of the ligand atom can be considered as the strength of this
metal- ligand bond. Since the hydrolysis reaction between MOF and water molecule is
governed by Gibbs free energy and activation energy of the reactant and product molecules,
thermodynamics and kinetics factors have great influence on the water stability of MOF [160].
Insight into the molecular structure, more specifically the metal–ligand strength, the weakest
part of MOF, and thermodynamics as well as kinetics study of hydrolysis reaction are very
important to improve water stability. Several strategies based on these two important aspects
have been taken into consideration.
Jasuja et al. [231] performed a study on the effects of functionalization of the organic ligand in
a series of isostructural MOFs in the Zn(BDC-X)-(DABCO)0.5 family on water stability. In this
experiment, they cyclically stabilized an unstable parent structure in humid conditions
through the incorporation of tetramethyl-BDC ligand. The results of molecular simulation
disclosed that the kinetic stability is improved due to the carboxylate oxygen in the DMOF-
TM2 structure which acted as a shield to prevent hydrogen-bonding interactions and subse‐
quent structural transformations. Hence, electrophilic zinc atoms in this structure became
inaccessible to the nucleophilic oxygen atoms in water, resulting in prevention of the hydrol‐
ysis reactions for the displacement ligand. They also performed another study to evaluate the
effect of strength of metal–ligand coordination bond and catenation in the framework on water
stability [232]. According to their results, the non-interpenetrated MOFs constructed from a
pillar ligand of higher pKa exhibited higher stability; however, interpenetrated MOFs con‐
structed from a pillar ligand of lower pKa values exhibited less stability. The interpenetration
in MOF with incorporation of ligands of relatively high basicity exhibited good water stability.
By considering the results of previous experiment, they synthesized cobalt-, nickel-, copper-,
and zinc-based, new pillared MOFs of similar topologies which exhibited good water stability
[233]. The grafted methyl group on the benzene dicarboxlate (BDC) ligand introduced steric
factors around the metal centers; consequently, water stability of MOF drastically improved.
The basicity of BTTB-based MOFs synthesized with bipyridyl pillar ligands had lower basicity
than DABCO; however, they exhibited better stability in the presence of humid condition.
Bae et al. [114] performed a study to modify Ni-DOBDC with pyridine molecules. The study
showed that pyridine molecule made the normally hydrophilic internal surface more hydro‐
phobic; as a result, water absorption was reduced, while substantial CO2 capture capacity was
retained to a certain level. Fracaroli et al. [132] improved the interior of IRMOF-74-III by
covalently functionalizing it with a primary amine, and used a MOF, IRMOF-74-IIICH2NH2,
for the selective capture of CO2 in 65% relative humidity.
Zhang et al. [234] performed a study to modify the surface of the MOF hydrophilic to hydro‐
phobic to improve water stability. They demonstrated a new strategy to modify hydrophobic
polydimethysiloxane (PDMS) on the surface to significantly enhance their water resistance by
a facile vapor deposition technique. In this study, they successfully coated three vulnerable
MOFs according to the water stability (MOF-5, HKUST-1, and ZnBT), while the porosity,
crystalline characteristics, and surface area were unchanged.
All these studies demonstrated that water stability of MOFs can be improved by incorporating
specific factors (e.g., metal–ligand strength, thermodynamic and kinetic factors, etc.) which
govern the structural stability of the framework.
Author details
Mohanned Mohamedali, Devjyoti Nath, Hussameldin Ibrahim and Amr Henni*
*Address all correspondence to: amr.henni@uregina.ca
Industrial/Process Systems Engineering, Faculty of Engineering and Applied Science,

University of Regina, Regina, SK, Canada
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Chapter 7
Carbon Dioxide Geological Storage (CGS) – Current

Status and Opportunities
Kakouei Aliakbar, Vatani Ali, Rasaei Mohammadreza and Azin Reza
http://dx.doi.org/10.5772/62173
Abstract
Carbon dioxide sequestration has gained a great deal of global interest because of the
needs and applications of mitigation strategy in many areas of human endeavors includ‐
ing capture and reduction of CO2 emission into atmosphere, oil and gas enhanced pro‐
duction, and CO2 geological storage. In recent years, many developed countries as well as
some developing ones have extensively investigated all aspects of the carbon dioxide
geological storage (CGS) process such as the potential of storage sites, understanding the
behavior of CO2, and its interaction with various formations comprising trapping mecha‐
nisms, flow pattern, and interactions with formation rocks and so on. This review
presents a summary of recent research efforts on storage capacity estimation techniques
in most prominent storage options (depleted oil and gas reservoir, saline aquifers and
coal beds), modeling and simulation means followed by monitoring and verification ap‐
proaches. An evaluation of the more interesting techniques which are gaining attention in
each part is discussed.
Keywords: carbon dioxide, geological storage, CGS
1. Introduction
Carbon dioxide (CO2) is one of the most emitted greenhouse gases (GHG) which causes heat
trapping of the earth and contributes to the global climate change. This global issue led to the
public concern and has become a serious problem in the developed and developing countries
[1]. Accordingly, the increase of GHG in the atmosphere has led to a rise in the average global
temperatures with a warming forecast of 1.8–4.0°C [2]. Recent surveys conducted, see [2–5],
show that the CO2 concentrations has risen from pre-industrial levels of 280 parts per million
(ppm) to present levels of ~380 ppm in the atmosphere and this increase in CO2concentration
depends on world’s expanding use of fossil fuels. Further studies, according to the CO2
emissions from fossil fuel power plants, represent the amount of emissions around 23 Gton-
CO2 per year and 26% of the total emissions approximately[1, 2, 6]. Reports from on-road
transportation emissions also indicate the high contribution of CO2 in atmosphere especially
in urban areas. It contributes around 10% of the total global and 20% of the European atmos‐
pheric CO2 emissions [7]. Based on the Intergovernmental panel on Climate Change (IPCC)
report in 2005, 72% of the anthropogenic greenhouse effect is due to the CO2 emission and it
is considered as the most important GHG contributor [1]. The Kyoto Protocol in 1997 also
recommends that the nations minimize their CO2 emissions up to 95% of 1990 levels by 2012.
In this regard, the mitigation options of the CO2 have been defined in many national and
international scales and the scientists have been looking and developing for the techniques
which reduce the CO2 emissions [8–11]. The options include reduction in using carbon-
intensive fuels and improving energy efficiency in order to decrease the CO2 emissions into
the atmosphere or carbon sequestration.
CO2 sequestration is the process of injecting CO2 into sub-surface to reduce the emissions of
anthropogenic CO2. According to the IPCC 2005, the storage options are classified into three
groups: (1) ocean storage, (2) mineralization, and (3) geological storage. Ocean storage consists
of injecting the CO2 into deep oceans and immobilizing it by dissolving or forming a plume
which is heavier than water under the ocean. The ocean is the largest storage option of CO2
and can contain 40000 Gton of carbon in contrast to the 750 Gton in the atmosphere. The ocean
storage has not yet been considered as a pilot scale since it is still in the research phase and
may also have dire consequences in marine life in case of leakage during and after the storage.
[1, 12]. Mineralization process provides an opportunity to store the CO2 for a long period of
time without any special concern about the permanent mitigation quality. It includes the
CO2 conversion to a solid inorganic carbonates which is stable for a long time. The only
considerable problem in this process is related to the high cost of implementation [13]. The
CO2 geological storage (CGS) is considered as the main process for CO2 sequestration in the
developed world [14–16]. The candidate CO2 storage facilities consist of deep saline aquifer
and unmineable coal deposits, as well as depleted and mature oil and gas reservoirs which
can contain 2200 Gton of carbon dioxide [17]. Based on an estimation reported by the European
technology platform for zero emission fossil fuel power (ZEP), the contribution of each option
for the storage potential of CO2 is shown in Figure1. [18]
As for CGS’s regulation in Europe in 2009, the European Union approved that seven million
tons of CO2 could be stored by 2020 and up to 160 million tons by 2030, assuming a 20%
reduction in GHG emissions by 2020 [19]. Over the past decade, many developed countries
have extensively investigated the potential of CO2 storage sites as well as understanding the
behavior of CO2 and its interaction with different reservoir formations as a prerequisite to
increase the effectiveness and integrity of the CGS projects. These comprise advanced scientific
knowledge about CO2 behavior such as trapping mechanisms (physical and chemical), flow
patterns, and interactions with formation rocks that can be achieved by improved techniques
such as flow simulation, reservoir modeling, reservoir monitoring, and verification [20].
www.ebook3000.com
emission fossil fuel power (ZEP), theCarbon Dioxide Geological
contribution of eachStorage (CGS) – Current
option for theStatus and Opportunities
storage potential157of CO2
http://dx.doi.org/10.5772/62173
is shown in Figure1. [18]
9% 1%
Deep Saline Aquifers
Depleted & Matured oil and

gas reservoirs
Deep unmineable Coal
Deposits & Others
90%
Figure1.The contribution of most important CGS techniques in the world’s CGS projects.
Figure 1. The contribution of most important CGS techniques in the world’s CGS projects.
As for CGS’s regulation in Europe in 2009, the European Union approved that seven million
tons of CO 2.2CGS:
couldStorage
be stored Capacity
by 2020 and up to 160 million tons by 2030, assuming a 20%
reduction in GHGyears,
In recent emissions
there have by been
2020a number
[19]. Over the past
of surveys decade,
related manycapacity
to the storage developed countries have
estimation
extensivelymethods in CGS fields
investigated [21]. The first
the potential of CO groups of estimation
2 storage sites assessments
as well as were simple with no
understanding the behavior
technical component similar to the estimations held in Europe by Holloway
of CO2 and its interaction with different reservoir formations as a prerequisite to increase the and van der
Straaten, in 1995, while the other recent ones have taken into account the complexities and
effectiveness and integrity of the CGS projects. These comprise advanced scientific knowledge
more sophisticated methods of estimating the CO2 storage capacity [22–28]. One should keep
about CO2inbehavior
mind that the
such capacity estimationmechanisms
as trapping in any different(physical
scale (global, reservoir,
and basin, or
chemical), region)
flow patterns, and
and time frame is a difficult process due to our lack of knowledge about
interactions with formation rocks that can be achieved by improved techniques such as flow subsurface in most
areas of the world and also the uncertainties and inaccessibility of the available data [29].
simulation,However,
reservoir modeling, reservoir monitoring, and verification [20].
there is a wide variety of estimation techniques proposed by different authors (CSLF,
IPCC, and Bradshaw et al.) which mainly rely on a simple algorithm depending on various
storage mechanism [26, 28, 30].
CGS: Storage Capacity
In 1979 and 1988, the concept of resource pyramids was developed by Masters and McCabe
for the first time and was later proposed to demonstrate the accumulation and quality of the
CO2 storage
In recent years, therepotentials
have beenin the form of three
a number pyramidsrelated
of surveys as an important factor for
to the storage capacityestimation
capacity
estimation, including (1) high level, (2) techno-economic, and (3) trap-type
methods in CGS fields [21]. The first groups of estimation assessments were simple with no and effectiveness
pyramid [31, 32]. This concept consists of the main aspects of CO2 storage such as different
technical component similar to the estimations held in Europe by Holloway and van der Straaten,
time scales and assessment scales, various assessment types, and different geological storage
in 1995, options
while the [29]. other recentas ones
For instance, it has have taken into inaccount
been demonstrated Figure2, the complexities and more
the techno-economic
sophisticated methods of estimating the CO2 storage capacity [22–28]. One and
resource pyramid calculates the storage capacity in mass instead of the volume includes
should keep in mind
the maximum upper limit of capacity estimate with various time and assessment scales. On
that the capacity estimation in any different scale (global, reservoir, basin, or region) and time
the other hands, it reveals three levels of theoretical, realistic and viable estimates in which the
frame is atheoretical
difficult portion
processincludes
due totheour lackpyramid
entire of knowledge
whereas the about subsurface
realistic and viablein most
parts areas of the
have
covered the top two portions and only the top portion of pyramid respectively
world and also the uncertainties and inaccessibility of the available data [29]. However, there is a [28, 30].
In an
wide variety ofinvestigation
estimationwhich was performed
techniques proposedby Kopp
by et al. in 2009,
different to estimate
authors the effective
(CSLF, IPCC, storage
and Bradshaw
capacity, some models were proposed by authors, including(1) CSLF model (proposed by
et al.) which mainly rely on a simple algorithm depending on various storage mechanism [26,28,
Bachu et al. in 2007 in which the effective storage volume is calculated by reducing the capacity
30].
In 1979 and 1988, the concept of resource pyramids was developed by Masters and McCabe for
the first time and was later proposed to demonstrate the accumulation and quality of the CO2
storage potentials in the form of three pyramids as an important factor for capacity estimation,
including (1) high level, (2) techno
techno-economic, and (3) trap-type and effectiveness pyramid
Viable capacity: Applies technical cut off

Applies economic barriers to limits, technically viable
estimate and so on.
realistic capacity and so on.
Better quality of
Realistic capacity
Injection site
Increasing Theoretical capacity

cost of storage
Includes large volumes of

“uneconomic” opportunities.
Figure 2. Techno-Economic Resource Pyramid for capacity estimation in CO2 geological storage.
Figure 2. Techno-Economic Resource Pyramid for capacity estimation in CO2 geological storage.
In an investigation which was performed by Kopp et al. in 2009, to estimate the effective storage capacity, some
coefficient
models were proposedfrom theoretical
by authors, capacity),CSLF
including(1) (2) Doughty model (proposed
model (proposed by Bachu etbyal.Doughty
in 2007 inetwhich
al. in the
2001effective
which isestimated
storage volume calculatedthe effective the
by reducing capacity as coefficient
capacity a volumefromfraction for COcapacity),
theoretical 2 storage), and (3) Kopp
(2) Doughty model
(proposedmodel (basedet
by Doughty onal.Doughty modelestimated
in 2001 which while thethepores containing
effective capacitydissolved CO2fraction
as a volume is muchforlarger than
CO2 storage), and
(3) Kopp those
modelcontaining free gas [33]).
(based on Doughty model while the pores containing dissolved CO 2 is much larger than those
containing free gas [33]).

According to CO2 storage capacity estimation surveyed by Bachu et al., based on a summary
of carbon
According to COsequestration leadership
2 storage capacity forum (CSLF),
estimation surveyeddifferent timeframes
by Bachu et al.,and fieldon
based scales are
a summary of
carbon accounted considering
sequestration variousforum
leadership trapping mechanisms
(CSLF), (physical
different and chemical
timeframes andmechanisms)
field scales are
[26].considering
accounted Bachu et al. have demonstrated
various the approaches(physical
trapping mechanisms based on different
and chemicalgeological potential [26].
mechanisms)
with generally assessing the opportunity of other storage options like man-made
Bachu et al. have demonstrated the approaches based on different geological potential with underground
cavity
generally and the basalts
assessing such as Deccan
the opportunity Plateau
of other in India;options
storage however, theyman-made
like need more investigations.
underground cavity
and the basalts such as Deccan Plateau in India; however, they need more investigations.
2.1. Estimation techniques in depleted oil and gas reservoir
Estimation techniques in depleted oil and gas reservoir
DOE (2006), ‘Methodology for development of carbon sequestration capacity estimates’ and
CSLF (2007), ‘Estimation of CO2 storage capacity in geological media – phase II’ are the major
DOE (2006), ‘Methodology for development of carbon sequestration capacity estimates’ and
investigations regarding the storage capacity estimation approaches in geological formations.
CSLF (2007),
The CSLF ‘Estimation of CO
(2007) employs storage capacity
a 2techno-economic in geological
resource pyramidmedia
in the – phase II’
capacity are the major
estimation
investigations regarding the storage capacity estimation approaches in geological
process for depleted oil and gas reservoir based on McCabe (1998), while the DOE (2006) formations.
The CSLF (2007) employs a techno-economic resource pyramid in the
utilizes volumetric equations and Monte Carlo approach to estimate the uncertainty and capacity estimation
processcapacity
for depleted
storage by incorporating various trapping mechanisms in depleted oil and gas (2006)
oil and gas reservoir based on McCabe (1998), while the DOE
utilizes reservoirs
volumetric equations
[31]. and MonteofCarlo
Another integration approach
DOE and CSLF withto estimate the uncertainty
simple version andofcapacity
of SPE (Society
storage Petroleum Engineering)
by incorporating petroleum
various resource
trapping management
mechanisms system isoilproposed
in depleted and gasand called [31].
reservoirs
AnotherCO2CRC storage
integration ofcapacity
DOE classification
and CSLF [34, 35].simple
with They have reported
version of that
SPE on (Society
account of ofgreater
Petroleum
amountpetroleum
Engineering) of data in term of oil management
resource and gas fields, system
the estimation process and
is proposed is thecalled
easiestCO2CRC
among thestorage
capacity classification [34,35]. They have reported that on account of greater amount of data in
term of oil and gas fields, the estimation process is the easiest among the geological formations.
It should be noted that the other methods which are employed in saline aquifers can be used here
for CO2 storage volume estimation: ‘volumetric-based estimation’ and ‘production-based
estimation’ [35,36].
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Carbon Dioxide Geological Storage (CGS) – Current Status and Opportunities 159
http://dx.doi.org/10.5772/62173
geological formations. It should be noted that the other methods which are employed in saline
aquifers can be used here for CO2 storage volume estimation: ‘volumetric-based estimation’
and ‘production-based estimation’ [35, 36].
Bachu et al., provided a good overview of storage capacity estimates in oil and gas reser‐
voirs to compare the other geological formation such as coal beds and saline aquifers [26].
Based on Bachu et al., the capacity estimation in oil and gas reservoirs is more convenient
than other geological formations, and these geological formations are discrete in contrast to
the continuous coal beds and saline aquifers [26]. Estimation of the CO2 storage capacity is
also difficult for a number of reasons: In estimation process, some assumption would be
made, such as volume occupied by hydrocarbons is available for CO2 after production for
pressure-depleted reservoirs with no hydrodynamic contacts. On the other hand, forma‐
tion water influx as the consequence of pressure decline and water trapping can be in‐
versed due to the CO2 injection and increase in the pore spaces which may cause some pores
to be unavailable for CO2 storage. Thus, the original reservoir pressure has the maximum
limitation for CO2 injection into the depleted reservoirs [37]. According to the volume of
original oil and gas at surface conditions, theoretical mass storage capacity can be account‐
ed through an equation proposed by Bachu et al.[26]. They also provided an extrapolation
to account the theoretical storage capacity in another correlation. In some cases, the actual
volume availability to CO2 storage can be reduced and would be stated by capacity coeffi‐
cient (equation expressed by Doughty and Press, 2004) [38]. But based on Bachu and Shaw,
in 2005, enough data are not available for assessing these coefficients, and estimations are
mostly carried out by numerical simulations [9, 38]. One of the specific issues in CO2 storage
in depleted reservoirs is CO2 flood-enhanced oil recovery. Because of some reasons, the
capacity estimation in this case is already an effective estimation. The promising storage sites
for CO2 enhanced recovery can be performed at regional and basin scales such that this
criterion decreases the effective capacity to practical storage capacity [39–41].
2.2. Estimation techniques in saline aquifers
As it has been illustrated in recent studies, deep saline aquifers are the most favorable storage
option in comparison to the depleted reservoirs and coal beds [1, 27, 28, 39]. In contrast, the
numbers of projects which have been conducted by the industries are not considerable due to
some reasons, including availability of anthropogenic CO2 and the related data, site assessment
difficulties, poor injectivities, and high cost of monitoring [42]. According to the DOE, a
volumetric equation is proposed to CO2 storage estimation in saline aquifers, while each type
of trapping mechanisms is also needed for calculation of the basin-scale assessments [35]. In
CSLF methodology for deep saline aquifers, storage estimations based on structural and
stratigraphic trapping mechanisms are similar to depleted oil and gas reservoirs, whereas the
mass of CO2 related to the effective storage volume would be more difficult to calculate.
Moreover, the storage estimation based on solubility trapping at the basin and regional scales
can be calculated by the relation proposed by Bachu and Adams [36, 41].
Bachu et al. proposed a theoretical approach to CO2 storage estimation considering each type
of trapping mechanism in deep saline aquifers [26]. They introduced a simple time-independ‐
ent volumetric equation used for depleted oil and gas reservoirs in which the traps have been
saturated by water rather than being occupied with hydrocarbons. Similar to equation
mentioned above, a relation related to the CO2 mass storage limitation also has developed
here for basin- and regional-scale assessments, which can be utilized for theoretical and
effective capacity estimations. For residual gas trapping method, the storage volume can be
calculated with a time-dependent equation proposed by the authors with regard to the
concept of actual CO2 saturation at flow reversal by Juanes et al. [43]. The solubility mecha‐
nism is a time-dependent, continuous, and slow process which can be performed effective‐
ly after finishing the injection process. If this trapping system occurs in thick and high
permeable aquifers, a convection cell can be constituted and the dissolution process will be
improved, while in the case of thin aquifers, this mechanism is less efficient [44, 45]. Capacity
storage at the basin and regional scale can be assessed through an equation proposed by
Bachu and Adams whereas at the local and site scale, numerical simulation is required for
precise estimation of the storage capacity [41]. Estimation through mineral trapping cannot
be applied at the regional and basin scales due to the lack of available data and the com‐
plex intrinsic of mineral trapping and the chemical and physical related mechanisms. The
only remaining approach is numerical simulation which is suitable for site and local scale
during a long period of time. According to recent research, mineral trapping mechanism can
be compared to the solubility mechanisms with regard to the long time period required here
[46, 47]. Hydrodynamic trapping mechanism consists of all the mentioned features of the
mechanism and it needs various time scales for acting. This process cannot be evaluated at
regional and basin scale estimations due to the different acting time scales through various
trapping mechanisms. Hence, it should be considered in a specific point of time and the
numerical simulation applied to estimate the storage capacity at local and site scales [26, 48].
De Silva and Ranjith conducted a complete investigation related to the CO2 estimation
methods on saline aquifers and assessed different aspects of the estimation process such as
operating time frame, resource circles (pyramids), and trapping mechanisms and factors
affecting the storage capacity [50]. The proposed equations in each trapping system are based
on the relations recommended by Bachuet al. [26]. The evaluated parameters which can affect
the storage capacity consist of in-situ pressure, injectivity, temperature, permeability, and
compressibility. According to De Silva and Ranjith, eight methods have been introduced to
estimate theoretical and effective capacity of CO2 storages (volumetric method, compressibil‐
ity method, flow simulation, flow mathematical models, dimensional analysis, analytical
investigation, Japanese methodology, and Chinese methodology), while to calculate the
practical and matched capacities, the local conditions need to be considered [26, 49, 50]. In a
quick and simple volumetric method, the porosity, area, thickness, and storage efficiency of
the storage reservoirs are important in capacity estimation according to an equation
mentioned by DOE and Ehlig-Economides and Economides [see 51, 52], while van der Meer
and Yavuz have proposed another equation to measure the CO2 mass [53]. To calculate the
volume of CO2 per volume of the aquifers, Eccles et al. have introduced another relation
including measuring the effective capacity storage at a special depth [54]. The more compre‐
hensive equation to calculate the storage capacity by compressibility method was shown by
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http://dx.doi.org/10.5772/62173
Zhou et al. [55]. The most effective method to assess the capacity is the flow simulation which
includes volumetric formulas and more reservoir parameters rather than other methods [56].
Mass balance and constitutive relations are accounted in mathematical models to capacity
assessment and dimensional analysis consists of fractional flow formulation with dimension‐
less assessment and analytical approaches [33]. From the formulations demonstrated by
Okwen and Stewart for analytical investigation, it can be deduced that the CO2 buoyancy
and injection rate have affected the storage capacity [57]. Zheng et al. have indicated the
equations employed in Japanese and Chinese methodology and have noted that some
parameters in Japanese relation can be compared to the CSLF and DOE techniques [58].
2.3. Estimation techniques in coal beds
According to the IPCC 2005, the coal bed storage process is currently in the demonstration
phase. MacDonald of Alberta Energy reported the storage in coal bed in 1991 for the first time
[59]. One of the most prominent factors to guarantee the successful economic CO2 storage
process is the permeability of coal and it should be more than 1 mD (miliDarcy) [60]. The main
problem in CO2 storage in coal bed process is the limitation of available data about location
and capacity of promising sites [30, 26, 28]. It should be noted that the main trapping mecha‐
nism in storage process regarding the coal beds is adsorption, and it is necessary to assess the
rank, grade, and type of the coal in order to achieve more information about adsorption
capacity of the coals [35].
The CSLF and DOE proposed models such as volumetric equation to estimate the coal capacity
through substituting the intrinsic methane by injected CO2 process. Bachu et al. have reported
the relation demonstrating the initial gas in place after coal adsorption process proposed by
van Bergen et al. and White et al. [59, 61, 62]. One should keep in mind is that since the
adsorption is one of the main parts of the storage process, adsorbed gas capacity estimation is
also important to investigate [63]. Langmuir equation is a simple and efficient relation for
single-layer adsorption capacity estimation in low-pressure conditions [64–66]. In case of high
pressure and high temperature, other methods are more suitable such as Bi Langmuir,
extended Langmuir, Sips, Langmuir-Freundlich, Toth, UNILAN, two-dimensional EOS, LRC
(loading ratio correlation), Dubinin-Radushkevich (D-R) and Dubinin-Astakhov (D-A) [59, 67–
73]. A modified Langmuir and Toth correlation was expressed by Himeno et al. and Bae and
Bhatia, which includes the substitution of pressure by fugacity high dense phase conditions
[74, 75]. Another mathematical power equation proposed by Saghafi et al. can be used to
estimate the adsorption capacity [66].
Storage capacity estimation for the stored gas content can be performed through the equation
suggested by White, van Bergen et al., CSLF, and Vangkilde et al. [61, 76, 77]. Palarski and
Lutynski expressed another relation to estimate the CO2 storage components in coal seams [78].
To estimate the large-scale storage capacity of 45 important coal basins during Enhanced Coal
Bed Methane Recovery (ECBM) in China, Li et al. used an equation which can be modified to
a simpler form without considering the different coal bed basins [63, 79].
3. CGS: Modeling and Simulation
To study the behavior of CO2 during and after the CGS process, numerical modeling is
considered as the only effective tool prior to the experimental and field demonstrations instead
of analytical and semi-analytical solutions on account of some limitations and simplifications
[80–83]. In the past few years, various numerical modeling and reservoir simulations ap‐
proaches have been documented in the literature at the pilot and commercial scales which are
using common numerical methods such as finite difference, finite element, and finite volume
methods. One of the most efficient means for reservoir modeling is TOUGH2 simulator
developed by Pruess et al. and used successfully in Rio Vista reservoir. In this study, an
extension of EOS7R and EWASG modules have been developed to simulate the gas and water
flow called EOS7C [84-88]. Omambia and Li carried out a CO 2 numerical modeling in a deep
saline aquifer (Wangchang basin, China) using a fluid/property module of TOUGH2 called
ECO2N which is adapted from EWASG module [89]. This module was evaluated in a separate
study for the CGS process in saline aquifers by Pruess and Spycher [86, 90]. TOUGHREACT,
a non-isothermal reactive geochemical transport code, was utilized to simulate the CO2
disposal in deep aquifers by Xu et al., which was performed by merging the reactive chemistry
term into the TOUGH2 framework [91–95]. An efficiency evaluation of CGS was performed
in Frio brine pilot project using the TOUGH2 simulator to identify the uncertainties related to
nature of the earth by Hovorka et al. [96]. In a previous study at the University of Stuttgart,
the MUFTE-UG simulator has been evaluated for CO2 sequestration in various fields of
application such as simulation, CO2SINK, and CO2TRAP [97, 98]. At the Ketzin CO2 storage
site, the ECLIPSE 100/300 and MUFTE-UG codes were employed to perform a history matching
[99]. Pawar et al. have investigated a preliminary study to model and simulate the CGS in a
depleted oil reservoir by ECLIPSE 100 [100]. Another 2/3 dimensional simulation survey with
consideration of reactive flow and transport in deep saline aquifers has been performed by
Kumar et al. with GEM simulator (computer modeling groups) [101]. ECLIPSE and DuMux
simulators are also taken into consideration to understand the thermal effect during CO2
injection and movement in the porous medium.
According to the CGS simulation methods, there have been some comparative investigations
between the various simulators, such as reported by David et al. and Jiang [102]. David et al.
have compared six simulators for numerical simulation of CGS in coal beds: (1) GEM, (2)
ECLIPSE, (3) COMET2, (4) SIMED II, (5) GCOMP, and (6) METSIM 2. Additional features are
needed to be taken into consideration based on Law et al., such as coal matrix swelling,
diffusion of mixed gas, non-isothermal effect, water movement, and so on [103]. According to
the recent survey by David et al. GEM and SIMED II are suitable to consider multi-component
liquids while ECLIPSE and COMET 2 can handle only two component fluids [103, 104]. In
2011, Jiang demonstrated an overview of the various simulator applications and their numer‐
ical features including TOUGHREACT, MUFTE, GEM, ECLIPSE, DuMux, COORES, FEHM,
ROCKFLOW, SUTRA, and other types of simulators. Numerical methods and physical models
play an important role in the simulators outcomes. Selecting the best simulator among those
presented above is highly based on the desired application. For example, the ELSA simulator
can be applied efficiently in semi-analytical estimation of fluid distributions; ROCKFLOW is
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suitable in the case of multi-phase flow and solute transport modeling; GEM is an aqueous
geochemistry tool while for the low-temperature situation PHREEQC is more applicable; and
for the multi-component, three phase, and 3D fluid flow simulation with consideration of
reservoir heterogeneities, COORES would be a robust means [85, 102, 104, 105]. Zhang et al.
had a quick look on different types of simulators mentioned earlier and have suggested a new
parallel multi-phase fluid flow simulator for CGS in saline aquifers called TOUGH+CO2 which
has been developed on the basis of a modified TOUGH2 family of cods, TOUGH+ and
TOUGH2-MP including all the ECO2N features capabilities [83]. This brand new simulator
has proved to be a successful and robust means, which has been used in a number of large-
scale simulation projects [106–113].
Another group of surveys has focused on the direct modeling of some effective transport
phenomena which are essential for predicting parameters that have an important role in
underground gas sequestration process such as diffusivity and convection. Azin et al., in
2013, have conducted study regarding correct measurement of diffusivity coefficient [114].
The modeling was based on a method proposed by Sheika et al. to analyze pressure decline
data and the impact of pressure and temperature on the measurement of diffusivity coefficient
[114]. GholamiY., et al., in 2015, have also investigated the measurement of CO2 diffusivity
in synthetic and saline aquifer solutions at reservoir conditions with emphasis on the role of
ion interactions [114–117]. A non-iterative thermodynamic predictive model has investigat‐
ed by Azin et al. to calculate the effect of gas solubility [118–120]. The effects of convective
dissolution and diffusivity mixing have also been surveyed with finite-element method by
GholamiY., et al. They have used Streamline Upwind Petrov-Galerkin (SUPG) method and
crosswind artificial diffusion and found that the dissolution is controlled by convective
dissolution in bulk water [115, 121]. Another numerical simulation was done by Azin et al.
to predict the onset of instability in CO2 underground injection [114]. It was found that
depending on Rayleigh number, there is a wave number at which instability occurs earlier
and grows faster [114].
4. CGS: Monitoring and Verification
Precise monitoring and verification is required to have an appropriate risk management

strategy for the CGS projects [1]. The monitoring and verification process should be com‐
menced from site selection and characterization followed by atmospheric and remote sensing,
near and deep surface methods, as well as well bore-monitoring techniques. Different types
of monitoring tools are introduced and used in recent literature: acoustic velocity structure
imaging by seismic, density distribution imaging by gravity, electrical resistivity structure
imaging, and fluid content imaging of potential reservoir rocks by the electromagnetic
methods [20, 122]. After injecting the CO2 into the sequestration sites, electromagnetic and
gravitation sensors are employed for seismic surveys of storage integrity such as CO2 flow and
transportation quality in porous media and behavior of cap rock in contact to the CO2. The
leakage measurement in atmospheric level can be done by open path, flux tower, and InSAR
systems (satellite-based infrared and interferometric synthetic aperture radar) [20].
Otway Basin Pilot project in Australia is the first CGS project in which monitoring techni‐
ques were used [122]. In 2010, the CSEM have considered landing base imaging and passive
magnetotelluric in deep crustal scales surveys by Sreitch and colleagues [124]. According to
the surveys performed by Arts et al. and Chadwick et al., the 4D gravity and seismic
techniques have been successfully accomplished in Sleipner site [125–127]. The 4D vertical
seismic profiling (VSP) has been commonly used to quantitative monitoring of the CO2 plume
with tracer injection, well logging, micro-seismic and pressure–temperature measurements
which is applied successfully at Frio and Nagaoka project [128–144]. In Frio Brine and Otway
Pilot projects, tracer monitoring has been employed to assess the CO2 breakthrough [145,
146]. The Eddy covariance and hyperspectral imaging in a shallow subsurface site are
important computational issues that were examined to monitor the CO2 leakage in Monta‐
na [147, 148]. Another successful surface monitoring technique tested at In Salah project was
InSAR which was incorporated into other monitoring techniques such as seismic, gravity,
and electromagnetic [149–153]. At Ketzin sequestration site, the monitoring methods included
cross-hole resistivity, seismic, and microbiology with temperature and pressure profiling
[154-160].
5. Conclusions
In summary, the methods of theoretical and effective capacity estimation of CO2 storage
comprise volumetric and compressibility methods, flow mathematical and simulation models,
dimensional analysis, analytical investigation and Japanese/Chinese methodology.
The CSLF model employs a techno-economic resource pyramid in the capacity estimation
process for depleted oil and gas reservoir, while the DOE model utilizes volumetric equations
and Monte Carlo approach by incorporating various trapping mechanisms. According to the
CO2CRC, storage capacity classification in terms of oil and gas fields is the easiest among the
other geological options due to the greater amount of data. A volumetric equation has been
proposed to CO2 storage estimation in the most favorable storage option (saline aquifers) while
each type of trapping mechanism is also needed for calculation of the basin-scale assessments.
The CSLF methodology has been considered for deep saline aquifers as well as depleted oil
and gas reservoir based on structural and stratigraphic trapping mechanisms. Estimation
through mineral trapping cannot be applied at the regional and basin scales due to lack of data
availability. The only remaining approach, numerical simulation, is suitable for site and local
scale for a long period of time. Despite the application of the hydrodynamic trapping mecha‐
nism in various time scales, it cannot be evaluated at regional- and basin-scale estimation. To
calculate the storage capacity based on compressibility concept, a more comprehensive
equation has been addressed recently including flow simulation employing volumetric
formulas and more reservoir parameters.
In coal bed capacity estimation, the Langmuir equation provides a simple and efficient relation
for single layer low-pressure conditions. In the case of high pressure and high temperature, Bi
Langmuir, extended Langmuir, Sips, Langmuir-Freundlich, Toth, UNILAN, two-dimensional
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http://dx.doi.org/10.5772/62173
EOS, LRC (loading ratio correlation), Dubinin–Radushkevich (D-R), and Dubinin-Astakhov

(D-A) are more suitable.
One of the most efficient means for reservoir modeling is the TOUGH2 simulator developed
in Rio Vista reservoir and an extension of EOS7R and EWASG modules also has been proposed
to simulate the gas and water flow called EOS7C. A fluid/property module of TOUGH2 called
ECO2N has been utilized for CO2 modeling in saline aquifers. TOUGHREACT, a non-isother‐
mal reactive geochemical transport code, was utilized to simulate the CO2 disposal in deep
aquifers by entering the reactive chemistry term into the TOUGH2 framework. MUFTE-UG
simulator has been evaluated for CO2 sequestration in various fields of application such as
simulation, CO2SINK, and CO2TRAP. Another survey with consideration of reactive flow and
transport in deep saline aquifers has been performed using the GEM simulator. ECLIPSE and
DuMux simulators are also taken into consideration in a study to understand the thermal effect
during CO2 injection and movement in the porous medium.
Six simulators including GEM, ECLIPSE, COMET2, SIMED II, GCOMP, and METSIM2 have
been compared for CGS in coalbeds. GEM and SIMED II simulators are suitable for multi-
component liquids while ECLIPSE and COMET2 can handle only two component fluids. Other
comparison studies including TOUGHREACT, MUFTE, GEM, ECLIPSE, DuMux, COORES,
FEHM, ROCKFLOW, SUTRA, and other types of simulators have been carried out throughout
the world. Selecting the best simulator among those presented is highly based on the desired
application. The ELSA simulator can be applied efficiently in semi-analytical estimation of
fluid distributions. ROCKFLOW is suitable in the case of multi-phase flow and solute transport
modeling. GEM is an aqueous geochemistry tool, while for the low temperature situation
PHREEQC is more applicable. For multi-component, three phase, and 3D fluid flow simulation
with consideration of reservoir heterogeneities, COORES would be a robust means. The new
parallel multi-phase fluid flow simulator for CGS in saline aquifers called TOUGH+CO2 has
been developed on the basis of a modified TOUGH2 family of cods, TOUGH+ and TOUGH2-
MP including all the ECO2N feature capabilities and has proved to be a successful and robust
means in a number of large scale simulation projects.
The CSEM have considered landing base imaging and passive magnetotelluric in deep crustal
scale surveys in 2007. The 4D gravity and seismic methods have performed well in the Sleipner
project. The 4D vertical seismic profiling (VSP) has been commonly used for quantitative
monitoring of the CO2 plume with tracer injection, well logging, and micro-seismic and
pressure-temperature measurements with successful application at Frio and Nagaoka. In Frio
Brine and Otway Pilot projects, tracer monitoring has been employed to assess the CO2
breakthrough. The Eddy covariance and hyperspectral imaging in a shallow subsurface site
are important computational issues that were examined to monitor the CO2 leakage in
Montana. Another successful surface monitoring technique tested at In Salah project was
InSAR which incorporated to other monitoring techniques such as seismic, gravity, and
electromagnetic. At Ketzin sequestration site, the monitoring methods included cross-hole
resistivity, seismic, and microbiology with temperature and pressure profiling.
Author details
Kakouei Aliakbar1, Vatani Ali1*, Rasaei Mohammadreza1 and Azin Reza2
*Address all correspondence to: avatani@ut.ac.ir
1 Chemical Engineering Department, College of Engineering, University of Tehran, Tehran,

Iran
2 Department of Petroleum Engineering, Faculty of Petroleum, Gas and Petrochemical

Engineering, Persian Gulf University, Bushehr, Iran
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Chapter 8
Methane Emissions from Rice Production

in the United States — A Review
of Controlling Factors and Summary of Research
Kristofor R. Brye, Alden D. Smartt and Richard J. Norman
http://dx.doi.org/10.5772/62025
Abstract
Flooded rice (Oryza sativa L.) cultivation has been identified as one of the leading global
agricultural sources of anthropogenic methane (CH4) emissions. Furthermore, it has been
estimated that global rice production is responsible for 11% of total anthropogenic CH4
emissions. Considering that CH4 has a global warming potential that is approximately 25
times more potent, on a mass basis, than carbon dioxide (CO2) and rice production is
globally extensive and concentrated in several mid-southern and southern states and Cal‐
ifornia, the purpose of this review is two-fold: (i) discuss the factors known to control
CH4 production in the soil and transport to the atmosphere from rice cultivation and (ii)
summarize the historic and recent research conducted on CH4 emissions from rice pro‐
duction in the temperate United States. Though some knowledge has been gained, there
is much more that still needs to be learned and understood regarding CH4 emissions
from rice production in the United States, its contribution to climate change, and poten‐
tial mitigation strategies. Extending the current knowledge base surrounding CH4 emis‐
sions from rice cultivation will help regulatory bodies, such as the Environmental
Protection Agency, refine greenhouse gas emissions factors to combat the potential nega‐
tive effects of climate change.
Keywords: Methane, emissions, rice production, agriculture, soil texture
1. Introduction
Methane (CH4) is a known and potent greenhouse gas that is produced by anaerobic Archaea
under anoxic conditions. Agricultural activities have been recognized as contributing an
estimated 50% to global anthropogenic CH4 emissions [1], while an estimated 31% of anthro‐
pogenic CH4 emissions have been attributed to agricultural activities in the United States (US)
[2]. Due to the anaerobic conditions that form in saturated soils, which is a prerequisite for
CH4 production, flooded rice (Oryza sativa L.) cultivation has been specifically identified as
one of the leading global agricultural sources of anthropogenic CH4 emissions, accounting for
approximately 22% of the total global agriculturally related CH4 emissions [3]. Furthermore,
it has been estimated that global rice production is responsible for 11% of total anthropogenic
CH4 emissions [1,3].
While numerous factors have been determined to impact CH4 emissions from rice cultivation,
due to a general lack of field data, the United States Environmental Protection Agency (USEPA)
currently uses a single emissions factor for all non-California-grown, primary rice crops [4].
Therefore, the purpose of this review is two-fold: (i) discuss the factors known to control
CH4 production in the soil and transport to the atmosphere from rice cultivation and (ii)
summarize the historic and recent research conducted on CH4 emissions from rice production
in the temperate United States.
2. The greenhouse effect
The greenhouse effect is a mechanism by which certain gases such as carbon dioxide (CO2),
CH4, nitrous oxide (N2O), and water (H2O) vapor absorb and release infrared radiation,
interfering with the ability of solar radiation to leave Earth’s atmosphere. The absorption of
thermal radiation by H2O and CO2 was discovered through laboratory experiments in 1859 [5].
However, other gases including CH4 and N2O were not recognized as greenhouse gases until
the 1970s [6].
Global warming potential (GWP) is a metric that allows the warming impact of various
greenhouse gases to be quantitatively compared on the same scale. The assignment of GWP
values to gases requires knowledge of the contribution to global warming of gas emissions
over time based on the amount of radiation per mass that the gas can absorb and emit as well
as the atmospheric lifetime of the gas. Global warming potentials are assigned relative to that
of CO2, thus the 100-yr GWP of CO2, CH4, and N2O are 1, 25, and 298, respectively [7]. For
example, 1 kg of CH4 released to the atmosphere is equivalent to 25 kg of CO2 being released.
Global warming potentials allow greenhouse gas emissions to be reported as CO2 equivalents
in order to compare warming effects of various gases on a single scale.
The current climate change problem is not a result of the greenhouse effect itself, but rather
from an increasing greenhouse effect resulting from anthropogenic activities that have
increased atmospheric concentrations of greenhouse gases. Prior to 1750, the atmospheric
CO2 mixing ratio was about 280 parts per million (ppm) [8]. Since the beginning of the
industrial era, atmospheric CO2 has risen drastically to 379 ppm in 2005 [7] and 395 ppm as of
April 2013 [9]. Between 1750 and 2005, atmospheric CH4 increased from about 700 parts per
billion (ppb) to 1,774 ppb [7]. Nitrous oxide was more variable ranging from 180 to 260 ppb
prior to 1750, but has similarly increased to a mixing ratio of 319 ppb in 2005 [7]. While
atmospheric N2O and CO2 concentrations have increased steadily over the past several
decades, the growth rate (i.e., concentration increase) of atmospheric CH4 seems to be declin‐
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Methane Emissions from Rice Production in the United States — A Review... 181
http://dx.doi.org/10.5772/62025
ing. The growth rate of atmospheric CH4 has decreased from highs of about 1% per year in the
1970s and 1980s to nearly zero between 1999 and 2005. However, the decreasing growth rate
is poorly understood [7].
3. Greenhouse gas emissions
Globally, CO2 accounted for about 76% of greenhouse gas emissions in 2004, with around 75%
of CO2 emissions resulting from fossil fuel use and much of the remainder from deforestation
and biomass decomposition [10]. Methane and N2O accounted for 14 and 8%, respectively, of
the estimated global greenhouse gas emissions in 2004. Major CH4 sources include agricultural
activities, waste management, and energy use, while N2O emissions are primarily a result of
agricultural activities, such as fertilizer use and soil management [10]. In the US in 2013, an
estimated 82% of the total greenhouse gas emissions were CO2, 10% were CH4, and 5% were
N2O [2]. Major sources of greenhouse gas emissions are generally the same in the US as the
global sources mentioned above. The major global sectors responsible for greenhouse gas
emissions are energy supply (26%), industry (19%), forestry (17%), agriculture (14%), and
transportation (13%) [10]. In comparison, the major US sectors responsible for greenhouse gas
emissions are energy supply (31%), transportation (27%), industry (21%), commercial and
residential (12%), and agriculture (9%) [2].
Although agricultural activities do not dominate total greenhouse gas emissions, agriculture
contributes an estimated 50 and 60% of global anthropogenic emissions of CH4 and N2O,
respectively [1]. Agriculture in the US is responsible for an estimated 36% of anthropogenic
CH4 emissions and 79% of anthropogenic N2O emissions [2]. Enteric fermentation, rice
cultivation, and manure management contribute an estimated 64, 22, and 8%, respectively, to
global anthropogenic agricultural CH4 emissions, while agricultural N2O emissions are
dominated by agricultural soil management (80%) [3]. In comparison, enteric fermentation,
rice cultivation, and manure management contribute to 70, 4, and 26% of US anthropogenic
agricultural CH4 emissions [2]. Although rice cultivation makes up a small portion of CH4
emissions in the US, globally rice cultivation accounts for approximately 11% of total anthro‐
pogenic CH4 emissions.
Methane emissions from US rice cultivation were estimated to be 8.3 Tg CO2 equivalents in
2013, a reduction from 9.3 Tg CO2 equivalents in 2012 due to a decline in rice production area
[2]. Arkansas was responsible for 36% of the estimated CH4 emissions from rice cultivation,
although Arkansas accounted for 43% of the total US rice production in 2013. Louisiana was
the next leading contributor to CH4 emissions accounting for 27% of 2013 emissions, while
harvesting 16% of 2013 production [2,11]. Louisiana and Texas CH4 emissions are large relative
to their production areas due to extensive ratoon cropping in 2013, which occurred on an
estimated 38 and 68%, respectively, of the production area in those states [2]. A ratoon crop is
a second crop that is managed and produced after the first or primary crop is harvested.
California, Mississippi, and Missouri, none of which reported any ratoon cropping, contrib‐
uted 14, 3.6, and 4.5%, respectively, to the estimated 2013 CH4 emissions from US rice culti‐
vation [2].
The USEPA periodically publishes CH4 emissions factors based on research data. Separate
emission factors of 178 kg CH4-C ha–1 season–1 and 585 kg CH4-C ha–1 season–1 were used in the
inventory estimates for non-California-grown, primary rice cropping and ratooned cropping
areas, respectively, as is consistent with the Intergovernmental Panel on Climate Change [3],
which recommends calculating separate emissions factors for as many different factors and
cultural practices as is possible. Emissions factors for California rice production are 200 and
100 kg CH4-C ha–1 season–1 for winter-flooded and non-winter-flooded rice, respectively [2].
While it is known that factors such as water management, soil properties, rice cultivar, fertilizer
management, and residue management have strong impacts on CH4 emissions from rice
cultivation, data available from US studies limit the further disaggregation of these factors [2].
The non-California-grown, primary crop emissions factor is based on US studies with
emissions ranging from 46 to 375 kg CH4-C ha–1 season–1 [13–20] and the ratoon crop factor is
based on studies conducted in Louisiana with emissions ranging from 361 to 1118 kg CH4-C
ha–1 season–1 [21,22]. The California-specific emissions factors include studies with emissions
ranging from 47 to 166 kg CH4-C ha–1 season–1 for the non-winter-flooded and from 98 to 277
kg CH4-C ha–1 season–1 for the winter-flooded rice [23,24].
4. Rice production
Rice is a semi-aquatic, cereal grain that makes up about 21% of total global grain production
[25]. The importance of rice is further exemplified by the fact that rice is a staple food crop for
about half of the global population, with direct human consumption accounting for 85% of
rice production compared to 72% of wheat (Triticum aestivum L.) and 19% of maize (Zea mays
L.) production [26,27]. In Southeast Asia, 60% of human food intake is provided by rice as well
as 35% of food intake in both East Asia and South Asia [26]. Rice has the ability to support
more people per unit of land area than wheat or maize because rice produces, on an average
yield basis, more food energy and protein per hectare than wheat or maize [28]. Therefore, any
potential negative environmental consequences associated with rice production have to be
taken seriously.
4.1. Rice production extent
Common rice (Oryza sativa) is commercially produced in 112 countries worldwide, spanning
latitudes from 53°N along the Amur River at the China–Russia border to 35°S in central
Argentina [26]. In 2012, more than 158 million ha globally were planted to rice, with average
yields of 4.4 Mg ha–1 for a total global production of 470 Tg of rice. Comparatively, nearly 216
million ha were planted in wheat in 2012, with average yields of 3.0 Mg ha–1 for a total of 656
Tg of global wheat production. More than 174 million ha were planted in maize in 2012, with
an average yield of 4.9 Mg ha–1 and a total global production of 857 Tg of maize [25]. Global
rice production peaked in 1994 at 534 Tg of rice, with Asia being responsible for 90% of that
production [29]. The majority of global rice production occurs in east, south, and southeast
Asia, which together accounted for 90% of global production in 2012. Substantial production
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http://dx.doi.org/10.5772/62025
also occurs in South America (Brazil and Peru), Sub-Saharan Africa (Nigeria and Madagascar),
Europe (Italy and Spain), Egypt, and the US [25].
China and India currently dominate global rice production accounting for 30 and 22%,
respectively, of the total global production in 2012. The third-, fourth-, and fifth-ranked global
producers in 2012 were Indonesia (8%), Bangladesh (7%), and Vietnam (6%). The remaining
top 10 producers, in order, were Thailand, the Philippines, Burma, Brazil, and Japan, followed
by the eleventh-ranked US, which accounted for 1.3% of global production [25]. The US,
however, plays a larger role in global exports contributing 9% of 2012 global exports and
ranking fifth after Thailand (21%), India (20%), Vietnam (20%), and Pakistan (10%). Global
exports in 2012 were estimated to be 8% of total production, while the US exported 55% of 2012
production [30]. Global rice yields in 2012 were estimated to be 4.4 Mg ha–1 compared to 8.3
Mg ha–1 in the US, which was second only to Egypt (8.8 Mg ha–1) among the major rice-growing
countries. The two top rice-producing countries, China and India, had estimated yields of 6.7
and 3.6 Mg ha–1, respectively [25].
Nearly 1.1 million ha of rice were planted in the US in 2012, yielding an average of 8.3 Mg
ha–1 for a total production of 9.0 Tg of rice prior to milling, compared to 23 million ha planted
with an average yield of 3.1 Mg ha–1 for a total of 62 Tg of wheat production, and over 39 million
ha of planted maize with average yields of 7.7 Mg ha–1 for a total production of 274 Tg [11].
The four major regions that produce rice in the US are the Arkansas Grand Prairie, the
Mississippi Delta, which is made up of portions of Arkansas, Missouri, Mississippi, and
Louisiana, the Gulf Coast (Texas and southwest Louisiana), and California’s Sacramento
Valley. Most US states produce primarily long-grain cultivars, while much of the medium-
grain rice and nearly all of the short-grain rice is produced in California [11]. Although
Oklahoma and Florida are often included as rice-producing states, the six previously men‐
tioned states have made up essentially all of US production in recent years [11]. Arkansas is
the leading state in both area of cultivation and total production, contributing 48% of total US
rice production in 2012, followed by 23% of production by California and 13% of production
by Louisiana [11]. Arkansas rice production takes place in the eastern portion of the state with
the top five rice-producing counties in 2012 being Poinsett, Lawrence, Arkansas, Greene, and
Cross, which made up 35% of the state’s production area [31].
4.2. Global rice production practices
Rice production practices vary globally based on economic, cultural, and climatic factors, each
of which show temporal and spatial variability throughout the rice-growing countries. A
simple classification or characterization of rice production systems is nearly impossible on a
global scale due to the variability of factors that influence production. Classifications of rice
production techniques are commonly based upon flood presence (e.g., upland or lowland),
water source (e.g., irrigated or rainfed), and stand establishment technique (e.g., transplanting,
direct-seeding, or water-seeding) with many combinations and variations of these techniques
occurring throughout the globe [32]. In one of the most recent classification attempts, Chang
[33] classified global rice production into five major agroecosystems: (i) irrigated wetland,
which made up 53% of global rice production area and had the greatest yield potential at 3 to
5 Mg ha–1, (ii) rainfed wetland, making up 26% of global area and yielding 2 to 4 Mg ha–1, (iii)
flood-prone or tidal swamps, which made up an insignificant area, (iv) deep water (1–5 m),
making up 8% of global area, and (v) dryland, which made up an estimated 13% of global
production area with average yield potentials of 1 to 1.5 Mg ha–1.
While a small portion of rice is produced under upland conditions, the majority of rice
production requires substantial quantities of water in order to maintain a flood on the semi-
aquatic crop. In much of the tropical rice-growing area, particularly south and southeast Asia,
rainfed rice is the main production system, where most of the production comes from wet-
season harvests and the cropping season is determined by rainfall patterns [32]. In temperate
production areas, rice production must coincide with suitable temperatures for the crop which,
coupled with inadequate rainfall, requires that temperate rice be almost entirely irrigated in
order to maintain a flood for the duration of the growing season [32]. The utilization of
irrigation in temperate areas allows greater control of environmental factors, which ultimately
tends to increase yields, while rainfed systems may suffer from droughts and floods that may
substantially damage crops and reduce yields [32].
Direct-seeding and transplanting are common establishment techniques in both irrigated- and
rainfed-wetland systems, while direct-seeding is the major practice in dryland and deep-water
agroecosystems [33]. While transplanting does occur in irrigated- and direct seeding occurs in
rainfed-wetland systems, it is more common for irrigated systems to utilize direct-seeding and
for rainfed systems to use transplanting techniques [32]. Transplanting systems involve raising
seedlings in a nursery seedbed area at the beginning of the season and transplanting into
puddled paddy soils early in the vegetative growth stage. Transplanting is the major estab‐
lishment system for rainfed rice in tropical Asia, with the majority of production in northeast
India, Bangladesh, and Thailand relying upon transplanting techniques [32]. Direct-seeding
by grain-drilling or broadcasting pre-germinated seeds onto puddled soil is practiced in parts
of India, Sri Lanka, Bangladesh, and the Philippines, while drill-seeding into dry soil is the
most common practice in the US and other mechanized regions such as Australia [32]. Rice
seed may be broadcast onto dry or moist soil by airplane followed by harrowing to cover seeds,
but this establishment method requires more seed and stand establishment is often poorer than
with drill-seeding [32]. Water-seeding is an establishment technique that originated and is
practiced in parts of Asia, where pre-germinated seeds are broadcasted from an airplane into
already flooded paddies or fields [32]. The rice-production system, and associated specific
production practices, can significantly affect CH4 production and emissions.
4.3. Rice production practices in the US
Rice production under mechanized US systems requires high temperatures, nearly level land,
plentiful water, and soils that inhibit percolation of floodwater, so production is limited to
Arkansas, Louisiana, Mississippi, Missouri, Texas, California, and Florida [34]. All US rice is
produced using high-input, mechanized production practices, but practices vary somewhat
from region to region based on differences in climate, soils, weed proliferation, and other
factors that influence production. Essentially, all US rice is irrigated and sources of irrigation
water include shallow or deep groundwater, runoff reservoirs, rivers, bayous, and lakes [34].
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It is estimated that between 1000 and 2500 m3 ha–1 of water are required to produce a rice crop
in the southern US and generally less than one third of that requirement is met by rainfall [35].
Levees, which separate fields into bays, or paddies, and control flood depth (i.e., by use of
gates or spills), are commonly constructed on contours that were surveyed on 3 to 6 cm vertical
intervals. This creates winding, contour-shaped levees in fields that are not precision-leveled,
whereas precision leveling to a uniform grade of 0.2% or less allows the construction of
uniformly spaced, straight levees and may reduce the number of levees required [34].
The two stand establishment techniques utilized in the US are dry-seeding and water-seeding.
Dry-seeding techniques, particularly drill-seeding, are predominant in most of the US, while
water-seeding techniques are used extensively in California and to a small degree in southwest
Louisiana and other regions as a weed control method [34]. A continuously flooded, water-
seeding technique is used in California, where pre-germinated seeds are broadcast by airplane
into flooded fields and the seedlings grow through a standing flood, while a pinpoint-flood,
water-seeding technique is used in Louisiana, where seeds are broadcast into a flooded field
that is drained within a few days and then permanently flooded after drying for 3 to 5 days
[34,36]. In dry-seeded systems, seed is most often drilled into a well-pulverized, firm, and
weed-free seedbed in 15- to 25-cm rows to a depth of 2.5 cm or less. When rice is following a
high-residue crop, such as rice, maize, or wheat, it is necessary to till the land in the fall or early
spring so that decomposition of the residue does not immobilize nutrients after the subsequent
rice crop is planted, whereas rice following soybean (Glycine max L.), a crop that produces
relatively little residue, may not require as much preparation because crop residues are not as
abundant or as persistent compared to that of rice or maize [34,37].
Water management at and shortly after planting varies across US systems, but a permanent
flood is established in all systems usually by the four- to five-leaf vegetative growth stage/
beginning tillering (V4-5) [38]. Flush irrigation is used as necessary to promote germination
and seedling growth in dry-seeded rice systems prior to establishment of a permanent flood,
which typically occurs three to four weeks after emergence (i.e., the V4 to V5 growth stage).
Drainage during the season is typically avoided except if a nutrient deficiency, such as zinc,
is detected, to aerate the soil in order to treat or prevent disorders, such as straighthead and
hydrogen sulfide toxicity, or to apply pesticides. Fields are drained prior to harvest in order
to dry the soil enough for operation of harvest equipment [34]. Fields are flooded again within
five to seven days after primary-crop harvest in ratoon cropping systems, which are common
in southwest Louisiana, Texas, and Florida, and the flood is again maintained until harvest of
the ratoon crop [34].
Crop rotations are important in rice, especially where weedy/red rice is problematic and
difficult to control during rice cropping seasons. In order to suppress weedy rice, nearly all
rice in Louisiana is grown either in a 1:1 rotation with soybean or a 1:1:1 rotation where crawfish
(Procambarus clarkia) are double-cropped following rice, with soybean produced the following
season [34]. In 2012, greater than 70% of Arkansas rice was produced in rotation with soybean,
with most of the remaining production in a rice–rice rotation [39]. In California, approximately
70% of rice is produced in a rice–fallow or rice–rice rotation [40].
4.4. Arkansas rice production practices
Arkansas is the leading rice-producing state, accounting for 40 to 50% of total annual produc‐
tion in the US [11]. Rice production in Arkansas began in 1902 when 0.4 ha were planted in
Lonoke County. Production increased over time until 1955 when government quotas limited
production to 202,350 ha. The limitation was lifted in 1974 and production increased again,
peaking in 1981 at 623,240 ha, again in 1999 with 667,755 harvested hectares, and finally in
2010 with 724,413 ha [31]. In 2012, 518,016 ha rice were harvested in Arkansas [11]. Rice
production in Arkansas is highly mechanized with a heavy dependence upon synthetic
fertilizers, chemical pest control, and machinery. Planting of rice in Arkansas generally begins
the last week of March and extends into early June with floods typically being established by
the end of May or early June. Harvesting operations usually begin in mid-August and peak in
early- to mid-September [31].
Arkansas rice is produced on a wide variety of soils ranging from sandy to clay soils with the
differing textural classes generally requiring different management, especially with regards
to tillage practices and nutrient management [39, 41]. Production on sands and sandy loams
is minor and has been decreasing from 3.1 and 5.2% of Arkansas area, respectively, in 2007 to
0.7 and 3.7%, respectively, in 2012. Arkansas production on clay and clay-loam soils, however,
has increased from under 40 to 48% between 2007 and 2009 but declined to 43% in 2012.
Production on silt-loam soils has remained fairly steady at 52% in 2007 and 53% in 2012 [39,42].
Dry-seeding techniques have always dominated in Arkansas. Water-seeding has varied

between 2 and 8% of the production area between 2007 and 2012, with an estimated 5% of the
2012 Arkansas rice area being water-seeded [39,42]. Approximately 80% of 2012 Arkansas rice
area was drill-seeded, compared to approximately 20% being broadcast-seeded [39]. Conven‐
tional tillage accounted for over half of Arkansas planted-rice area, while stale-seedbed (i.e.,
tillage and floating, or leveling the field, in the fall or winter) and no-tillage accounted for 35
and 10% of the planted-rice area, respectively, in 2012 [39]. Stale-seedbed and no-tillage are
oftentimes utilized on clay soils where conventional tillage produces a cloddy seedbed with
poor seed-to-soil contact [41].
While pinpoint, water-seeding techniques do occur in Arkansas, over 90% of the Arkansas rice
production area utilizes a delayed-flood system, where the permanent flood is not established
until the four- to five-leaf growth stage, which generally occurs approximately three to four
weeks after emergence [39]. Fields are drained two to three weeks prior to harvest and most
fields remain unflooded until the subsequent rice crop is produced, while nearly 20% of
Arkansas rice area is winter-flooded [34,39]. Over 75% of Arkansas rice is irrigated by
groundwater with 10 and 13% of the rice area utilizing water stored in reservoirs and from
streams/rivers, respectively [39].
The two methods of nitrogen (N) fertilization in Arkansas are (i) the standard two-way split
system, where 65 to 75% of the total N is applied pre-flood with the remainder applied at mid-
season in one or two applications between beginning internode elongation and half-inch
internode elongation [i.e., reproductive stage 0 (R0) to 1 (R1)], and (ii) the single optimum pre-
flood system, where a single N application is made immediately prior to flooding. Nitrogen
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fertilizer rate recommendations have previously been based only on cultivar, soil texture, and
previous crop. Implementation of the new N-Soil Test for Rice (N-STaR) enables recommen‐
dations to be adapted to the soil’s ability to supply N to the rice crop on a field-by-field basis,
reducing the likelihood of over- and under-fertilization of N [43]. Ammonium-N sources, such
as urea and ammonium sulfate, are used in order to prevent N loss through denitrification that
occurs with nitrate-containing fertilizers. Phosphorus and potassium are incorporated prior
to planting as recommended by routine soil tests [43]. Organic amendments are uncommon,
although poultry litter is utilized to a small degree, especially in precision-leveled fields.
5. Flooded soils
The saturated soils that occur during wetland, or lowland, rice cultivation give rise to a set of
physical, chemical, and biological properties that are quite different from upland soils. Rice is
the only major row crop produced under flooded-soil conditions and the absence of air-filled
pores along with reduced soil–atmosphere interactions result in an almost entirely different
set of processes than those occurring in upland cropping systems.
5.1. Physical characteristics of flooded soils
The major physical difference between saturated and unsaturated soils involves the availabil‐
ity and rates of movement for gases and solutes. Under aerated conditions, the soil atmosphere
contains essentially the same gases as the atmosphere although the proportions of oxygen
(O2) and CO2 differ from the atmosphere due to soil respiration [44]. Carbon dioxide diffuses
into the atmosphere from the soil due to production during respiration and O2 diffuses into
the soil as it is consumed during respiration. The saturation and ponding of flooded soils
greatly reduce gas transport between the soil and atmosphere compared to aerated soils and
plant-mediated transport of gases by diffusion is often the main exchange mechanism between
the soil and atmosphere in saturated or flooded systems [45]. As a flooded soil dries, gases
trapped in the soil may escape due to increases in diffusion and convective flow rates that
occur as water escapes soil pores.
While solute movement by diffusion may be greater in saturated soils due to an increase in
water-filled pore space, diffusion of gases through water is roughly three to four orders of
magnitude slower than diffusion of gases through air [46,47]. Both diffusive and convective
flow of gases and solutes are related to pore connectivity and tortuosity, so it is expected that
movement of gases and solutes are slower in fine-textured soils, such as clays and clay loams,
than in coarser-textured soils, such as silt loams and sands, which generally have larger, more
connected pores [47]. Convective flow of gases in saturated soils can occur as dissolved gases
move with moving soil water, which is dependent largely upon soil texture and structure, and
as ebullition, which is where gases escape as bubbles through ponded water [47]. Generally,
diffusion dominates gas transport in fine-textured soils, such as clay loams and clays, and
diffusion rates typically decrease as particle size decreases, which is due to differences in size,
orientation, and shape of soil pore spaces [45,48]. Soil texture also affects the amount of time
it takes for a soil to become saturated with infiltration rates in clayey soils estimated to be 1 to
5 mm hr–1 compared to 10 to 20 mm hr–1 in soils such as silt loams [47]. The amount of time a
soil takes to become saturated has an effect on chemical and biological processes that develop
as the system becomes anaerobic.
5.2. Soil redox potential
Isolation of flooded soils from the atmosphere and depletion of soil O2 induces biological and
chemical reactions that create anaerobic and reducing conditions rather than the aerobic and
oxidized conditions that generally occur in upland soils. Organic matter decomposition slows
under anaerobic conditions, but as organic matter is oxidized, transformations such as
denitrification and manganese (Mn) and iron (Fe) reduction occur as well as production of
gases such as hydrogen sulfide (H2S) and CH4. Soil reduction/oxidation (redox) reactions are
coupled half-reactions where the oxidation of organic matter, which provides electrons, is
coupled with the reduction of elements or compounds that act as electron acceptors [49].
Oxygen is the major electron acceptor under aerobic conditions, but as O2 is depleted, the
sequence of electron acceptors shifts to NO3–, MnO2, Fe(OH)3, SO42–, and CO2, which are
theoretically reduced in that order based on thermodynamic favorability [44,50]. The reduced
forms of the previously mentioned terminal electron acceptors are H2O, N2, Mn2+, Fe2+, H2S,
and CH4, respectively. Soil redox reactions in a controlled laboratory environment may follow
the theoretical sequence, but environmental conditions in the field result in spatial variability
of oxidizable organic compounds, electron acceptors, and microorganisms that cause sub‐
stantial overlap of the terminal electron acceptor sequence [44,49].
Soil redox potential (Eh) is a measure of the electrical potential status of a system that results
from the tendency of substances in the system to donate or acquire electrons [51]. Soil redox
potential is measured in millivolts (mV) using a platinum electrode along with a mercury
chloride (HgCl) or silver chloride (AgCl) reference electrode, both connected to a voltmeter
[49]. Combination platinum electrodes are also available that can continuously monitor soil
Eh when connected to a logger box. When using AgCl electrodes, a correction factor of
approximately +200 mV is added to field-measured voltages in order to adjust measurements
to the standard hydrogen electrode [52]. In well-aerated soils, soil Eh may be as great as +700
mV, but Eh values near –300 mV may be observed in saturated organic-matter-rich soils [51].
As a system shifts from aerobic to anaerobic and soil redox potential declines, atmospheric
O2 is reduced first at +380 to +320 mV, followed by NO3– (+280 to +220 mV), MnO2 (+220 to +180
mV), Fe(OH)3 (+110 to +80 mV), SO42– (–140 to –170 mV), and CO2 (–200 to –280 mV), based on
measurements by Patrick and Jugsujinda [53].
6. Methane emissions from rice
Methane emissions from any ecosystem, particularly a rice agroecosystem (Figure 1), are
governed by the magnitude and balance of microbial CH4 production (methanogenesis) and
oxidation (methanotrophy), which occur by separate microbial communities. The two groups
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of microorganisms are adapted to different environmental conditions, and, as a result, are

affected differently based on the structure and conditions of an ecosystem, which results in
variability of CH4 production and oxidation potentials across time and space [54]. With low
CH4 production rates or long diffusion pathways, it seems that the majority of the CH4 produced
is oxidized. Conversely, in cases where CH4 production rates are high or diffusion paths are
short, less CH4 is oxidized and a greater portion reaches the atmosphere [54] (Figure 1).
1
2 Figure 1. Chamber-based measurements of methane emissions from small plots at the Rice
Figure 1. Chamber-based measurements of methane emissions from small plots at the Rice Research and Extension
3 Research and Extension Center near Stuttgart, AR (top), and at the Northeast Research
Center near Stuttgart, AR (top), and at the Northeast Research and Extension Center at Keiser, AR (bottom). Photo‐
4 and Extension Center at Keiser, AR (bottom). Photographs taken by K. Brye.
graphs taken by K. Brye.
43
6.1. Methane production and oxidation
Methane production occurs toward the end of a complex anaerobic decomposition process in
which soil organic matter (SOM) is degraded to acetate, hydrogen gas (H2), and CO2 by a
community of various fermenting microorganisms, which are mostly bacteria. Methanogenic
Archaea are then able to split acetate into CH4 and CO2 (i.e., acetoclastic methanogenesis) or
utilize H2 and CO2 to produce CH4 (i.e., hydrogenotrophic methanogenesis) [55,56]. Metha‐
nogens encompass a large group of strictly anaerobic, obligate Archaea, which is currently
composed of three classes, six orders, 12 families, and 35 genera [56]. Rice Cluster I is a specific
group of methanogens identified by Grosskopf et al. [57] that contains enzymes in order to
detoxify highly reactive O2 species, allowing the methanogens to survive in aerated soils or
oxygenated rhizospheres, and occurs preferentially in environments that undergo transient
aerobic conditions, such as in rice fields [55,58]. Rice Cluster I has been detected in almost all
rice field soils tested [59,60] and occurs in great abundance in rice soils and on rice roots,
representing up to 50% of total methanogens in rice fields [61]. Rice Cluster I has been identified
as occupying a niche on rice roots by producing CH4 from photosynthates released as root
exudates [55,62]. Recent research has confirmed that methanogens are ubiquitous in aerobic
soils and have the ability to produce CH4 as soon as anoxic conditions form and substrate is
available [56]. Conrad [63] reported that methanogens isolated from the soil of rice fields were
not killed but only inhibited by high redox potentials or O2 exposure, allowing them to survive
drainage and maintain their population size throughout the year in a state of low activity.
Most methanogens are mesophiles and neutrophiles, with optimal growth occurring between
30 and 40oC and between a pH of 6 and 8 [54]. Methanogens are highly sensitive to variations
in temperature and pH and CH4 production is greatly reduced when soil temperatures are low
or in acidic or alkaline soils [56]. Within the optimal temperature range, which is generally the
case during the rice growing season, temperature has a positive effect on methanogenesis,
causing an increase in CH4 production as temperature increases [54,56].
Methane oxidation is achieved by a group of aerobic Proteobacteria known as methanotrophs,

which only utilize CH4 or methanol as a source of C and energy and are currently classified
into two phyla, three orders, four families, 21 genera, and 56 species [56]. One group, known
as low-affinity methanotrophs, is capable of oxidizing high CH4 concentrations (>100 ppm)
and exists at oxic–anoxic interfaces, where the methanotrophs consume CH4 produced in
anoxic environments [56]. Another group, known as high-affinity methanotrophs, exists in
upland soils and possesses the ability to oxidize CH4 at low atmospheric levels (<2 ppm) [64].
Unlike methanogenesis, methanotrophy is not impacted greatly by temperature, although
CH4 oxidation is decreased below 10oC and above 40oC, or pH, as similar CH4 oxidation has
been observed in soils with pH values ranging from 3.5 to 8 [56]. Due to the differing effect of
temperature on methanogenesis and methanotrophy, CH4 production increases as soil
temperatures increase, while CH4 oxidation changes little, resulting in a general increase in
CH4 emissions as soil temperature increases throughout the rice growing season. This effect
has been confirmed in a laboratory incubation of anaerobic soils at various temperatures
between 5 and 25oC [65].
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6.2. Substrate for methane production
Available SOM stimulates CH4 production due to enhanced fermentative production of acetate
and H2/CO2 and, in principle, CH4 production could be expected to be proportional to organic
C inputs, but the reduction of nitrate (NO3-), iron (Fe), manganese (Mn), and sulfate (SO42-) all
precede methanogenesis and reduce the amount of available C for CH4 production [54].
Methane production may be stimulated by root exudates [66–68] or the application of animal
manures [69], green manures [70–73], or rice straw [67,70,73–75], while the application of
composted organic C sources does not greatly increase CH4 production [73,75,76]. This
indicates that the amount of available organic C (OC) is more important in determining CH4
production than total OC (TOC), as composted residue contains lower amounts of degradable
C, on a mass basis, compared to fresh residues [77]. Yagi and Minami [73] and Wang et al. [78]
confirmed a positive correlation between CH4 production and readily mineralizable C, while
studies have indicated no clear relationship between soil TOC and CH4 production [68,79–
81]. Research conducted by Denier van der Gon and Neue [76] determined that increasing
fresh OM inputs would result in increases in CH4 production up to a point where another
factor becomes limiting; however, fresh green manure inputs up to 20 Mg ha–1 still indicated
OC limitations. In most rice production situations, organic residue inputs are below 20 Mg
ha–1 and will generally exhibit an increase in CH4 emissions as organic inputs increase.
Using 13C-labeled rice straw incorporated at 6 Mg ha–1, Watanabe et al. [82] determined that
42% of season-long CH4 emissions originated from rice straw C, 37 to 40% from the rice plant,
and 18 to 21% from SOM. The contribution of SOM to CH4 production was fairly consistent
over the growing season, while the contribution from rice straw decreased from nearly 90% at
14 days after transplanting to only 11 to 16% during heading and grain fill. In contrast, the
contribution of living rice plants to CH4 production increased over time and amounted to 65
to 70% during heading and grain fill [82]. Chidthaisong and Watanabe [83] also observed that
the contribution of rice straw to CH4 production was greatest at 20 to 40 days after flooding,
while plant-derived C became increasingly more influential as the season progressed. The link
between root exudates and CH4 production has been observed directly by Aulakh et al. [84],
who showed a positive correlation between TOC in root exudates and CH4 production. Several
others have observed an inverse relationship between grain yield and CH4 production [19,85],
indicating that lower grain yields are accompanied by greater CH4 production as a result of
greater root exudation, which was confirmed by Aulakh et al. [66]. Using 13C-labeled CO 2, it
was observed that photosynthates were a major source of CH4 and accounted for 4 to 52% of
CH4 under field conditions [86,87].
6.3. Duration and timing of methane production
Methane production occurs some period of time following a period of prolonged saturated
conditions and continues until the C substrate becomes limiting or environmental conditions
limit methanogenesis (i.e., the soil becomes too cold, hot, or aerated). In flooded soils, the rate
of reduction processes is determined by the composition and texture of a soil as well as the
content of inorganic electron acceptors [i.e., NO3–, MnO2, Fe(OH)3, SO42–] and available C, so
the amount of time between flooding a soil and the onset of methanogenesis can vary from
several days to several weeks [88]. From the onset of methanogenesis, CH4 emissions from rice
systems generally increase over time as the soil becomes more reduced and usually shows one
or more of three general peak flux trends. Early season peak fluxes are generally attributed to
decomposition of freshly incorporated residues and generally occur within 20 to 40 days after
flooding [83,89] and late-season peaks are thought to result from decomposition following
senescence of rice roots [90,91]. The other time period of peak fluxes generally occurs near the
time of 50% heading (i.e., approximately the time of anthesis) and has been linked to the sink-
source relationship of photosynthates in the plant when CH4 fluxes have been observed to
increase during vegetative growth as root exudates increase and decrease following heading
as fixed-C is translocated to developing grain. This plant-related peak has been observed in
several studies [15–17,80,92–94,95] and similar seasonal trends have been observed in root
growth [96–98], root exudation rates [66], and anaerobic root respiration rates [99].
6.4. Transport mechanisms
The three mechanisms by which CH4 is transported from a ponded soil to the atmosphere are
diffusion through the floodwater, ebullition, and plant-mediated diffusion. Diffusion of CH4
through overlying floodwater is minor as diffusion of gases is approximately 10,000 times
slower through water than through air [46]. Ebullition, bubbles forming and forcing their way
to the surface, may be a significant transport mechanism early in the season, especially with
high OM inputs, soil disturbances, and in coarse-textured soils, but generally plays only a small
role in CH4 transport, which diminishes as plants mature and plant-mediated transport (PMT)
increases [76,100]. The majority of CH4 emissions from a rice system occur through the rice
plants via aerenchyma cells, where studies have indicated that about 90% of season-long
emissions are released through the rice plants, compared to 8 to 9% released by ebullition and
1 to 2% by diffusion through the floodwater [100–104].
Based on experiments using artificial atmospheres of various gas compositions, Denier van
der Gon and van Breemen [105] determined that PMT is driven by molecular diffusion and
not affected by transpiration or stomatal opening. Others have observed a decreasing CH4
concentration gradient from the soil to the rice root aerenchyma, shoot aerenchyma, and
atmosphere, indicative of a diffusive transport pathway from the soil to the atmosphere
through the plant [104,106]. Other studies have also confirmed that CH4 transport is not related
to transpiration and is unaffected by cutting plants just above the water surface [103,104,107].
However, Hosono and Nouchi [108] determined that PMT was reduced linearly as roots were
cut and increased with root growth up to heading, indicating that the surface area of roots in
contact with soil solution is important in determining PMT. Several studies have determined
that the most restrictive zone of CH4 transport through the rice plant is the root–shoot transition
zone where dense intercalary meristem cells restrict movement from the root aerenchyma to
the shoot aerenchyma [101,105,106,109,110].
It has been postulated that CH4 in the gaseous form or dissolved in water enters into root
aerenchyma, which forms by degeneration of cortical cells between the exodermis and the
vascular bundle, where the dissolved CH4 is gasified and moves by diffusion from the root
aerenchyma through the restrictive transition zone into the aerenchyma of the culm and then
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to the atmosphere [104,107,109]. It has been determined that CH4 is released from the rice plant
mainly through the lower leaf sheaths. Examining the cultivar “Koshihikari” with a scanning
electron microscope, Nouchi et al. [104] and Nouchi and Mariko [107] observed CH4 release
from 4-µm diameter, hook-shaped micropores arranged regularly approximately 80 µm apart
on the abaxial epidermis of leaf sheaths as well as from the connections of leaf sheaths to the
culm at nodes. Butterbach-Bahl et al. [106] also determined that CH4 is primarily released
through the lower leaf sheaths, however, micropores were not observed in the cultivars ‘Roma’
or ‘Lido’. More research is required to determine differences in CH4 release from various
cultivars. It has been determined that rice cultivars have differences in CH4 transport capacity,
likely in relation to differences in aerenchyma morphology and the root–shoot transition zone
[101] and that CH4 transport capacity increases as soil temperature increases [108]. Research
indicates that PMT is the dominant mechanism of CH4 release from rice soils and that the rate
of transport can be influenced by cultivar or environmental conditions.
7. Factors affecting methane emissions from rice
Through numerous research efforts since the 1980s, several factors have been determined to
affect CH4 emissions from rice cultivation. Due to the complex balance of methanogenesis and
methanotrophy that determines how much CH4 escapes the rice system to the atmosphere
along with the large variety of cultural and environmental conditions around the globe, there
is large variability in the impact of different factors across time and space. There are a few soil,
environmental, and plant factors, however, that seem to have somewhat consistent impacts
on CH4 emissions from rice.
7.1. Soil factors affecting methane emissions from rice

Various studies have observed inconsistent results of N fertilizer application on CH4 emissions
including an increase in emissions with added N [85,90,111,112], a decrease in emissions with
added N [113,114], or no impact of added N on CH4 emissions [15,75,115]. Banger et al. [116]
conducted a meta-analysis and determined that CH4 emissions were significantly greater from
N-fertilized rice in 98 out of 155 data pairs, indicating that the increase in plant growth and C
fixation resulting from N-fertilization generally increases CH4 emissions. Wang et al. [78]
postulated that the effect of urea on CH4 emissions may be impacted by pH, where it was
observed that urea may cause a decrease in emissions in alkaline soils as urea hydrolysis
increases soil pH, limiting the neutrophilic methanogens. In acidic soils, however, the increase
in pH from urea hydrolysis shifts the soil pH toward neutral and enhances methanogenesis.
Research has consistently indicated that ammonium sulfate reduces CH4 emissions relative to
urea application [70,113,116], likely due to the impact of soil acidification and sulfate reduction
decreasing the available C substrate for methanogenesis. Similarly, other studies have
determined that oxidized Fe [80,117–120] or NO3– [120] amendments have the ability to reduce
CH4 emissions. In addition, Lu et al. [121] observed a 19 to 33% reduction in CH4 emissions
with the application of P due to enhanced root growth and root exudation that was measured
in the P-deficient treatment.
Multiple studies have indicated no significant correlations between CH4 emissions and any
static soil properties [68,81] or between CH4 emissions and total soil C [79,80], while readily
mineralizable C has been shown to be positively correlated with CH4 emissions [75,78].
Particle-size distribution is one soil property that has been regularly related to CH4 emissions
as emissions have been positively correlated with soil sand content [78,80,118,119,122] and
inversely correlated with soil clay content [71,78,118,119,122,123]. Studies have observed an
increase in CH4 entrapment resulting from increasing clay contents [71,78], and Sass and Fisher
[91] attributed the reduction in CH4 emissions from clay soils to the entrapment and slow
movement of CH4 that allows more CH4 to be oxidized in aerated zones surrounding roots
and at the soil surface. In a laboratory incubation study, Wang et al. [78] observed varying
degrees of CH4 entrapment, even among soils with similar sand and clay contents, where the
greatest entrapment (98%) was measured from a Sharkey clay (very-fine, smectitic, thermic
Chromic Epiaquerts) soil compared to 81 and 68% entrapment from a Beaumont clay (fine,
smectitic, hyperthermic Chromic Dystraquerts) and a Sacramento clay (very-fine, smectitic,
thermic Cumulic Vertic Endoaquolls), respectively. This research indicates that clayey soils
have the capability of restricting movement of CH4 to the atmosphere and that other factors,
such as clay minerology and soil chemical properties, may impact emissions more than simply
the total amount of clay.
7.2. Environmental factors affecting methane emissions from rice
Two major environmental factors that impact CH4 emissions from rice are temperature and
soil saturation status. Numerous studies have observed increases in CH4 fluxes in relation to
increasing soil temperatures [100,108,124]. A study conducted in Japan observed a 1.6-fold
increase in emissions from one year to another under the same management and location
resulting from an increase in average air temperature from 24.6 to 26.9oC [119]. Methanotrophic
activity changes only slightly between 10 and 40oC, while temperature has a strong influence
on methanogenesis [56], which leads to a decrease in the proportion of CH4 oxidized and an
increase in emissions as soil temperature increases. Van Winden et al. [65], for example,
reported 98% CH4 oxidation at 5oC compared to 50% oxidation at 25oC.
Soil saturation status has a profound influence on CH4 emissions through the impact of
saturation on soil redox processes, such as methanogenesis. Methane emissions have been
observed from soils at an Eh as great as –100 mV [125], while emissions increase as Eh
decreases. The amount of time required after saturation to reach low redox potentials condu‐
cive to methanogenesis varies based on soil textural and chemical properties [119], but
generally occurs within several days or weeks after flooding. Studies have indicated that a
single mid-season drainage can reduce CH4 emissions by as much as 65% [68,70,75,95,113,126],
however, the potential for greenhouse gas mitigation is reduced or negated due to an increase
in N 2O emissions resulting from the drainage [70,113,126,127]. Further research is needed in
order to more adequately understand the balance between CH4 and N2O emissions under
various water management regimes as well as the impact that N management has on emissions
when fields are drained.
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7.3. Plant factors affecting methane emissions from rice

Due to the strong impact of rice plants on CH4 transport and CH4 production from root
exudates and residue, there are several plant factors that significantly impact emissions from
rice cultivation. A strong relationship between plant growth and CH4 emissions has been
observed in many studies [16,17,80,92–95], particularly in temperate regions, where much of
the previous crop’s residue decomposes during the winter. Studies have indicated that CH4
emissions are up to 20 times greater from soil planted with rice than from unvegetated soil
[67,107,123], indicating the large influence of rice plants on emissions.
One of the major plant factors impacting CH4 emissions from rice is whether or not a ratoon
crop is grown. This impact is reflected in the USEPA’s emissions factors, which are 178 kg
CH4-C ha–1 for non-California primary rice crops and an additional 585 kg CH4-C ha–1 when a
ratoon crop is produced [2], based on ratoon crops studied in Louisiana [21,22]. The large
increase in emissions from ratoon crops is likely a result of large quantities of residue inputs
from the harvest of the primary crop in addition to well-developed root systems that further
increase the available C for methanogenesis. Lindau et al. [22] observed a significant positive
correlation between rice straw additions from a primary crop and resulting emissions from
the following ratoon crop.
Another plant factor that has a substantial impact on CH4 emissions is biomass accumulation.
Huang et al. [128] determined that CH4 fluxes measured during the growing season were
positively correlated to aboveground and belowground dry matter on the dates of flux
measurements. Additional studies have observed positive correlations between season-long
CH4 emissions and aboveground [16,72,102,128] and belowground dry matter [129]. These
studies have indicated a strong relationship between plant growth and CH4 emissions, which
may result from an increase in available substrate as root exudates have been correlated to
biomass [66].
Cultivar selection has also been shown to be an important plant factor influencing CH4
emissions from rice. While the mechanisms for cultivar differences in CH4 emissions have not
been extensively studied, it appears that differences likely arise from variability in CH4
transport capacity, biomass or dry matter production, root exudation, and microbial com‐
munity dynamics among cultivars. Butterbach-Bahl et al. [101], for example, attributed a 24 to
31% difference in emissions between two pure-line cultivars to differences in CH4 transport
capacities, as no differences were observed between CH4 production or oxidation. Aulakh et
al. [84] observed a positive correlation between TOC from root exudates and CH4 production
potential, indicating the potential for cultivar differences in emissions based on variable root
exudation rates. Previous studies have reported reduced emissions from semi-dwarf relative
to standard-stature cultivars [22,91,130]. The difference in CH4 emissions between semi-dwarf
and standard-stature cultivars observed in these studies may be a result of the positive
correlation between dry matter and C exudation rates from roots [84] or between aboveground
dry matter and CH4 emissions [16,72,102,128]. While a reduction in emissions from semi-dwarf
cultivars is oftentimes linked to reduced dry matter accumulation, Rogers et al. [93] observed
a reduction in aboveground dry matter that was not accompanied by a reduction in emissions.
Furthermore, Sigren et al. [130] measured greater emissions accompanied by greater soil
1
2 Figure 2. Methane emissions from standard-stature, conventional rice varieties, such as
Figure 2.3 Methane emissions from standard-stature, conventional rice varieties, such as “Taggart” (top left) and
“Taggart”
“Wells” (top
4 right), and
(tophybrids
left) andvarieties,
“Wells” such as “CLXL745”
(top right), and hybrids(bottom) have
varieties, recently
such been studied
as “CLXL745” in the field at the
(bottom)
Rice Research
5 and Extension Center
have recently near
been Stuttgart,
studied in theAR. Photographs
field taken by and
at the Rice Research K. Brye.
Extension Center near
6 Stuttgart, AR. Photographs taken by K. Brye.
acetate concentrations from a standard stature 44 (“Mars”) relative to a semi-dwarf cultivar
(“Lemont”), while aboveground dry matter was similar between the two cultivars. Huang et
al. [128] indicated that, while biomass may explain differences in emissions within one cultivar,
the intervarietal differences in biomass are small in comparison to differences in emissions,
indicating that another factor besides aboveground dry matter impacts intervarietal differen‐
ces in CH4 emissions.
Cultivar differences, however, extend beyond the impact of biomass production on emissions.
Ma et al. [131] observed a 67% increase in CH4 oxidation from a hybrid cultivar accompanied
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by a reduction in emissions and soil CH4 concentration relative to pure-line cultivars. Addi‐
tional studies have also identified 25 to 37% reductions in fluxes from hybrid relative to pure-
line cultivars [93,132,133] (Figure 2). This indicates that greater methanotrophic activity in the
rhizosphere of hybrid cultivars may reduce CH4 fluxes by oxidizing a greater proportion of
the produced CH4. It is clear that cultivar selection has the potential for mitigation of CH4 from
rice cultivation. However, due to the lack of understanding the mechanisms for differences in
emissions, it appears that direct CH4 flux measurements from various cultivars are necessary
in determining emissions differences until further research clarifies the understanding for
cultivar differences in CH4 emissions (Figure 2).
8. Conclusions
Though some knowledge has been gained, there is much more that still needs to be learned
and understood regarding CH4 emissions from rice production in the US, its contribution to
climate change, and potential mitigation strategies. Additional field research needs to be
conducted to better assess the magnitudes and relative contributions the various known factors
have on CH4 production and emission from soils used for rice production.
It is possible that a single CH4 emissions factor for application to all non-California-grown,
primary-crop rice in the US is too general. Consequently, the single CH4 emissions factor may
be a severe overestimation for some rice-producing areas, while being an underestimation for
other areas. Only after additional data have been generated can regulatory agencies, such as
the USEPA, further refine greenhouse gas emissions factors to reflect the large variety of soils
and agronomic cultural practices throughout the temperate US and combat the potential
negative effects of climate change.
Author details
Kristofor R. Brye, Alden D. Smartt and Richard J. Norman
*Address all correspondence to: kbrye@uark.edu
Department of Crop, Soil, and Environmental Sciences, University of Arkansas, Fayetteville,

USA
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[99] Tolley MD, DeLaune RD, Patrick WH. The effect of sediment redox potential and soil
acidity on nitrogen uptake, anaerobic root respiration, and growth of rice (Oryza sati‐
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[100] Schutz H, Seiler W, Conrad R. Processes involved in formation and emission of

methane in rice paddies. Biogeochemistry. 1989;7:33–53.
[101] Butterbach-Bahl K, Papen H, Rennenberg H. Impact of gas transport through rice

cultivars on methane emission from rice paddy fields. Plant Cell Environ.
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[102] Cicerone RJ, Shetter JD. Sources of atmospheric methane: Measurements in rice pad‐
dies and a discussion. J. Geophys. Res. 1981;86:7203–7209.
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methane from submerged paddy soil. Plant Soil. 1986;92:223–233.
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to the atmosphere through rice plants. Plant Physiol. 1990;94:59–66.
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of the aerenchyma in two rice cultivars. Phyton. 2000;40:43–55.
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RS, editor. Biogeochemistry of Global Change: Radiatively Active Trace Gases. New
York: Chapman & Hall; 1993. pp. 336–352.
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[111] Aerts R, Ludwig F. Water table changes and nutritional status affecting trace gas
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Carex-dominated peat soils. Soil Biol. Biochem. 1997;29:1683–1690.
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ide emissions from rice paddy fields as affected by nitrogen fertilisers and water
management. Plant Soil. 1997;196:7–14.
[114] Wang Z, DeLaune RD, Lindau CW, Patrick WH. Methane production from anaerobic
soil amended with rice straw and nitrogen fertilisers. Fert. Res. 1992;33:115–121.
[115] Adviento-Borbe MA, Pittelkow CM, Anders M, van Kessel C, Hill JE, McClung AM,
Six J, Linquist BA. Optimal fertilizer nitrogen rates and yield-scaled global warming
potential in drill seeded rice. J. Environ. Qual. 2014;42:1623–1634.
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trous oxide emissions from two types of paddy soils. Soil Sci. Plant Nutr.
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[118] Mitra S, Wassmann R, Jain MC, Pathak H. Properties of rice soils affecting methane
production potentials: 1. Temporal patterns and diagnostic procedures. Nutr. Cycl.
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[119] Watanabe A, Kimura M. Influence of chemical properties of soils on methane emis‐

sion from rice paddies. Comm. Soil Sci. Plant Anal. 1999;30:2449–2463.
[120] Yu KW, Wang ZP, Chen GX. Nitrous oxide and methane transport through rice
plants. Biol. Fertil. Soils. 1997;24:341–343.
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[121] Lu Y, Wassmann R, Neue HU, Huang C. Impact of phosphorus supply on root exu‐
dation, aerenchyma formation and methane emission of rice plants. Biogeochemistry.
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fields: Effects of soil properties. Global Biogeochem. Cyc. 1994;8:135–140.
[123] Brye KR, Rogers CW, Smartt AD, Norman RJ. Soil texture effects on methane emis‐
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[124] Wang B, Neue HU, Samonte HP. The effect of controlled soil temperature on diel
CH4 emission variation. Chemosphere. 1997;35:2083–2092.
[125] Hou AX, Chen GX, Wang ZP, Van Cleemput O, Patrick Jr WH. Methane and nitrous
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esses. Soil Sci. Soc. Am. J. 2000;64:2180–2186.
[126] Zou J, Huang Y, Jiang J, Zheng X, Sass RL. A 3-year field measurement of methane
and nitrous oxide emissions from rice paddies in China: Effects of water regime, crop
residue, and fertilizer application. Global Biogeochem. Cyc. 2005;19:GB2021.
[127] Kreye C, Dittert K, Zheng X, Zhang X, Lin S, Tao H, Sattelmacher B. Fluxes of meth‐
ane and nitrous oxide in water-saving rice production in north China. Nutr. Cycl.
Agroecosyst. 2007;77:293–304.
[128] Huang Y, Sass RL, Fisher FM. Methane emission from Texas rice paddy soils. 2. Sea‐
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lands. Nature. 1993;364:794–795.
[130] Sigren LK, Byrd GT, Fisher FM, Sass RL. Comparison of soil acetate concentrations
and methane production, transport, and emission in two rice cultivars. Global Bio‐
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[131] Ma K, Qiu Q, Lu Y. Microbial mechanism for rice variety control on methane emis‐
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BA. Seasonal methane and nitrous oxide emissions of several rice cultivars in direct-
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Chapter 9
Greenhouse Gases Production from Some Crops

Growing Under Greenhouse Conditions
Fernando López-Valdez , Fabián Fernández-Luqueño ,

Carolina Pérez-Morales and Mariana Miranda-Arámbula
http://dx.doi.org/10.5772/62236
Abstract
Greenhouse gases, such as carbon dioxide (CO2), nitrous oxide (N2O) and methane (CH4),
play an important role in global climate change. For example, CO2 production occurs as a
result of the seasonal cycles of the biotic processes of photosynthesis and respiration, as
well as through anthropogenic activities and abiotic processes such as the burning of fos‐
sil fuels. Many activities, such as Agribusiness (the production of crops and animals for
food) create greenhouse gases. Our research group has studied several soil treatments
such as wastewater, wastewater sludge, vermicomposting, and urea among others, in or‐
der to study the effects of soil treatments on the production of greenhouse gases (CO2,
N2O, and CH4) in several cultivars, but mainly in maize, sunflower and the common
bean. The principal aim of this chapter is to show how these greenhouse gases are affect‐
ed by the type of treatment, the properties of the soil, and the cultivar in question. We
also look at which processes are involved in the production of CO2, N2O, and CH4 from
cultivated soil. We present a review of several experiments carried out under in vitro or
greenhouse conditions.
Keywords: Greenhouse gases production, wastewater sludge, fertilizers, treatments
1. Introduction
Global food demand is increasing rapidly, while the associated potential negative environ‐
mental impacts are also growing. Land clearance, the intensive use of existing croplands,
inadequate agricultural management systems, and soil pollution could all contribute to an
increase in the production of greenhouse gases (GHG). Understanding the future environ‐
mental impacts of global crop production, while at the same time achieving greater yields with
lower impacts, requires quantitative assessments of future crop demand and an understanding
of how different production practices affect yields and environmental variables [1].
It is well known that crop management systems, the quality of the soil and the weathering
conditions are just some of the factors used in order to assess production of GHG. Therefore,
an understanding of the future environmental impacts of crop production is essential in order
to achieve greater crop yields without decreasing the quality of the environment and social
welfare. Additionally, Tilman [2] reported that the recent intensification of agriculture,
coupled with the prospect of even further intensification in the future, will have major
detrimental impacts on the world’s ecosystems.
Agriculture is rightly recognized as a source of GHG production, with concomitant opportu‐
nities for its mitigation. In fact, agricultural soils can constitute either a net source or sink of
the three principal GHG [3]. Soil management practices can influence GHG flux by changing
at least one of the following soil properties and its associated management: 1) The soil climate
(temperature and water content); 2) The physicochemical environment of the soil; 3) The soil’s
microorganisms (diversity and abundance); 4) The amount and chemical composition of
organic or mineral fertilizers applied to the soil; and 5) Pesticides might have a strong effect
on the soil microbiota (type and amount). Even a minimal change in one or more of the
properties described above could control the rate and extent of GHG production and also affect
the aeration and diffusion of these gases.
The objective of this chapter is to discuss how the soil production rate of GHG is affected by
treatment type, soil properties, and cultivar. This review will also discuss which processes are
involved in the production of CO2, N2O, and CH4 when crops are grown under in vitro or
greenhouse conditions, and will discuss how these processes work.
2. The Atmosphere, Global Climate Change and Greenhouse Gases
The atmosphere of the Earth has evolved and changed over time and had reached a point of
equilibrium. However, anthropogenic activities arising from the Industrial Revolution and
subsequent development have changed Earth’s atmospheric conditions. Since the industrial
era began, a new phenomenon has been observed — that of global climate change (GCC). Many
different sources are involved in the production of gases, with concern centering on the
production of GHG in particular, as these gases are the ones implicated in the increasing rate
of global warming on Earth. The main gases involved in this warming are methane (CH4),
nitrous oxide (N2O), and carbon dioxide (CO2). Additional and important GHGs include water
vapour, which has an effect on global climate change that can be used as a baseline with which
to compare the remaining GHG. The production of these gases arises as a result of anthropo‐
genic activities, mainly the combustion of fossil fuels (CO2), extensive livestock and cattle
farming (CH4), and agriculture (N2O) through denitrification or nitrification processes, and
occasionally CO2 depending on the type of fertilization employed.
As we can see, global climate change is a phenomenon caused by GHG that are emitted into
the atmosphere. However, the main problem is not the emission of these gases, because these
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Greenhouse Gases Production from Some Crops Growing Under Greenhouse Conditions 211
http://dx.doi.org/10.5772/62236
gases have actually been present in the Earth’s atmosphere for thousands of years and they
are the products of natural processes such as volcanic eruptions, plant and animal respiration
and the microbial decomposition of organic matter. The contribution of human activity has
resulted in the production of large amounts of these gases and their increased concentration
in the atmosphere results in global warming. The most obvious effects of global warming are
the continuous increase of global temperature and the changes in atmospheric conditions. All
the elements of the environment are interrelated, and as a consequence, changes in one of them
lead to changes in others. Sometimes these changes are small and imperceptible, while others
can be very obvious. The rate of these changes is very important because if they are too rapid,
then the ability of organisms to adapt to the new conditions might not be sufficient to ensure
their survival as the natural process of adaptation takes thousands and thousands of years as
a part of the evolutionary processes of life on Earth. The effects of these phenomena are the
extinction of species and other serious negative effects on both the agriculture and fishing
industries that are important economic activities the world over.
It is important to mention that the likely impacts of global warming could be different in
different types of ecosystems because of the difference in climatic conditions in those ecosys‐
tems, but the effects on the abundance and distribution of biodiversity will be constant. All of
these facts suggest that the natural conditions of the planet are being seriously affected by
global climate change, global warming and GHG production, so we have a serious and
worldwide environmental problem to address. However, there are many strategies, such as
the use of alternative sources of energy, which could be implemented around the world to
mitigate the damage being caused to the planet and to promote environmental awareness with
favorable results in the future.
3. Experiments under in vitro conditions
We are interested in understanding which soil processes are involved in GHG production, and
how they work, in several treatments or fertilizers. The production of CO2, N2O, and CH4 when
crops were grown under in vitro or greenhouse conditions was studied. These experiments
were carried out using different types of soil (nitrogen depleted and/or alkaline-saline) and
several crops were studied.
One of the experiments was conducted in order to investigate the evolution of nitrogen and
its loss as a part of the nitrogen cycle. Different fertilizers or treatments were tested. These were
ammonium sulphate [(NH4)2SO4, 200 mg NH4+ kg-1], wastewater sludge (200 mg NH4+ kg-1),
sterile wastewater sludge (200 mg NH4+ kg-1) and a control (distilled H2O). All of the treatments
were added with KNO3 at 100 mg N kg-1, in two different soils (one agricultural and N depleted
soil, and the second a saline-alkaline and N depleted soil) at 40% of water holding capacity
(WHC) under in vitro conditions for 56 days. The variables were CO2, N2O, NH4+-N, NO2--N,
and NO 3--N, and were measured and assessed [4]. The soils used were specifics, i.e. the first
soil was an agricultural soil which had mainly been cultivated with maize (> 25 years), low
fertilization (< 50 kg N ha-1) and was both C and N depleted (6.5 g organic C kg-1, 0.2 g total N
Kjeldahl kg-1, pH 7.8, electrolytic conductivity (EC) 1.0 dS m-1, and the textural soil classification
was loamy sand) from Otumba, in the State of Mexico (Mexico) (19° 42’ N, 98° 49’ W). The
second soil was classified as an uncultivated soil (some grasses and small trees could be found)
as a result of its former lake bed origin. It was found to be N depleted and alkaline-saline, pH
10.3, EC 12.4 dS m-1, 49 g organic C kg-1, and 0.6 total N Kjeldahl kg-1, from Texcoco, State of
Mexico (Mexico) (19° 30’ N, 98° 53’ W). The results showed that production of CO2 from the
Otumba soil was not affected by the addition of NH4+ or NO3-, i.e. both fertilizers produced a
similar amount of CO2, approximately 350 mg CO2-C kg-1 dry soil. The sterilized sewage sludge
increased the production of CO2, > 1,000 mg CO2-C kg-1 dry soil, i.e. over twice the production
compared with that of the controls (soils treated with ammonium or nitrate). When wastewater
sludge was added, the CO2 production was ~ 3,100 mg CO2-C kg-1 dry soil, a value twice that
of sterilized sludge and eight times that of the controls. In the Texcoco soil, a similar contour
was found in the CO2-C dynamics. The control treatments present > 350 mg CO2-C kg-1 dry
soil. The soil treated with sterilized sludge showed a concentration of CO2 that was > 1,100 mg
CO2-C kg-1 dry soil (2.1 times that of the controls) while the treatment with sewage sludge was
~ 2,100 mg CO2-C kg-1 dry soil (over five times that of the controls). Different soils showed
similar contours in C dynamics, and these results revealed that CO2 production was not
particularly different and that the processes involved were rather similar in the different soils
investigated. Wastewater sludge is characterized by large amounts of organic matter (organic
C) and it’s suppose got a large amounts of organic matter easily decomposable. So, the sludge
is easily and rapidly mineralized in both soils [4]. When sewage sludge was sterilized, the
microbiota were destroyed and this might have affected the properties of the organic matter
in the sludge [4]. It could be that the organic matter was more readily accessible for the soil
microorganisms, so that the production of CO2 should be higher in soils with sterilized sludge,
but the results revealed that this is not necessarily true. The results also showed that the soil
microorganisms and the sludge microorganisms could be exerting a synergistic action on the
degradation of organic matter because the degradative action of the microorganisms of the
soil or the sludge alone cannot improve the degradation of organic matter in the treated soil
or in the sludge [4].
The ammonium dynamics showed that the initial concentrations of N were reduced after the
first 3 days, and after that, a release of the mineral occurred from day 3 up to day 14. Later still,
the concentration of ammonium decreased by up to < 14 mg N kg-1 dry soil for all the treatments
in both the Otumba and Texcoco soils, and the ammonium concentration decreased by up to
< 2 mg N kg-1 dry soil for all treatments, except for the soil treated with sterilized sludge, < 31
mg N kg-1 dry soil. The contour of the ammonium dynamics was similar in both the Otumba
and Texcoco soils. Many abiotic and biotic processes might affect the concentration of NH4+ in
soil, such as NH4+ fixation in the soil matrix, volatilisation of NH3, and immobilization or
oxidation of NH4+. Some soil processes were occurring at too low a level to be detectable, such
as NH4+ fixation and the volatilisation of NH3. The nitrate dynamics were similar in both soils.
The concentration of NO3- was ~120 mg N kg-1 dry soil in the control treatment in both soils.
The ammonium concentration was similar in both soils, > 200 mg N kg-1 dry soil, treatments
with sludge reached > 255 mg N kg-1 dry soil and > 300 mg N kg-1 dry soil in the Texcoco and
Otumba soils respectively, and soils treated with sterilized sludge increased the concentration
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to > 300 mg N kg-1 dry soil in the Texcoco soil, while in the Otumba soil it was > 325 mg N
kg-1 dry soil. These results suggest that soil fertilized with wastewater sludge showed an
increased NO3- concentration with a hypothetic mineralisation of ~ 60% at day 56 [4].
The production of N2O was measured in both soils for seven days under C2H2 (10% v/v)
conditions. The control treatment showed a N2O production of < 0.02 mg N kg-1 with or without
C2H2 in the Otumba soil. N2O production increased when ammonium was added to the
Otumba soil, 0.04 mg N kg-1, but the addition of C2H2 reduced it to 0.01 mg N kg-1. When the
sterilized and non-sterilized sludge were added to the Otumba soil, N2O production increased
to 1 mg N kg-1 dry soil without C2H2 and 0.49 mg N kg-1 dry soil with C2H2. In the Texcoco soil,
the control treatment was below 0.005 mg N kg-1 dry soil, but when C2H2 was added an increase
to 0.09 mg N kg-1 dry soil was observed. Soil treated with ammonium increased the production
of N2O (0.04 mg N kg-1), but under C2H2 conditions the concentration was low at 0.01 mg N
kg-1 dry soil when compared with the control treatment. Soils treated with sterilized and non-
sterilized sludge increased the production of N2O (2.1 mg N kg-1 and 0.75 mg N kg-1) compared
with the control treatment, however, the addition of C2H2 increased the N2O concentration of
soil treated with sludge (2.1 mg N kg-1 dry soil) compared with soil treated with sterilized
sludge (1.8 mg N kg-1). It could be argued that the addition of easily decomposable organic
matter into the soil will induce the denitrification process, where NO3- is reduced to N2O and
N2 as final products. There are factors that could be important in controlling the production
of N2O in denitrification, such as oxygen, pH and the ratio of nitrate / available carbon [5].
There are additional parallel factors for NO that are less well understood [5]. It was evident
that in a soil treatment of wastewater sludge or sterilized sludge, the N loss was increased.
The microorganisms from the soil and the sludge were found to be working together in order
to degrade the organic matter in the sludge. In addition, it could be suggested that more
denitrifiers may be present in the Texcoco soil than in the Otumba soil, and a decrease of 50
mg NO3--N was counted at day 56, and the N2O concentration was approximately double (plus
1 mg N2O kg-1 dry soil) that of the Otumba soil on the day 7 [4]. When NO3- (an e- acceptor) is
present in excess compared to organic C (an e- donor), the denitrifiers could be said to be
“spendthrift” with respect to NO3- and in general produce N2O as the major product. When
the same NO3- is limited, the denitrifiers use it to its maximum potential as an e- acceptor and
reduce it all to N2 (dinitrogen) [5]. Schimel and Holland (2005) explain that while the major
producer of NO is nitrification, N2O can also be produced in large quantities by nitrification
or denitrification due to the fact that it is less reactive and can outflow from soils — even wet
soils.
In our study, the microorganisms in the soil and sludge acted together synergistically in the
reduction process, i.e. N2O to N2, the denitrification process, and in the Texcoco soil under
C2H2 conditions, but the main contribution was from the soil microorganisms under the same
conditions. In particular, the production of N2 was almost 50% of the total gas evolved. When
sterilized sludge was applied to the Texcoco soil, minimal N2 was produced (~0.2 mg N 2O-N
kg-1). Furthermore, untreated soil showed an increase in N2O when C2H2 was added (~0.07 mg
N2O-N kg-1) and the N2 produced was approximately 75% of the total gas evolved, under the
conditions established. In the Otumba soil, the N2O was produced by nitrification process (at
40% WHC), and showed in the soil treated with ammonium, sludge and sterilized sludge at
0.04, 1.0, and 1.0 mg N2O-N kg-1 respectively, when compared with untreated soil. N2O
production was low when C2H2 was added to the Otumba soil, and no N2 was produced under
these conditions. It can be established that when organic matter with a high N content is added
to soil, it significantly increases N2O production compared to untreated soil or soil fertilized
with ammonium [(NH4)2SO4] in both soils (an ordinary soil and an alkaline-saline soil). The
major source of production of N2O was found in all treated soils to be as a result of the
nitrification process, and the production of N2 was not recorded in the Otumba soil in this
experiment. In the Texcoco soil, the major source of production of N2O was as a result of the
denitrification process by microorganisms in the soil, and the production of N2 was approxi‐
mately 50% of the total gas evolved (1.1 mg N2O-N kg-1).
4. Experiments under greenhouse conditions
4.1. First experiment under greenhouse conditions
Subsequent studies were established in order to better understand plant growth and the
production of GHG (CO2 and N2O) when a regular Bacillus subtilis strain was inoculated on
the surface of the sunflower (Helianthus annuus L.) cultivar seeds under greenhouse conditions.
The B. subtilis strain was characterized as PGPR, i.e. showing antagonistic activity against
Fusarium oxysporum and Rhizoctonia solani AG1, phosphate solubilizing activity, 1-aminocy‐
clopropane-1-carboxilate deaminase, and indole-3-acetic acid production. The strain was
found as regular PGPR, for more details see [6].
The soil was collected from Alcholoya (Acatlán, in the State of Hidalgo, Mexico). This soil is
an agricultural soil with a pH of 6.5, electrolytic conductivity (EC) 0.7 dS m-1, 846 g kg-1, organic
C content was 11.1 g C kg-1 soil, and total N content 1.0 g N kg-1 soil. The soil was sampled
from three different plots (400 m2), ~ 800 kg was obtained and each plot was pooled separately
and passed through a 5 mm sieve. Thirty-six sub-samples of 6.5 kg of soil from each plot were
placed in cylindrical pots (Ø = 16 cm, 50 cm) with 7 cm of gravel in the bottom. Four treatments
were applied, with nine pots for each of the three soil sites sampled (n = 27). The first treatment
was unfertilized and uncultivated soil (used as the CONTROL treatment), the second treat‐
ment was unfertilized soil cultivated with sunflowers (SUNFLOWER treatment), the third
treatment was soil cultivated with sunflowers and fertilized with 0.5 g urea (75 kg N ha-1, UREA
treatment), and the fourth treatment was soil cultivated with sunflowers (seeds were dressed
with B. subtilis) and fertilized with 0.5 g urea (BS treatment). All treatments were irrigated with
tap water, with an additional input of 19 kg mineral-N ha-1 as NO2--N and NO3--N. In addition,
twelve days after the emergence of the plantlets, they were fertilized with another 0.5 g of urea
(the UREA and BS treatments), giving a total amount of 150 kg N ha-1; and three weeks after
sowing the plantlets were drenched with 4 mL of a bacterial suspension (at the same concen‐
tration as described above) adjacent to the plantlet roots at a depth of 3 cm. From the beginning
of the experiments and approximately every two days for the following 30 days, the pots were
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closed air-tight and their atmosphere was analysed for CO2 and N2O at times of 0, 3, 15 and 30
mins. The experiment was repeated twice [6].
The daily CO2 production rate for some treatments was large at the beginning of the experi‐
ments (data not shown). The daily CO2 production rate showed a drop, remaining < 5 mg C
kg-1 day-1 on day 2 and after that it remained at < 8 mg C kg-1 day-1 for all treatments up to end
of the experiments. The mean CO2 production rate was not significantly different between
treatments. The daily N2O production rate remained ≤ 0.75 µg N kg-1 day-1 for the SUNFLOW‐
ER and CONTROL treatments. Meanwhile, in the BS and UREA treatments, the daily N2O
production rate remained ≤ 2.1 µg N kg-1 day-1 with a maximum score of production in the first
14 days. The mean of the N2O production rate of BS treatment was significantly high when
compared with the SUNFLOWER and CONTROL treatments. Cultivating soil with sunflow‐
ers (SUNFLOWER treatment) did not affect the production of CO2 compared with the
CONTROL treatment (uncultivated soil). It is well known that cultivated soil frequently
increases the production of CO2, possibly due to the activities of the microorganisms degrading
the easily decomposable organic matter such as the dying roots and root exudates in the
rhizosphere, thereby increasing the production of CO2 from the soil. Soils cultivated with
sunflowers and fertilized with urea did not affect the production of CO2. Applying urea to soil
commonly has no effect on the production of CO2 from soils. However, the production of
CO2 might be stimulated when urea is applied to N depleted soil as reported in Phillips and
Podrebarac (2009), where the CO2 production was tripled when 112 kg urea-N kg-1 was applied
to an arable soil. Increases in CO2 production with several doses of urea-N application indicate
that agronomic-scale N inputs might stimulate microbial carbon cycling in arable soils [7]. The
inoculation of B. subtilis on sunflower roots in soils fertilized with urea did not show any effect
on the production of CO2 compared with the UREA treatment. The application of UREA to the
soil resulted in more than a doubling of the mean N2O production rate when compared with
the CONTROL treatment. The production of N2O and NO in the soil is the result of factors
such as ion concentrations and soil conditions under chemical disequilibrium, i.e. the oxidative
process of NH4+ to NO3- under aerobic conditions, nitrification, and a reductive process of
NO3- to N2 under anaerobic conditions, and denitrification or the nitrifier denitrification [5, 8,
9]. According to the IPCC, N2O is the main gas produced and released to the atmosphere by
soil microorganisms [9]. So, when urea is applied into the soil, hydrolysis of the urea is
immediately started, releasing NH4+ into the soil, which is rapidly transformed to NO3- with
the simultaneous production of N2O by the same process. A high concentration of NO3- in soil
favours the production of N2O due to the presence of anaerobic micro-sites in highly com‐
pacted soil.
A principal component analysis (PCA) was undertaken to investigate several plant biometric
parameters and soil properties in the production of N2O and CO2. The analysis was carried
out to include all variables. The PCA revealed that BS treatment has an effect on the shoots of
plants, i.e. the shoot length, dry weight of shoot, and the fresh weight of shoot. UREA treatment
has an effect on roots, i.e. the dry weight of roots, length of roots, and fresh weight of roots,
and a minimal effect on seed weight. Otherwise, the soil properties PCA showed that both the
BS and UREA treatments had an effect on NO3- and EC at depths of 0-15 cm and 15-30 cm. The
BS treatment also has effect on the production of N2O and the UREA treatment has an effect
on NH4+ at a depth 0-15 cm and a slight effect on CO2 production. These results were found to
correspond with a production rate of N2O that was ≤ 2.1 µg N kg-1 day-1 with a maximum
production in the first 14 days of more than that in the UREA treatment (< 1.5 µg N kg-1 day-1).
Additionally, the PCA showed that B. subtilis, as a regular strain, had a marked effect on the
production of N2O but not on CO2 production. This strain might be involved in nitrifier
denitrification (or aerobic nitrification-denitrification) as was reported by Kim et al. [10] and
Yang et al. [11]. Both research groups demonstrated that the Bacillus genus is involved in
nitrification and denitrification, namely B. subtilis, B. cereus and B. licheniformis, where B.
subtilis is involved in the nitrification process and B. licheniformis is involved in denitrification
or aerobic denitrification [10]. Yang et al. reported that the strain of Bacillus subtilis A1 is an
aerobic heterotrophic nitrifying–denitrifying bacterium, which is able to convert NH4+ to N2
under fully aerobic conditions, while growing either autotrophically or heterotrophically [11].
In our experiment, the environmental condition of the soil was aerobic throughout the
experiment, so it could be hypothesized that the B. subtilis strain could be involved in the
nitrification process or the nitrifier denitrification process (or aerobic denitrification).
4.2. Second experiment under greenhouse conditions
The second experiment was carried out using wastewater sludge as an organic fertilizer. It
tested the effect of the sludge or urea on sunflower growth, and the effect of some soil
properties on the production of CO2 and N2O. The plant characteristics were also evaluated.
Wastewater sludge or sewage sludge is generated during wastewater treatment and is an
unavoidable by-product. However, the sludge can be seen as an invaluable by-product when
it is applied to the soil as stabilized sludge. Also, this waste management is the most economical
form of disposal employed to reduce the large amount of sewage sludge. In addition, waste‐
water sludge is organic matter rich in minerals and is an outstanding source of C and N, inter
alia. Applying sludge to the soil offers the opportunity of recycling nutrients for use by plants,
while at the same time returning C as organic matter to the soil in order to improve agriculture
processes.
This experiment was carried out in the same way as the previous experiment (described above).
The wastewater sludge was collected from the Reciclagua treatment plant, S.A. de C.V., where
wastewater from various industries (including the food industry) and households is treated.
The properties of the sewage sludge were pH 8.1, EC 7.9 dS m-1, water content 847 g kg-1, organic
C content 288 g kg-1, total N content 41.8 g kg-1, NH4+ 13 g N kg-1, NO2- 8.3 mg N kg-1, and
NO3- 122 mg N kg-1. For more details of these, see [12]. Four treatments were established in
cylindrical pots, comprising nine soil samples from three sampled plots (n = 27). The treatments
were: i) unfertilized and unsown soil (CONTROL treatment), ii) unfertilized soil cultivated
with sunflowers (SUNFLOWER treatment), iii) cultivated soil fertilized with 0.5 g urea (0.5 g
urea × 2 applications, equivalent to 150 kg N ha-1, UREA treatment), and iv) soil cultivated and
fertilized with 30 g sludge (SLUDGE treatment). The sludge was added so as to be equivalent
to 150 kg N ha-1, assuming that sludge mineralisation was 40% mineral N during the crop cycle.
Tap water supplied a total amount of 19 kg mineral-N ha-1 through irrigation in all treatments
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and throughout the experiment. In order to measure the production of gases, the pots were
closed airtight approximately every two days for the first 30 days, and their atmospheres were
analysed for CO2 and N2O at sequential times of 0, 3, 15 and 30 mins. The experiment was
replicated twice [12].
The results showed that the CONTROL, SUNFLOWER and UREA treatments were not
significantly different with respect to the production rate of CO2 (1.59, 2.03 and 2.6 mg C kg-1
day-1, respectively) (Table 1). The CO2 production rate of sunflowers cultivated in soil fertilized
with sewage sludge (SLUDGE treatment) was 2.96 mg C kg-1 day-1 and was significantly
different compared with the CONTROL treatment. In other words, soil cultivated and
fertilized with sewage sludge was equivalent to both the soil cultivated and fertilized with
urea, and the unfertilized soil. It should be taken in account that several factors affect CO2
production in the soil, such as rhizosphere respiration and soil microbial respiration, soil
moisture, soil temperature, substrate quantity and quality, vegetation type, and land use and
management regimes [13].
CO2 N2O
Treatment
mg C kg day
-1 -1
µg N kg-1 day-1
CONTROL 1.59 B 0.18 B
SUNFLOWER 2.03 AB 0.27 B
UREA 2.60 AB 0.66 B
SLUDGE 2.96 A 2.50 A
Least significant difference 1.14 0.74
Standard error of estimate (P < 0.05) 0.41 0.26
Values with the same letter show no significant difference between treatments (P < 0.05).
Table 1. The production rates of CO2 and N2O from soil cultivated with H. annuus under greenhouse conditions.
On the other hand, the rate of production N2O was significantly different in cultivated soil
fertilized with sludge, 2.5 µg N kg-1 day-1 compared with the remaining treatments, 0.7, 0.3,
and 0.2 µg N kg-1 day-1 for the UREA, SUNFLOWER, and CONTROL treatments respectively.
As previously discussed, wastewater sludge is an organic matter which is rich in easily
decomposable material. In addition, it has been demonstrated that microorganisms from the
sludge plus those from the soil work together synergistically to accelerate the decomposition
of organic matter [6]. The high levels of microbial activity stimulated by the addition of material
with high C and N contents could increase the production of both CO2 and N2O. According to
Kool et al. [9], the loss of N in our experiment might primarily be as a result of the nitrifier
nitrification process (from ammonium oxidation) followed by the nitrifier denitrification
process. As a result, the wastewater sludge had a NH4+ concentration of 13 g N kg-1, an amount
of ammonium which might not be oxidized to N2O so rapidly. The chemical composition of
organic or mineral fertilizers — or even residues applied to the soil — is an important factor
in regulating the magnitude of N2O production.
A PCA was performed on all relevant properties of the soil. The first principal component
explained about 22% of the observed variation, while the second accounted for 17% of the
observed variation. On the related scatter plot, the UREA treatment lies in upper right
quadrant and the SLUDGE treatment is in the upper left quadrant. The SUNFLOWER and
CONTROL treatments were found in lower left and right quadrants respectively (Figure 1).
1.5
1.2
SLUDGE
0.9 NO2 -, 0-15 cm
EC, 0-15 cm
EC, 15-30 cm
0.6
NH4 + , 15-30 cm NO3 -, 0-15 cm Production of N2 O
0.3 NH4 + , 0-15 cm pH, 15-30 cm

NO3 -, 15-30 cm UREA pH, 0-15 cm
0
Factor 1: 22% Production of CO2
NO2 -, 15-30 cm
-0.3
CONTROL
-0.6
-0.9 SUNFLOWER
-1.2
Factor 2: 17%
-1.5
-1.5 -1.2 -0.9 -0.6 -0.3 0 0.3 0.6 0.9 1.2 1.5
Figure 1. Results of a principal component analysis (PCA) performed on soil properties under greenhouse conditions
(n = 27).
The UREA treatment seems to have an effect on the pH of soil at both depths (0–15 and 15–30
cm) and also affects the production of CO2 and N2O. The PCA also revealed that the SLUDGE
treatment affected EC at a depth of 0–15 cm and had a slight effect on both ammonium and
nitrate concentrations at both depths.
4.3. Third experiment under greenhouse conditions
In this study, the effect of urea, wastewater sludge and vermicomposting on the production
of CO2 and N2O was investigated. The Otumba soil (State of Mexico, Mexico), which was
characterized as a sandy loam with pH 7.6, EC 1.15 dS m-1, and an organic C content of 7.2 g
C kg-1, was used in this study. Wastewater sludge was again collected from Reciclagua S.A. de
C.V. (as described above). The vermicompost was prepared with wastewater sludge from
Reciclagua and Eisenia fetida. The vermicompost was obtained from a mixture of sludge (1,800
g) and manure (800 g) with 70% water content, and was added to 40 individuals of E. fetida
with the mixture being conditioned over three months. The properties of the vermicompost
were pH 7.9, EC 11 dS m-1, organic C content 163 g kg-1, and a total N content of 2 g kg-1. As
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well, the vermicompost presented < 3 CFU g-1 Salmonella sp., no Shigella sp., and no helminth
ova.
Forty-five sub-samples of 3.25 kg soil were prepared, i.e. three soil samples, three replicates,
and five treatments were established. The treatments were: i) soil fertilized with 0.07 g urea
kg-1, (UREA treatment), ii) soil fertilized with 21.2 g sewage sludge kg-1 (H-SLUDGE treat‐
ment), iii) soil fertilized with 12.8 g sewage sludge kg-1 (L-SLUDGE treatment), iv) soil fertilized
with 81.5 g vermicompost kg-1 (VERMI treatment), and v) unfertilized soil (CONTROL
treatment). The amount of urea was 80 kg N ha-1 for the UREA, H-SLUDGE, and VERMI
treatments, while the L-SLUDGE treatment was 48 kg N ha-1. The production of CO2 and N2O
was analysed every two days at 0, 3, 15 and 30 mins, until day 97. The cultivar of common
bean used was Negro-8025 (from Universidad Autónoma Chapingo, Texcoco, State of Mexico).
Tap water was used for irrigation at a rate of 500 mL every seven days. The experiments were
triplicated and ran for 117 days in total.
A large amount of CO2 was recorded at the end the experiment (from day 45 until day 82). The
UREA treatment had no significant effect on CO2 production when compared with the
CONTROL treatment (0.043 mg C kg-1 dry soil). Wastewater sludge was found to increase the
mean production of CO2 in the soil at 0.064 mg C kg-1 compared with the untreated soil, and
the VERMI treatment showed the largest mean CO2 production at 0.1 mg C kg-1. Urea had no
significant effect on CO2 production when compared with the CONTROL treatment. Occa‐
sionally, urea might stimulate the production of CO2 in N depleted soils. Wastewater sludge
increased CO2 production through the mineralization of organic C and the increasing of
microbial activity in the rhizosphere. Similarly, vermicomposting stimulated plant growth and
increased root exudates and microbial activity in the rhizosphere. The high levels of CO2
produced towards the end of the experiments could be related to rapid root growth and the
beginning of root decomposition. For example, common bean plants at 49 days after sowing
(flowering and nodule senescence begins) showed a decrease in the number of nodules, and
their nodule cell walls slowly became thinner and degraded [14] thereby improving the
environment for the growth of microorganisms and increasing the production of CO2 towards
the end of the experiments.
The mean production of N2O was -0.004 µg N kg-1 in the CONTROL treatment. Soil fertilized
with urea increased the mean production of N2O to 0.015 µg N kg-1. Wastewater sludge
increased the mean production to 0.11 µg N kg-1 and 0.58 µg N kg-1 in the L-SLUDGE and H-
SLUDGE treatments respectively, and the vermicompost mean was 0.32 µg N kg-1 dry soil.
N2O production in order of effect size of treatment was: wastewater sludge (H-SLUDGE) >
vermicomposting > wastewater sludge (L-SLUDGE) > urea > unfertilized soil. Nitrifier
nitrification and nitrifier denitrification were presumably the processes that contributed the
most to the production of N2O under aerobic conditions.
4.4. Fourth experiment under greenhouse conditions

Juárez-Rodríguez et al. applied the sludge derived from anaerobically digested cow manure
in the production of biogas (methane-air), to maize (Zea mays L.) cultivated in a nutrient-low,
alkaline-saline soil with EC 9.4 dS m−1 and pH of 9.3. The results showed that the CO2
production increased 3.5-fold in the soil cultivated with maize and sludge, and increased 3.1-
fold after the sludge was added to the soil. The production of CO2 from soil cultivated with
maize showed a 1.6-fold increase compared with the uncultivated and unfertilized soil, 1.5 mg
C kg−1 day−1. N2O production was -0.0004 µg N kg−1 soil day −1 in unfertilized soil, and in soil
cultivated with maize was 0.3 µg N kg−1 day−1. Soil treated with sludge increased the produc‐
tion of N2O up to 4.6 µg N kg−1 soil day−1. Nevertheless, it was found that cultivated soil
produced 2.4 µg N kg−1 soil day−1, reducing N2O production. It was also found that applying
the anaerobically digested cow manure stimulated the growth of maize cultivated in an
alkaline and saline soil, and the production of CO2 and N2O was increased.
4.5. Fifth experiment under greenhouse conditions
In this study, the main aim was to investigate how maize fertilized with wastewater at 120 kg
N ha−1 affected crop growth, soil properties and the production of carbon dioxide (CO2),
methane (CH4) and nitrous oxide (N2O) compared with plants fertilized with urea [16].
The soil was collected from the Mezquital Valley, located near Pachuca in the State of Hidalgo
(Mexico). The irrigation water used was slightly alkaline with a pH of 8.4. The experiment was
carried out under greenhouse conditions. Soil collected from three sub sites was placed into
cylindrical pots. Five treatments were established in order to study the effect of wastewater
and urea on the cultivation of maize (Zea mays L.). The treatments were: a) SMWW, maize plant
plus wastewater; b) SMUREA, maize plant plus urea as fertilizer; c) SUREA, uncultivated soil
and urea as fertilizer; d) SWW, uncultivated soil plus wastewater; and e) SCONTROL
treatment, soil plus tap water. Soils from the SMWW and SWW treatments were irrigated with
1000 mL of wastewater every 7 days from the first day onwards, making a total of 13 times
overall. This means that a total amount of mineral N equivalent to 120 kg N ha−1 was added to
each maize plant, i.e. the recommended amount of N fertilizer for maize.
The concentration of NH4+ was larger in the soil treated with urea and wastewater than in the
untreated soil, as the urea was hydrolysed and the wastewater contained high concentrations
of NH4+. The addition of wastewater to the soil doubled the production of CO2 and approxi‐
mately 0.2 g C was produced from the soil due to the decomposition of the wastewater after
70 days. In other words, 34% wastewater C was mineralized. However, urea may only
occasionally stimulate CO2 production when a soil is N depleted. Plants take CO2 from the
atmosphere, but mineralization of root exudates increases the production of CO2. The pro‐
duction of CO 2 increased towards the end of the period of maize growth. This indicated that
the phenological stage of the plants affected CO2 production. The growth of maize plants was
similar under the SMWW (wastewater) and the SMUREA (urea) treatments, even when the
release of nutrients was delayed by mineralisation from the organic matter in the wastewater.
When wastewater was applied to the soil, the mean production rate of CO2 increased signifi‐
cantly at 2.4-fold, 1.7 µg C kg−1 h−1, compared with the SCONTROL treatment at 0.7 µg C kg−1
h−1 (Table 2). Meanwhile, cultivating maize increased CO2 production 3.2-fold, 5.6 µg C kg−1 h
−1
. The SWW, SMWW or SUREA treatments did not show a significant difference in the
production of N2O compared with the SCONTROL (1.5×10−3 µg N kg−1 h−1). The addition of
urea did not affect the CH4 oxidation rate (0.1×10−3 µg C kg−1 h−1), nor did the SMUREA
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treatment (cultivated soil fertilized with urea), but the addition of wastewater to the soil
significantly increased CH4 production to 128.4×10−3 µg C kg−1 h−1. Soil irrigated with waste‐
water increased the global warming potential (GWP) up to 2.5-fold compared with the SUREA
treatment (soil plus urea), whereas cultivated soil increased the GWP 1.4-fold. Crops irrigated
with wastewater might limit the use of N fertilizer and water from aquifers. Nevertheless, the
amount of fertilizer applied must be limited due to nitrate (NO3-) leaching and the production
of CO2, N2O and CH4 – that they could be produced in significant amounts –, and at the same
time the salt content of the soil will accumulate, limiting the growth of the crop.
Soils can be either a net sink or a net source of CH4, depending on several factors such as the
moisture level, N level, and the nature of the ecosystem in question. Methane is used up by
methanotrophic microorganisms, which are ubiquitous in several soils, and is produced by
methanogenic microorganisms in the soil under anaerobic conditions. Agricultural systems
are not normally large sources or sinks of CH4. Only under certain conditions are they sources
of CH4 — after application of manure or other organic materials, or moderate to high levels of
irrigation. Our results showed that soil irrigated with wastewater — with or without maize —
increased CH4 production significantly (SMWW and SWW treatments) particularly after
irrigation, due to temporary anaerobic conditions.
CO2 N2O CH4 GWP a

Treatment
(µg C kg−1 h−1) (µg C kg−1 h−1) (µg C kg−1 h−1) (g C kg−1 soil)
SMWW 5.6 Ab 2.8×10-3 A 163.6×10-3 A 1.97
SMUREA 4.95 A 4.5×10-3 A 8.4×10-3 C 1.44
SUREA 0.9 C 3.3×10 A

-3
0.1×10 C
-3
0.36
SWW 1.7 B 2.5×10 A

-3
128.4×10 B -3
0.90
SCONTROL 0.7 C 1.5×10-3 A 1.5×10-3 C 0.26
a
The global warming potential (GWP) of the gases produced was calculated considering CO2 production equivalent to
310 for N2O, 21 for CH4 and 1 for CO2 (IPCC, 2007) over a 90-day period, minus the C that was stored in the roots per kg
soil.
b
Values with the same letter show no significant difference between treatments (P < 0.05).
Table 2. Production of greenhouse gases, CO2, CH4 (µg C kg−1 soil h−1), and N2O (µg N kg−1 soil h−1) from five
treatments: a) soil + plant + wastewater (SMWW), b) soil + plant + urea (SMUREA), c) soil + urea (SUREA), d) soil +
wastewater (SWW), and e) soil + water (SCONTROL).
Fertilizing maize with urea or wastewater had a similar effect on plant growth, so wastewater
might be useable as a crop fertilizer. The treatments with urea or wastewater had no effect on
the pH of soil in this experiment due to the fact that the soil is a vertisol, characterized by a
clay type 2:1, with a large capacity for the exchange of protons and consequently, a high
buffering capacity. The addition of wastewater increased the production of both CO2 and
CH4 compared with the soil treated with urea, but did not increase the production of N2O. The
irrigation of crops with wastewater might in the long term be a far more environmentally
friendly approach to that of using water from aquifers that take long periods of time to fill, as
long as the amount of wastewater applied is restricted to the amount required by the cultivated
crop due to possible substantial losses of mineral N through several process such as the
production of CO2, CH4 and N2O, and the fact that soil salinization could increase rapidly.
5. Conclusions
The organic fertilizers or treatments (vermicompost, wastewater sludge, anaerobically

digested cow manure, and wastewater) might increase the production of greenhouse gases,
as do several abiotic and biotic factors involved in microbial activity within the soil. Sludge as
a soil fertilizer offers the opportunity for the recycling of plants nutrients and the recovery of
C as organic matter and its use in soil to improve agriculture. The high levels of microbial
activity stimulated by the addition of this high C and N content material could increase both
CO2 and N2O production. It should be taken in account that several factors are involved in the
production of gases in the soil such as rhizosphere respiration, vegetation type, and soil
microbial respiration, as well as abiotic factors such as soil moisture, soil temperature, substrate
quantity and quality, and land use and management regimes.
Environmental and economic implications must be considered in order to make well-informed

decisions on the management of soil treatments, i.e. how many, how often and what kind of
organic fertilizer should be used in order to improve crop production and simultaneously limit
soil deterioration and greenhouse gases production.
Acknowledgements
We would like to thank the Instituto Politécnico Nacional and CONACyT for their financial
support and the grant-aided support received.
Author details
Fernando López-Valdez 1*, Fabián Fernández-Luqueño 2, Carolina Pérez-Morales 1 and

Mariana Miranda-Arámbula1
*Address all correspondence to: flopez2072@yahoo.com
1 Agricultural Biotechnology Group, Research Centre for Applied Biotechnology, Instituto

Politécnico Nacional, Tlaxcala, Mexico
2 Sustainability of Natural Resources and Energy Program, Cinvestav-Saltillo, Saltillo, C.P.

Coahuila, Mexico
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References
[1] Tilman D, Balzer C, Hill J, Befort BL. Global food demand and the sustainable inten‐
sification of agriculture. P Natl Acad Sci USA.. 2011;108:20260-20264. DOI: 10.1073/
pnas.1116437108
[2] Tilman D. Global environmental impacts of agricultural expansion: The need for sus‐
tainable and efficient practices. P Natl Acad Sci USA. 1999;96:5995-6000. DOI:
10.1073/pnas.96.11.5995
[3] Gregorich EG, Rochette P, VandenBygaart AJ, Angers DA. Greenhouse gas contribu‐
tions of agricultural soils and potential mitigation practices in Eastern Canada. Soil
Till Res. 2005;83:53-72. DOI: 10.1016/j.still.2005.02.009
[4] López-Valdez F, Fernández-Luqueño F, Luna-Guido ML, Marsch R, Olalde-Portugal

V, Dendooven L. Microorganisms in sewage sludge added to an extreme alkaline sal‐
ine soil affect carbon and nitrogen dynamics. Applied Soil Ecology. 2010;45:225–231.
DOI: 10.1016/j.apsoil.2010.04.009
[5] Schimel J, Holland EA.Global gases. In: David M. Sylvia, Jeffry J Fuhrmann, Peter G.
Hartel, David A. Zuberer, editors. Principles and Applications of Soil Microbiology.
2nd ed. USA: Pearson Prentice Hall; 2005. p. 491-509.
[6] López-Valdez F, Fernández-Luqueño F, Ceballos-Ramírez JM, Marsch R, Olalde-Por‐

tugal V, Dendooven L.A strain of Bacillus subtilis stimulates sunflower growth (Heli‐
anthus annuus L.) temporarily. Scientia Horticulturae. 2011;128:499–505. DOI:10.1016/
j.scienta.2011.02.006
[7] Phillips RL, Podrebarac F. Net fluxes of CO2, but not N2O or CH4, are affected follow‐
ing agronomic-scale additions of urea to prairie and arable soils. Soil Biology & Bio‐
chemistry. 2009;41:2011–2013. DOI: 10.1016/j.soilbio.2009.06.014
[8] Wrage N, Velthof GL, van Beusichem ML, Oenema, O.Role of nitrifier denitrification
in the production of nitrous oxide. Soil Biol. Biochem. 2001;33:1723-1732. DOI:
10.1016/S0038-0717(01)00096-7
[9] Kool DM., Dolfing J, Wrage N, Van Groenigen JW. Nitrifier denitrification as a dis‐
tinct and significant source of nitrous oxide from soil. Soil Biology & Biochemistry.
2011;43:174-178. DOI: 10.1016/j.soilbio.2010.09.030
[10] Kim JK, Park JK, Cho KS, Nam SW, Park TJ, Bajpai R. Aerobic nitrification–denitrifi‐
cation by heterotrophic Bacillus strains. Bioresource Technology. 2005;96:1897–1906.
DOI: 10.1016/j.biortech.2005.01.040
[11] Yang XP, Wang SM, Zhang DW, Zhou LX. Isolation and nitrogen removal character‐
istics of an aerobic heterotrophic nitrifying–denitrifying bacterium, Bacillus subtilis
A1. Bioresource Technology. 2011;102:854–862. DOI: 10.1016/j.biortech.2010.09.007
[12] López-Valdez F, Fernández-Luqueño F, Luna-Suárez S, Dendooven L. Greenhouse

gas emissions and plant characteristics from soil cultivated with sunflower (Helian‐
thus annuus L.) and amended with organic or inorganic fertilizers. Science of the To‐
tal Environment. 2011;412-413:257-264. DOI: 10.1016/j.scitotenv.2011.09.064
[13] Ding W, Meng L, Yin Y, Cai Z, Zheng X. CO2 emission in an intensively cultivated
loam as affected by long-term application of organic manure and nitrogen fertilizer.
Soil Biology & Biochemistry. 2007;39:669–679. DOI: 10.1016/j.soilbio.2006.09.024
[14] Fernández-Luqueño F, Dendooven L, Munive A, Corlay-Chee L, Serrano-Covarru‐

bias LM, et al. Micro-morphology of common bean (Phaseolus vulgaris L.) nodules un‐
dergoing senescence. Acta Physiologiae Plantarum. 2008;30(4):545-552. DOI: 10.1007/
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[15] Juárez-Rodríguez J, Fernández-Luqueño F, Conde E, Reyes-Varela V, Cervantes-San‐

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Chapter 10
Mitigating Greenhouse Gas Emissions from Winter

Production of Agricultural Greenhouses
Lilong Chai, Chengwei Ma, Baoju Wang, Mingchi Liu and Zhanhui Wu
http://dx.doi.org/10.5772/62271
Abstract
Consuming conventional fossil fuel, such as coal, natural gas, and oil, to heat
agricultural greenhouses has contributed to the climate change and air pollutions
regionally and globally, so the clean energy sources have been increasingly applied
to replace fossil energies in heating agricultural greenhouses, especially in urban area.
To assess the environment performance (e.g., greenhouse gas (GHG) emissions) of the
ground source heat pump system (GSHPs) for heating agricultural greenhouses in
urban area, a GSHPs using the shallow geothermal energy (SGE) in groundwater was
applied to heat a Chinese solar greenhouse (G1) and a multispan greenhouse (G2) in
Beijing (latitude 39°40′ N), the capital city of China. Emission rates of the GSHPs for
heating the G1 and G2 were quantified to be 0.257–0.879 g CO2 eq. m−2 day−1. The total
GHG emissions from heating greenhouses in Beijing with the GSHPs were quantified
as 1.7–2.9 Gt CO2 eq. year−1 based on the electricity from the coal-fired power plant
(CFPP) and the gas-fired power plant (GFPP). Among different stages of the SGE flow,
the SGE promotion contributed most GHG emissions (66%) in total due to the higher
consumption of electricity in compressors. The total GHG emissions from greenhous‐
es heating with the coal-fired heating system (CFHs) and gas-fired heating system
(GFHs) were quantified as 2.3–5.2 Gt CO2 eq. year−1 in Beijing. Heating the G1 and G2
with the GSHPs powered by the electricity from the CFPP, the equivalent CO2
emissions were 43% and 44% lower than directly burning coal with the CFHs but were
46% and 44% higher than the GFHs that burn natural gas. However, when using the
GFPP-generated electricity to run the GSHPs, the equivalent CO2 emissions would be
84% and 47% lower than the CFHs and the GFHs, respectively.
Keywords: urban agriculture, greenhouse heating, greenhouse gases, fossil en‐

ergy, shallow geothermal energy
1. Introduction
Agricultural buildings, such as horticultural greenhouse, usually require additional heating

during winter and cold days in high latitude regions of the Northern Hemisphere [1, 2]. In
northern China and many European countries, coal-fired heating system (CFHs) and the
natural gas-fired heating system (GFHs) are dominant heating methods in greenhouses [3, 4].
However, conventional fossil fuels, such as coal, natural gas, and oil, which are nonrenewable
and are the major greenhouse gas (GHG) contributors, may lead to the global climate change,
air pollution, and energy crisis [5-7].
Renewable and clean energy, such as solar, geothermal, and shallow geothermal energy (SGE),
has been increasingly applied to replace fossil energy systems in heating agricultural buildings
(especially in urban area) across the world [8-11]. The SGE is mainly the stored solar energy
in groundwater and soil layers less than 200 m deep from the earth soil surface [12, 13]. It can
be used as heat source or sink for air conditioning in residential, industrial, and agricultural
buildings with the ground source heat pump system (GSHPs), also known as geothermal heat
pumps (GHPs) [4, 14].
The GSHPs has been applied to heat agricultural greenhouse in many countries [15-18]. The
GSHPs could be considered with zero GHG emissions if the electricity was the only energy
source that could be consumed by the system. However, producing electricity in coal-fired
power plant (CFPP) or gas-fired power plant (GFPP) would emit a large quantity of GHG (e.g.,
CO2). Besides, the refrigerant (e.g., R22 and R134a) used by the heat pump unit has been
reported with the high risk of leaking in the year-round operation [19]. Therefore, assessing
GHG emissions of the GSHPs should consider both direct and indirect sources.
In northern China (the area with altitude higher than 30° in the Northern Hemisphere) [20],
there was mainly two kinds of horticultural greenhouses: the Chinese solar greenhouse
(denoted as G1), which may or may not require assisted heating depending on the building
design and the plants be cultivated, and the multispan greenhouses (denoted as G2), which
require 100% assisted heating systems (primarily in the form of coal burning or gas burning)
during winter time [21, 22]. The Chinese solar greenhouse, characterized with east-west
orientation, transparent camber south roof, and solid north roof and east and west walls,
usually has higher heat-preserving capacity than multispan greenhouse and requires less
heating [23, 24]. However, the healthy growth of thermophilic vegetables, such as cucumber
and tomato, and most flowers in Chinese solar greenhouse still requires assisted heating
especially during cold winter nights or consecutive days of snowing or cloudy [3].
By the end of 2007, about 19,300 ha of greenhouses and tunnels had been constructed and used
in Beijing, the capital city of China [25, 26], primarily for producing vegetables, flowers, and
fruits. About 6000 ha Chinese solar greenhouses (the structure similar to G1) and 1000 ha
multispan greenhouses (the structure similar to G2) may require assisted heating in winter
with the systems of the CFHs and GFHs [27]. Therefore, quantifying the heating rate and GHG
emission rate for the primary types of agricultural greenhouses with different heating systems
and energy sources is important for developing the national or regional GHG emissions
inventory of the greenhouse heating and mitigation strategies.
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Mitigating Greenhouse Gas Emissions from Winter Production of Agricultural Greenhouses 227
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The objectives of this chapter are to (1) address the environmental concern on agricultural
production over winter; (2) quantify the heating loads and the GHG emission rates for the two
primary agricultural greenhouses (the G1-Chinese solar greenhouse and the G2-multispan
greenhouses) in northern China; (3) assess the annual GHG emissions inventory of the
greenhouse heating with different energy sources in Beijing, the capital city of the China; and
(4) identify the difference between the shallow geothermal energy and the conventional fossil
energy systems in GHG emissions of agricultural greenhouses heating.
2. Materials and Methods
2.1. Selected/tested greenhouses and the GSHPs
A Chinese solar greenhouse (G1, Figure 1 and Table 1) and a multispan greenhouse (G2, Figure
2 and Table 1), two important types of greenhouse in Northern China, were equipped with
the groundwater-type GSHPs (Figure 3 and Table 2) in Beijing (latitude 39°40′N) and tested
for developing heating rate and GHG emission rate. Performances of GHSPs were compared
to CFHs and GFHs. In addition, different electricity generation methods (e.g., coal and gas
power plant) were considered for assessing the GHG emissions of the GSHPs.
(a) Cucumbers in the G1
(b) The profile of the G1
Figure 1. The Chinese solar greenhouse (G1)

Figure 1. The Chinese solar greenhouse (G1)
Table 1. Characteristics of the testing greenhouses.
Surface
Section Construction and coverage material
area, m2
Chinese solar greenhouse (G1)
(1) North wall 240 mm clay brick+100 mm polystyrene heat preservation layer+240 150
Surface area,
Section Construction and coverage material
m2
Chinese solar greenhouse (G1)

240 mm clay brick+100 mm polystyrene heat preservation layer+240 mm clay
(1) North wall 150
brick
(2) East and west end 240 mm clay brick+100 mm polystyrene heat preservation foam board+240 mm
36
walls clay brick
0.15 mm single layer transparent polyethylene (south roof was covered with 10
(3) South roof 510
mm needled felt heat blanket at winter nights)
(4) North roof 50 mm steel plate+100 polystyrene heat preservation layer+50 mm steel plate 108
(5) Floor Bare soil (clay) 480
Multispan greenhouses (G2)
5 mm coated steel sheet+100 mm polystyrene heat preservation layer+5 mm
(1) North wall 126
coated steel sheet
(2) East and west wall 20 mm double-layer glass 110
(3) South wall 20 mm double-layer glass 98
(4) North roof 20 mm double-layer glass 108
Bare soil for planting with concrete walkway (floor area was covered with
(5) Floor 756
aluminum film at horizontal height of 3.5 m at winter nights)
Table 1. Characteristics of the testing greenhouses.
(a) Cottons in the G2
(b) The profile of the G2
Figure 2 The multispan greenhouse. . .

Figure 2. The multispan greenhouse.
Table 2. Characteristics of the GSHPs.
Elements Performance parameters
Manufacturer: four Danfoss hermetic scroll compressor; rated power of electric
(1) Compressor motor driving: 16.08×4 kW; refrigerant: 58 kg R22. Rate of refrigeration capacity:
380 kW; rate of heating capacity: 450 kW.
(2) Condenser Horizontal shell–tube model
(3) Evaporator
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Dry evaporator model
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(a) The heat pump and water circulating system
G2 III
G2 Inlet G2 Outlet Pump3

i G1
TFM
G1 Inlet G1 Outlet Pump2
f e 4 1 b a
Throttling valve
Evaporator
Compressors
II
5 6
8 7
g c
h 3 Condenser 2 d
Pump4 Pump1
Groundwater refilling Groundwater drawing
Ground level
100m
Groundwater refilling wells Groundwater drawing well
(b) Diagram of the GSHPs greenhouse heating system
Figure 3. The groundwater type of GSHPs. (I is the stage of SGE extraction, II is the stage of SGE promotion, and III is
the stage of greenhouse heating. a–i are valves installed in different water pipes. Pump 1 is groundwater drawing
pump; pumps 2 and 3 are circulating water pumps; and pump 4 represent the groundwater backfilling pump. TFM is
the thermal flow meter installed position. 1−8 represent the thermodynamic points in each section of GSHPs [18].
The GSHPs started to heat greenhouses on October 15, 2007 and ended on February 4, 2008.
Cucumbers and strawberries were grown in G1 and cotton was grown in G2 during heating
tests. The fan coil units in two greenhouses were controlled by the T-type thermocouple
controllers automatically. For G1, the indoor air temperature was controlled in the range of
18°C–20°C, and for G2, the indoor air temperature was controlled in the range of 18°C–22°C,
considering the poor thermal stability caused by the larger volume in G2.
Elements Performance parameters
Manufacturer: four Danfoss hermetic scroll compressor; rated power of electric motor
(1) Compressor driving: 16.08×4 kW; refrigerant: 58 kg R22. Rate of refrigeration capacity: 380 kW; rate of
heating capacity: 450 kW.
(2) Condenser Horizontal shell–tube model
(3) Evaporator Dry evaporator model
(4) Throttle Copper capillary tube
In G1: FP-136; rated input power: 56 W; number: 6. In G2: 42VM006; rated input power: 87
(5) Fan-coil
W; number: 45
(6) Pumps Flux: 33.2 m3 h−1; rated input power: 11 kW; number: 4
(7) Control system PLC touching screen controller
Table 2. Characteristics of the GSHPs.
2.2. Power inputs and heating rate quantification
The heat provided by the GSHPs for heating greenhouses was quantified with the thermal
flow meter (TFM) (Model DN35 and DN100, Beijing Jingyuan Liquid Apparatus Company,
Beijing, China). A weather station (Qingsheng Electronic Science and Technology Co. Ltd.,
Handan, China) installed in the agriculture station was used to monitor outdoor environmen‐
tal factors. Total electricity consumption of the GSHPs was recorded with watt-hour meter
(Shanghai Huaxia Ammeters Manufactory, Shanghai, China).
2.3. Quantifying the GHG emissions
There are six kinds of gases (Table 3) highlighted as the GHG in Intergovernmental Panel on
Climate Change (IPCC 2006) [5]. For the greenhouse heating with the CFHs and GFHs, carbon
dioxide (CO2) is the only GHG to be considered. But for the GSHPs greenhouse heating, most
electricity consumed (in Beijing area) was generated in the CFPP or the GFPP, and the process
of the power generation could emit large amount of CO2 [25]. Besides, it has been reported that
the leaking fraction of the refrigerant (i.e., R22(HFC-22) in this study) used in the GSHPs is
around 0.02 kg −1 (2%) per year [19]. The R22 was not listed as one of the six primary GHG in
the IPCC (2006), but it was reported with 1.28 times of the global warming potential (GWP) of
the R134a (HFC-134a) [28]. Therefore, the GWP of R22 was estimated to be 4902, 1830, and 557
based on 20a, 100a, and 500a, respectively, based on the relationship of the GWP with the
R134a.
The GHG emissions from heating G1 and G2 with the GSHPs can be quantified with Eq. 1.
HEGSHPs ,Gi
EM GSHPs - Gi - j = MGSHPs - Gi - j * f j - co2 + MR 22,Gi * fR 22 - leak * fR 22 - co2 (1)
HEGSHPs,G
where HEGSHPs,G, total energy provided by the GSHPs for heating G1 and G2 during whole
winter (monitored with TFM), MJ; HEGSHPs,Gi, total energy provided by the GSHPs for heating
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GHG 20a 100a 500a
CO2 1 1 1
CH4 72 25 7.6
N2O 289 298 153
HFCs(HFC-134a) 3830 1430 435
PFCs (PFC-116) 8630 22,800 32,600
SF6 16,300 22,800 32,600
Note: Data were cited from IPCC 2006[5], expressed in CO2 eq.
Table 3. GWP of different greenhouse gases
the greenhouse of type i (G1 or G2) during whole winter (monitored with TFM), MJ; EMGSHPs
−Gi−j, equivalent CO2 emissions from the GSHPs for heating greenhouse i (G1 or G2) be driven
by electricity generated in power plant j (CFPP or GFPP), kg CO2 eq.; MGSHPS-Gi−j, the coal or
natural gas consumed in power plant j (CFPP or GFPP) for generating the electricity that the
GSHPs had used for heating greenhouse i (G1 or G2), kg C or kg CH4; MR22,Gi, the amount of
the refrigerant R22 in the GSHPs be allotted for heating greenhouse i (G1 or G2), kg; fj− co2 2,
the CO 2 emissions coefficient of fossil energy (coal or natural gas) in power plant j (CFPP or
GFPP), kg CO2 eq. (kg C)−1 or kg CO2 eq. (kg CH4)−1; fR22− co2, the equivalent CO2 emissions
coefficient of R22, kg CO2 eq. kg−1 R22; and fR22−leak, the leaking fraction of total R22, %.
The carbon (C) or natural gas (assumed to be 100% as CH4 in calculating CO2 emissions)
consumed to produce the electricity consumed by the GSHPs was estimated for the CFPP and
GFPP based on Eq. 2.
3600 ELEGSHPs ,Gi

MGSHPs - Gi - j = (2)
CVj
where ELEGSHPs,Gi, total electricity consumed by the GSHPs in heating greenhouse i (G1 or G2)
during winter production, kWh; and CVj, conversion factor between heat and electricity in
CFPP or GFPP, 0.27 was used for CFPP, and 0.42 was applied to GFPP in this study [29].
The GHG emissions from the GSHPs were compared with two primary greenhouse heating
systems used in northern China: the CFHs and the CFHs. The equivalent quantity of CO2
emissions from the GSHPs, CFHs, and GFHs was quantified based on the same heat energy
provided by the GSHPs during whole winter for the G1 and G2 (Eqs. 3–6). In northern China,
the heating efficiencies of CFHs and GFHs were considered as 0.6 and 0.8, respectively [27, 29].
HEGSHPs,Gi
Mcarbon - Gi = (3)
Fcarbon - heat * fC - HE
HEGSHPs,Gi
MGas - Gi = (4)
Fgas - heat* fG-HE
EM CFHs,Gi = MCarbon - Gi * fC - co2 (5)
EM GFHs,Gi = MGas - Gi * fG - co2 (6)
where EMCFHs, CO2 emissions from greenhouse CFHs, kg CO2; EMGFHs, CO2 emissions from
greenhouse GFHs, kg CO2; fC−CO2, CO2 emissions coefficient of the CFHs, kg CO2 (kg C)−1; fG−co2,
CO2 emissions coefficient of the natural GFHs, kg CO2 (kg CH4)−1; fC−HE, the heating efficiency
of the CFHs, dimensionless; fG−HE, the heating efficiency of the GFHs, dimensionless; Fcarbon−heat,
specific calorific value of burning per kg carbon, MJ (kg C)−1; Fcarbon−heat, specific calorific value
of burning per kg natural gas, MJ (kg CH4)−1; Mcarbon−Gi, the carbon consumed in heating
greenhouse i (G1 or G2) during whole winter, kg C; Mgas−Gi, the natural gas consumed in heating
greenhouse i (G1 or G2) during whole winter, kg CH4; and MR22−Gi, the R22 used in the GSHPs
be attributed to greenhouse i (G1 or G2) based on the proportion of heat energy received by
G1 and G2, kg.
Under the normal temperature and atmospheric pressure (288 K and 1 atm), burning a
kilogram of the standard coal (C) and natural gas (CH4) in oxygen (O2) completely has potential
to emit 3.67 and 2.75 kg CO2, respectively, with Eqs. 7 and 8 [30]. Meanwhile, the Fcarbon−heat and
Fgas−heat were quantified as 29.3 and 52.6 MJ for burning each kilogram of the C and CH4,
respectively.
1 kg C + 2.67 kg O 2 ® 3.67 kg CO 2 + 29.3 MJ energy (7)
1 kg CH 4 + 4 kg O 2 ® 2.75 kg CO 2 + 2.25 kg H 2 O + 52.6 MJ energy (8)
Total GHG emissions from greenhouses heating in Beijing can be estimated based on the total
area of greenhouses (similar to G1 or G2) and heat rate per square greenhouse floor (Eqs. 9–
11):
AG1, Beijing ´ fG1,heating EM GSHPs,G1- elej A G2, Beijing ´ fG2,heating EM GSHPs,G2 - elej
EMG Beijing ,GSHPs, j = + (9)
480 756
AG1, Beijing ´ fG2,heating EM CFHs ,G1 A G2, Beijing ´ fG2,heating EM CFHs ,G2
EMG Beijing ,Carbon = + (10)
480 756
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AG1, Beijing ´ fG2,heating EM GFHs,G1 A G2, Beijing ´ fG2,heating EM GFHs,G2

EMG Beijing ,gas = + (11)
480 756
Where, EMGBeijing,GSHPs, j , equivalent CO2 emissions from the GSHPs heating for greenhouses
similar to G1 and G2 be driven electricity generated in the power plant j (CFPP or GFPP), kg
CO2 eq. in Beijing; EMGBeijing,carbon, equivalent CO2 emissions from the CFHs heating for
greenhouses similar to G1 and G2 in Beijing, kg CO2 eq; and EMGBeijing,gas, equivalent CO2
emissions from the GFHs heating for greenhouses similar to G1 and G2 in Beijing, kg CO2 eq.
3. Results and Discussion
3.1. Emissions from the GSHPs
Total heat energy provided by the GSHPs for G1 and G2 were 149270.4 and 640659.1 MJ during
2007–2008 winter at the electricity consumptions of 10826.1 and 44372.2 kWh, respectively.
The electricity consumed by the GSHPs usually came from the power plants of CFPP and GFPP
in northern China. Therefore, the difference between the CFPP and GFPP in producing GHG
at different stages of the SGE in the GSHPs was compared (Table 4).
SGE extraction SGE promotion SGE heating Inventory
Electricity from CFPP

G1 electricity consumption, kWh 2440.6 7135.5 1250.3 10826.4
G1 standard coal consumption, kg C 1095.5 3202.7 561.2 4859.4
G1 GHG emissions, kg CO2 eq. 4020.3 11754.0 2059.5 17833.8
G2 standard coal consumption, kg C 4489.8 13126.4 2300.0 19916.2
G2 GHG emission, kg CO2 eq. 16477.4 48174.0 8440.9 73092.3
Electricity from GFPP
G1 natural gas consumption, kg CH4 397.7 1162.8 203.7 1764.2
G1 GHG emissions, kg CO2 eq. 1093.7 3197.6 560.3 4851.6
G2 natural gas consumption, kg CH4 1630.0 4765.6 835.0 7230.7
G2 GHG emission, kg CO2 eq. 4482.6 13105.4 2296.3 19884.3
Note: (1) G1=480m2, heated with GSHPs for 146 days; G2=756 m2, heated with GSHPs for 111 days. (2) In calculating the
CO2 emissions, the CH4 was assumed to be 100% chemical component of the natural gas.
Table 4. GHG emission from G1 and G2 heating with GSHPs.

In producing the amount of the electricity consumed by the GSHPs for G1 and G2, about 4.9
and 20 t of coal (C) were consumed in CFPP. If use the GFPP produced electricity, the total
natural gas burned could be 1.8 and 7.2 t (CH4). During 2007–2008 winter heating, the GWP
of the GHG emissions from G1 and G2 (Figure 4) was estimated to be 18.3 and 74.9 t CO2 eq.
with the CFPP and 5.3 and 21.7 t CO2 eq. with the GFPP, respectively, over a 20-year time
horizon. The GWP of 100a was 1.5%–1.6% lower than 20a for G1 and 5.3%–5.4 % lower than
20a for G2 due to the reduced GWP on R22. Similar to HCFC-22, R22 has shorter atmospheric
lifetime [5]. Generally, the CO2 eq. contributed by the leak of R22 accounted for 2.4% and 8.4%
in the scenarios of CFPP and GFPP, respectively.
100
Global warming potential, Mg CO 2 eq.
90
20a GWP
80 74.9 73.8
100a GWP
70
60
50
40
30
21.7 20.6
18.3 18.0
20
10 5.3 5.0
0
G1 CFPP G2 CFPP G1 GFPP G2 GFPP
Power Sources
Figure 4. GWP of the GHG emissions derived from the GHSPs heating in G1 and G2.
Among different stages of the SGE flow, most GHG emissions (66%) happened at the stage of
SGE promotion due to the higher consumption of electricity in compressors. Therefore,
improving the efficiency of the compressors has the potential to reduce the GHG emissions
from the GHSPs heating.
3.2. Greenhouse gas emissions from fossil energy systems
Providing G1 and G2 with the same quantity of heat that the GSHPs has provided (i.e., 149270.4
and 640659.1 MJ) requires the CFHs to consume 8.49 and 36.40 t of standard coal and the GFHs
to consume 3.55 mg (4964 m3 at 288 K and 1 atm) and 15.22 t (21,304 m3 at 288 K and 1 atm) of
natural gas (CH4), respectively. Accordingly, the GHG emissions from heating G1 and G2
(Figure 5) were estimated to be 32.7 and 133.7 t CO2 eq. for the CFHs system and 9.8 and 41.8
t CO2 eq. for the GFHs system.
3.3. Standardized GHG emissions from greenhouse heating
The unit electricity consuming rate of the GSHPs was 0.15 and 0.53 kWh m−2 d−1 for heating
G1 and G2 and which can be standardized as 1500 and 5300 kWh ha−1 d−1 in Beijing during
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Mg CO2 eq.
160
CFPP-GSHP
140 GFPP-GSHP
133.7
120 CFHs
The GHG emissions from different systems

GFHs
100
74.9
80
60
41.8
40 32.1
18.3 21.7
20 9.8
5.3
0
G1 G2
Greenhouse types
Figure 5. The GHG emissions from the GHSPs and the fossil energy systems.
2007–2008 winter. The 20a and 100a GWPs of the GHG emissions from the GSHPs heating for
G1 and G2 (Figure 6a) were 0.076–0.893 and 0.072–0.879 g CO2 eq. m−2 d−1, respectively. The
GHG emission rate of G2 is 3.42 times of G1 because Chinese solar greenhouse has better heat-
preserving capacity than multispan greenhouses.
Regarding to the CFHs and GFHs, the standardized GWPs of the GHG emissions (Figure 6b)
were 0.142–1.214 CO2 eq. m−2 day−1, and there were no difference between 20a and 100a because
the GWP of the CO2 will not change with the time.
1.0
0.893 0.879
The GHG emission rate, kg CO2 eq m-2 d -1
0.9
20a GWP
0.8
100a GWP
0.7
0.6
0.5
0.4
0.3 0.261 0.257 0.259 0.245
0.2
0.1 0.076 0.072
0.0
G1 CFPP G2 CFPP G1 GFPP G2 GFPP
Greenhouses and energy sources
(a) The shallow geothermal energy
1.4
1.214 1.214
sion rate, kg CO2 eq m-2 d -1
1.2 20a GWP

100a GWP
1.0
0.8
0.6
0.464 0.464
0.2
The G
0.1 0.076 0.072
0.0
236 Greenhouse Gases G1 CFPP G2 CFPP G1 GFPP G2 GFPP
(a) The shallow geothermal energy
1.4
1.214 1.214
The GHG emision rate, kg CO2 eq m-2 d -1

1.2 20a GWP
100a GWP
1.0
0.8
0.6
0.464 0.464
0.379 0.379
0.4
0.2 0.142 0.142
0.0
G1 CFHs G2 CFHs G1 GFHs G2 GFHs
(b) The fossil energy
Figure 6. Standardized GHG emissions (GWP) for different greenhouse types and energy sources.
3.4. Emissions inventory in Beijing, China
According to the areas of the G1 and G2 in Beijing that require assisted heating (6000 ha Chinese
solar greenhouses-G1 and 1000 ha multispan greenhouses-G2), the total GHG emissions from
greenhouses heating with the CFHs or GFHs were quantified as 5238 or 2294 Mt CO2 eq. in
Beijing, and there is no difference between 20a and 100a GWP (Figure 7).
6000
20a GWP 5238
The GHG emissions, Mt CO2 eq yr-1
5000 100a GWP
4013
4000
3000
2294
2000 1748
1225
1000
546
0
G1-CFHs G2-CFHs G1-GFHs G2-GFHs CFHs GFHs
Greenhouse types and energy sources
Figure 7. Total GHG emissions from heating greenhouses with fossil energies in Beijing.(G1-CFHs, heating all the G1-
type greenhouses in Beijing with CFHs; G2-CFHs, heating all the G2-type greenhouses in Beijing with CFHs; G1-GFHs,
heating all the G1-type greenhouses in Beijing with GFHs; G2-GFHs, heating all the G2-type greenhouses in Beijing
with GFHs).
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The total GHG emissions from heating greenhouses in Beijing with the GSHPs were quantified
as 1658 and 2909 Mt CO2 eq., based on 20a GWP or 1619 and 2839 Mt CO2 eq. based on 100a
GWP (Figure 8). The GHG emissions from heating G1-type greenhouses are higher than
heating G2-type of greenhouses due to the large area of the G1 built and used in Beijing during
2007–2008 winter.
3500
20a GWP
3000 2909
2839
The GHG emissions, Mt CO2 eq yr-1
100a GWP
2500 2255 2220
2000
1658 1619
1500 1285 1266
1000
654 619
500 372 353
0
G1-CFPP G2-CFPP G1-GFPP G2-GFPP CFPP GFPP
Greenhouse types and energy sources
Figure 8. Total GHG emissions from heating greenhouses with the GSHPs in Beijing (G1-CFPP, heating all the G1-type
greenhouses in Beijing with the GSHPs be powered with the electricity generated in CFHs; G2-CFPP, heating all the
G2-type greenhouses in Beijing with the GSHPs be powered with the electricity generated in CFHs; G1-GFPP, heating
all the G1-type greenhouses in Beijing with the GSHPs be powered with the electricity generated in GFHs; G2-GFPP,
heating all the G2-type greenhouses in Beijing with the GSHPs be powered with the electricity generated in GFHs).
Applying the GSHPs to heat G1 and G2 with the electricity from the CFPP, the equivalent
CO2 emissions were 43% and 44% lower than directly burning coal with the CFHs but were
46.4% and 44.2% higher than the GFHs that burning natural gas. However, when using the
GFPP generated electricity to run the GSHPs, the equivalent CO2 emissions would be 83.5%
and 83.8% lower than directly burning coal with the CFHs and were 45.9% and 48.1% lower
than the GFHs that burning natural gas.
3.5. Uncertainty evaluation
It was assumed that all the solar greenhouse and multispan greenhouses with the same heating
rate of G1 and G2 in this study, which would lead to errors due to the varying structures and
materials in different greenhouses. For the solar greenhouses with improved wall materials
and structures, the heat loss and heating rate would be lower [31]. Besides, heat-preserving
technologies, such as multilayer aluminum foil heat reflecting materials, would have lower
heat loss and heating rate than G2 in this study [3].
The shallow geothermal heat used in the GSHPs came from the groundwater (14°C), which
has different GHG emissions from the borehole or U-tube-based HPs [19, 32]. Besides, the
leaking factor of R22 was assumed to be 2% per year based on European studies, which may
be changing with the change of the pump unit and maintenance of the system.
The GHG emissions calculated in this study are based on the real heating quantity required
by G1 and G2 during winter heating, and the cycle of the SGE from extraction, enhance, and
greenhouse heating was considered, the analysis can be considered as a partial life cycle
assessment (LCA). However, a full LCA analysis could be applied to account the GHG
emissions from greenhouse constructing with different materials, the transportation of the coal
or natural gas for the location of the greenhouses, and the plants cultivated in the greenhouses
[33-35].
In this study, we assumed that all the G1-type Chinese solar greenhouses would need
additional heating in calculating the GHG emissions. However, novel structures and materials
were applied for building Chinese solar greenhouses in Beijing in recent years [36], which
improved the heat-preserving capacity of the greenhouse so that heating was not required in
winter time. Therefore, the GHG emissions from heating Chinese solar greenhouse could be
lower than the amount calculated in this study.
4. Summary
The unit electricity consuming rate of the GSHPs were 0.15 and 0.53 kWh m−2 d−1 for heating
the Chinese solar greenhouse (G1) and multispan greenhouse (G2) or expressed as 1500 and
5300 kWh ha−1 d−1 in Beijing. The 20a and 100a GWPs of the GHG emissions from the GSHPs
heating for G1 and G2 were 0.076–0.893 and 0.072–0.879 g CO2 eq. m−2 d–1, respectively.
The total GHG emissions from heating greenhouses in Beijing with the GSHPs were quantified
as 1658–2909 Mt CO2 eq. Among different stages of the SGE flow, most GHG emissions (66%)
happened at the stage of SGE promotion due to the higher consumption of electricity in
compressors.
The total GHG emissions from greenhouses heating with the CFHs or GFHs were quantified
as 5238 and 2294 Mt CO2 eq. in Beijing, respectively. Applying the GSHPs to heat G1 and G2
with the electricity from the CFPP, the equivalent CO2 emissions were 43% and 44% lower than
directly burning coal with the CFHs but were 46.4% and 44.2% higher than the GFHs that
burning natural gas. However, when using the GFPP-generated electricity to run the GSHPs,
the equivalent CO2 emissions would be 83.5% and 83.8% lower than directly burning coal with
the CFHs and were 45.9% and 48.1% lower than the GFHs that burning natural gas.
The glass-covered G2 consumed more heating energy than G1 during the heating period. This
demonstrated that the Chinese solar greenhouse design had better heat preservation than the
glass greenhouse. Besides, novel structures and materials applied for building Chinese solar
greenhouses in Beijing could further reduce the GHG emissions from heating.
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Acknowledgements
The study was sponsored by the “Beijing Natural Science Foundation (6132011),” “Young
Researcher Foundation (QNJJ201212)” in Beijing Academy of Agricultural and Forestry
Sciences, “Earmarked Fund for Modern Agro-industry Technology Research System
(CARS-25-D-04),” and “Twelve-Five-Year National Science and Technology Support Program
(2011BAD12B01).”
We also thank the support from the program of "Promotion network of research and applica‐
tion services on vegetables varieties (KJCX20140416)".
Author details
Lilong Chai1,2*, Chengwei Ma3, Baoju Wang1,4, Mingchi Liu3,4 and Zhanhui Wu3,4
*Address all correspondence to: lchaipurdue@gmail.com
1 National Engineering Research Centre for Vegetables, Beijing Academy of Agriculture and
Forestry Sciences, Beijing, P.R. China
2 Department of Agricultural and Biosystems Engineering, Iowa State University, Ames,

USA
3 College of Water Resource and Civil Engineering, China Agricultural University, P.R.
China, Beijing, P.R. China
4 Key Laboratory of Urban Agriculture (North), Ministry of Agriculture, P.R. China, Beijing,
P.R. China
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Chapter 11
Livestock as Sources of Greenhouse Gases and Its

Significance to Climate Change
Veerasamy Sejian, Raghavendra Bhatta, Pradeep Kumar Malik,

Bagath Madiajagan, Yaqoub Ali Saif Al-Hosni, Megan Sullivan and
John B. Gaughan
http://dx.doi.org/10.5772/62135
Abstract
This chapter outlines the role of livestock in the production of greenhouse

gases (GHGs) that contributes to climate change. Livestock contribute both di‐
rectly and indirectly to climate change through the emissions of GHGs such
as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). As animal
production systems are vulnerable to climate change and are large contribu‐
tors to potential global warming, it is vital to understand in detail enteric CH4
emission and manure management in different livestock species. Methane
emissions from livestock are estimated to be approximately 2.2 billion tonnes
of CO2 equivalents, accounting for about 80% of agricultural CH4 and 35% of
the total anthropogenic CH4 emissions. Furthermore, the global livestock sec‐
tor contributes about 75% of the agricultural N2O emissions. Other sources of
GHG emission from livestock and related activities are fossil fuels used for as‐
sociated farm activities, N2O emissions from fertilizer use, CH4 release from
the breakdown of fertilizers and from animal manure, and land-use changes
for feed production. There are several techniques available to quantify CH4
emission, and simulation models offer a scope to predict accurately the GHG
emission from a livestock enterprise as a whole. Quantifying GHG emission
from livestock may pave the way for understanding the role of livestock to
climate change and this will help in designing appropriate mitigation strat‐
egies to reduce livestock-related GHGs.
Keywords: climate change, enteric methane, GHG, livestock, manure management, mod‐
eling
1. Introduction
The Intergovernmental Panel on Climate Change (IPCC), convened by the United Nations,
has reported evidence that human activities over the past 50 years have influenced the global
climate through the production of GHG [1]. Increasing concentrations of GHGs in the atmos‐
phere have contributed to an increase in the Earth’s atmospheric temperature, an occurrence
known as global warming [2]. Indeed, average global temperatures have risen considerably,
and the IPCC [1] predicts increases of 1.8–3.9ºC (3.2–7.1ºF) by 2100. With business as usual,
Earth’s temperature may rise by 1.4–5.8ºC by the end of this century, and the scientific
community warns of more abrupt climatic change in the future [3].
The livestock sector accounts for 40% of the world's agriculture gross domestic product
(GDP). It employs 1.3 billion people and creates livelihoods for one billion of the world's
population living in poverty [2]. As animal production systems are vulnerable to climate
change and are large contributors to potential global warming through methane (CH4) and
nitrous oxide (N2O) production, it is vital to understand in detail enteric CH4 emission and
manure management in different livestock species [4]. Before targeting GHG reduction
strategies from enteric fermentation and manure management, it is important to under‐
stand the mechanisms of enteric CH4 emission in livestock, the factors influencing such
emission. In addition, an understanding of the available prediction models and estimation
methodology for quantification of GHGs is essential. A thorough understanding of these will
in turn pave way for formulation of effective mitigation strategies for minimizing enteric CH4
emission in livestock [5].
This chapter will focus on four main areas: (i) livestock’s role as a source of GHGs, and the
contribution that this makes to climate change; (ii) enteric CH4 emission and manure manage‐
ment related to CH4 and N2O as primary sources of GHGs related to livestock activities; (iii)
the methodologies used to quantify enteric emission; and (iv) modeling of GHGs in livestock
farms as important step towards finding solution for livestock-related climate change.
2. Livestock and climate change from global food security perspectives
FAO estimated that 1526 million cattle and buffaloes and 1777 million small ruminants are
being maintained globally. The population of cattle and buffaloes and small ruminants is
expected to be 2.6 and 2.7 billion, respectively, by the year 2050. Furthermore, livestock are an
integral element of agriculture that supports the livelihood of more than 1 billion people across
the globe. This sector satisfies more than 13% of the caloric and 28% of the protein requirements
of people worldwide. The global demand for milk, meat, and eggs is expected to increase by
30%, 60%, and 80%, respectively, by the year 2050 in comparison to the 1990 demand. This
increased requirement will be fulfilled either by increasing the livestock numbers or through
intensifying the productivity of existing stock.
Climate change is seen as a major threat to the survival of many species, ecosystems, and the
sustainability of livestock production systems in many parts of the world [6]. The growing
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Livestock as Sources of Greenhouse Gases and Its Significance to Climate Change 245
http://dx.doi.org/10.5772/62135
human population will almost doubled the global requirement for livestock products by 2050.
It is during the same period adverse changes in the climate are also expected. Recent industrial
developments have curtailed the land used for agricultural activities, considerably threatening
food security in both developed and developing countries. Hence, livestock production has a
key role to play in bringing food security to these countries. We need high-quality research in
animal science to meet the increasing demand for livestock products in the changing climate
scenario [7].
3. Livestock as source of greenhouse gas (GHGs)
Livestock contributes both directly and indirectly to climate change through the emissions of
GHGs such as CO2, CH4, and N2O [8]. Globally, the sector contributes 18% (7.1 billion tonnes
CO2 equivalent) of global GHG emissions. Although it accounts for only 9% of global CO2, it
generates 65% of human-related N2O and 35% of CH4, which has 310 times and 23 times the
global warming potential (GWP) of CO2, respectively [9] (Fig. 1).
Figure 1. Different sources of GHGs from livestock sector.
There are two sources of GHG emissions from livestock: (a) enteric fermentation where specific
microbes residing in the rumen produce CH4 as a by-product during digestion and (b)
anaerobic fermentation of livestock manure producing CH4 and denitrification and denitrifi‐
cation of manure producing N2O. Methane production appears to be a major issue and largely
arises from natural anaerobic ecosystems, and fermentative digestion in ruminant animal [10].
Much of the global GHG emissions currently arise from enteric fermentation and manure from
grazing animals. The development of management strategies to mitigate CH4 emissions from
ruminant livestock is possible and desirable. Carbon dioxide (CO2) are also produced in
livestock farms and are primarily associated with fossil fuel burning during operation of farm
machineries in the process of fertilizer production, processing and transportation of refriger‐
ated products, deforestation, desertification, and release of carbon from cultivated soils.
Enhanced utilization of dietary “C” will improve energy utilization and feed efficiency hence
animal productivity, decrease overall CH4 emissions, and thereby reduce the contribution of
ruminant livestock to the global CH4 inventory.
Ruminant animals, such as cattle, sheep, buffaloes, and goats, are unique due to their special
digestive systems, which can convert plant materials that are indigestible by humans into
nutritious food. In addition to food, these animals also produce hides and fibers that are
utilized by humans. This same helpful digestive system, however, produces CH4, a potent
GHG that can contribute to global climate change. Livestock production systems can also emit
other GHGs such as N2O and CO2. The most important GHGs are CO2, CH 4, and N2O, all of
which have increased in the last 150 years and have different global warming potential.
According to Sejian et al. [11], the warming potential of CO2, CH4, and N2O are 1, 25, and 310,
respectively. Taking into account the entire livestock commodity chain – from land use and
feed production, to livestock farming and waste management, to product processing and
transportation – about 18% of total anthropogenic GHG emissions can be attributed to the
livestock sector [2].
Livestock production is the largest global source of CH4 and N2O – two particularly potent
GHGs [12, 13]. The principal sources of N2O are manure and fertilizers used in the production
of feed. The biggest source of CH4 is from enteric fermentation. The rising demand for livestock
products therefore translates into rising emissions of CH4 and N2O. According to one study,
if current dietary trends (increasing global consumption of animal products) were to continue,
emissions of CH4 and N2O would more than double by 2055 from 1995 levels [14].
3.1. Enteric methane emission
Worldwide livestock emits around 7.1 Gt CO2-eq GHGs per year, which accounts for 15% of
the human induced GHGs emissions. Additionally, 5.7 Gt CO2-eq GHGs is also emitted from
the ruminant supply chain wherein cattle, buffaloes, and small ruminant production contrib‐
ute 81%, 11%, and 8%, respectively. Methane emissions from livestock have two sources, one
from enteric fermentation and another from excrement. Enteric fermentation in ruminants
annually contributes ~90 Tg CH4 to the atmospheric pool, while ~25 Tg comes from the
excrement. Apart from the role of enteric CH4 in global warming, its emission from the animal
system lead to a loss of biological energy (6–12% of intake), which otherwise would have been
utilized by the host animal for various productive functions. Reducing the loss of energy in
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the form of enteric CH4 is crucial, especially in developing countries like India where feed and
fodder availability is already in short supply.
3.1.1. Indian livestock and enteric methane emission
India has approximately 512 million livestock (19th Livestock census, Government of India).
Of the total livestock population, about 60% are cattle and buffaloes, which comparatively emit
more enteric CH4 than any other livestock species. Emissions of enteric CH4 can be elevated
when these species are fed fibrous feeds. Estimations of enteric CH4 emissions from Indian
livestock have been calculated using different approaches (Table 1). There is a lack of consis‐
tency in the published data; some have reported very high emissions from Indian livestock
while others have reported much lower emissions [15]. This large variation in predicted enteric
CH4 emission from Indian livestock is attributed to the different approaches used for the
calculation of emissions. The average of the published data is in the range of 9–10 Tg per year,
which appears to be a realistic value. Methane emissions from excrement in India are low
because the disposal system (generally stored as heap in the open environment) does not
support the favorable anaerobic conditions required by methanogens. However, in the
developed world where excrement is mainly stored in lagoons, manure is a major source of
CH4 emissions.
Source Base year Emission (Tg/yr) Approach
Ahuja [16] 1985 10.40 Default CH4 emission factors
ALGASa [17] 1990 18.48 IPCC methodology
In vitro gas production and dry matter

Singh [18] 1992 9.02
digestibility coefficients
Garg and Shukla [15] - 7.25 -
EPAb [19] - 10.04 -
Swamy and Bhattacharya [20] 1994 9.0 Methane emission factors
Jha et al. [21] 1994 8.97 IPCC tier II
Chhabra et al. [22] 2003 10.65 GIS approach
In vitro gas production, feeding practices in

Singh et al. [23] 2003 9.10
different agro-ecological regions
Patra [24] 2010 14.3 IPCC tier 1
a
Asia Least-Cost Greenhouse Gas Abatement Strategy.
b
United States Environmental Protection Agency.
Table 1. Estimates of enteric methane emission from Indian livestock

Based on the IPCC default emission factors, Kamra [25] determined the enteric CH4 emission
from Indian livestock. Buffalo, yak, and mithun contribute a maximum of 55 kg CH4/head/yr;
however, sheep and goat contribute only 5 kg/head/yr. The enteric CH4 emission from
crossbred cattle is much higher than the indigenous cattle (46 vs 25 kg/head/yr). Both cattle
and buffaloes aggregately emit more than 90% of the total enteric CH4 from livestock, while
sheep and goat together contribute around 7.70% (Fig. 2). Pig production is the next major
emitter contributing 0.57% of the total enteric CH4 emission from livestock in India. The
contribution from other livestock species is negligible.
Figure 2. % Species wise enteric methane emission (modified from Kamra [25]).
3.1.2. Why rumen methanogenesis is an obligation
The rumen is the harbor for diverse anaerobic microbe populations that accomplish different
functions from degradation of complex carbohydrates to the removal of fermentation metab‐
olites in a syntrophic way [26]. H2, which is produced in large volumes during enteric
fermentation, needs to be removed from the anaerobic vat in order to maintain favorable
rumen conditions for both the rumen microbes and host animal. Under normal rumen
functioning, metabolic H2 is used for the reduction of CO2 to CH4, which in turn is eructated
into the atmosphere via the mouth and nostrils. The microbes of the so-called archaea or
methanogens are the CH4 producing machinery inside the rumen. The majority of the rumen
methanogens are hydrogenotrophic, which utilize H2 as a substrate for methanogenesis.
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Rumen methanogenesis is a necessary but energy-wasteful process as it corresponds to a

significant loss of biological dietary energy (6–12% of intake) in the form of CH4.
Among the various end products of rumen fermentation, H2 is a central metabolite where its
partial pressure in the rumen determines the extent of methanogenesis and the possible extent
of oxidation of feedstuffs [27]. H2 in the rumen is generally referred as currency of fermenta‐
tion [27]. The removal of H2 from the rumen is a prerequisite for the continuation of rumen
fermentation. However, the methanogens constitute only a small fraction of the rumen
microbial community, but they are very crucial in H2 utilization [28]. Apart from the metha‐
nogenesis, other hydrogenotrophic pathways (reductive acetogenesis, sulfate and nitrate
reduction) are also present in the rumen, but the extent of H2 utilization through these
pathways is not clear. In order to keep the rumen functional and the animal alive, rumen
methanogenesis is the primary and thermodynamically efficient way of metabolic H2 disposal
from the rumen, and that is why it is generally regarded as a necessary but wasteful process.
3.1.3. Enteric methane estimation methodology
Several methods are available for measuring enteric CH4 production, and the selection of the
most appropriate method is based on several factors such as cost, level of accuracy, and
experimental design [29, 30].
3.1.3.1. Individual animal techniques
By far, the most suitable method to quantify individual ruminant animal CH4 measurement is
by using respiration chamber, or calorimetry. The respiration chamber models include whole
animal chambers, head boxes, or ventilated hoods and face masks. These methods have been
effectively used to collect information pertaining to CH4 emissions in livestock. The predom‐
inant use of calorimeters has been in energy balance experiments where CH4 has been
estimated as a part of the procedures followed. Although there are various designs available,
open-circuit calorimeter has been the one widely used. There are various designs of calorim‐
eters, but the most common one is the open-circuit calorimeter, in which outside air is
circulated around the animal’s head, mouth, and nose and expired air is collected for further
analysis.
3.1.3.2. Tracer gas techniques
Methane emission from ruminants can be estimated by using the ERUCT technique (Emissions
from Ruminants Using a Calibrated Tracer). The tracer can either be isotopic or nonisotopic.
Isotopic tracer techniques generally require simple experimental designs and relatively
straightforward calculations [31]. Isotopic methods involve the use of (3H-)CH4 or
(14C-)CH4 and ruminally cannulated animals.
3.1.3.3. Sulphur hexafluoride (SF6) technique
Nonisotopic tracer techniques are also available for measurement of CH4 production. John‐
son et al. [32] described a technique using SF6, an inert gas tracer. This method has been
widely used in sheep and cattle. Methane emission rates are calculated based on the equa‐
tion QCH4 = QSF6 × [CH4] / [SF6], where QCH4 is the emission rate of CH4 in g/day, QSF6 is
the known release rate (g/day) of SF6 from the permeation tube, and [CH4] and [SF6] are the
measured concentrations in the canister.
3.1.3.4. In vitro gas production technique (IVGPT)
Various aspects of in vitro gas production test have been reviewed by Getachew et al. [33], and
these authors reported that gas measurement were centered on investigations of rumen
microbial activities using manometric measurements and concluded that these methods do
not have wide acceptability in routine feed evaluation since there was no provision for the
mechanical stirring of the sample during incubation. Another in vitro automated pressure
transducer method for gas production measurement was developed by Wilkins [34], and the
method was validated by Blummel and Orskov [35] and Makkar et al. [36]. There are several
other gas-measuring techniques such as (i) Hohenheim gas method or Menke’s method [37];
(ii) liquid displacement system [38]; (iii) manometric method [39]; (iv) pressure transducer
systems: manual [40], computerized [41], and combination of pressure transducer and gas
release system [42].
3.2. Livestock manure as an important source of GHGs
In addition to enteric CH4 production, livestock manure contributes directly and indirectly to
GHG gas production via CH4, N2O, and CO2 production. Manure from livestock includes both
dung and urine. Manure management plays a key role in amount of CH4 and N2O produced
and liberated into the environment. The amount of CH4 produced in solid-state manure
management contribute less when compared to liquid state. However, dry anaerobic man‐
agement system provides suitable environment for N2O production. The liquid/slurry manure
systems provide favorable environments for the growth of the microbes, which in turn
enhances the CH4 gas production. Various factors that affect CH4 and N2O production include
the amount of manure, the VFA present, the type of feed, the management systems, and the
ambient temperature. In addition, the duration of the storage of waste also influences N2O
production,
3.2.1. Methane emission from manure management
Anaerobic digestion processes occur in manure with the help of microbial consortia to
produce CH4 and CO2 and consists of four phases: (i) hydrolysis of complex organic
particulate matter into simpler low molecular weight compounds; (ii) acidogenesis of simpler
low molecular weight organic compounds to organic acids and alcohol; (iii) acetogenesis of
organic acids and alcohols to H2, CO2, acetic acid, and acetate; and (iv) methanogenesis
involves the consumption of acids or hydrogen to produce CH4 and CO2. The aforemen‐
tioned four phases are done by four different groups of bacterial consortia, namely, hydrolyt‐
ic bacteria, acidogenic bacteria, acetogenic bacteria, and methanogenic bacteria, respectively
[43]. CH4 is also emitted from the collection yard, but it is a minor source. The greatest amount
of CH4 is emitted during storage especially in slurry, the reason being the prevalence of
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complete anaerobic environment. Solid manure also acts as a source of CH4 emission. CH4 is
emitted immediately after manure application to the field; however, once the O2 diffuses into
manure, it inhibits CH4 production [44].
3.2.1.1. Factors affecting methane production from manure
There are several factors that affect the CH4 production from manure, which includes tem‐
perature, organic matter present, microbe load, pH, moisture, and type of feed. However,
CH4 emitted from manure depends primarily on (i) the management system such as solid
disposal system, liquid disposal systems, e.g., ponds, lagoons, and tanks, which can emit up
to 80% of manure-based CH4 emissions, while solid manure emits little or no CH4. (ii) Envi‐
ronmental conditions are also important. The higher the temperature and moisture, the more
CH4 produced. (iii) CH4 emissions also depend on the quantity of the manure produced, which
depends on the number of animals housed, the amount of feed the consumed, and the
digestibility of the feed. (iv) Manure characteristics depend on the animal type, feed quality,
and rumen microbes present in the rumen and digestive tracks. Manure handled in liquid form
tends to release more amount of CH4 when compared to solid or manures thrown into the
pasture, which do not decompose anaerobically. High temperatures with neutral pH and high
moisture content enhance CH4 production [45].
3.2.2. Nitrous oxide emission from manure management
Nitrous oxide is produced from manure by nitrification, denitrification, leaching, volatiliza‐

tion, and runoff. Nitrification and denitrification are direct emissions. N2O is 16 times more
potent than CH4 and 310 times more potent than CO2 over a 100-year period [46]. N2O acts as
a source of NO in the stratosphere, which indirectly causes depletion of ozone (O3), increasing
UV radiation reaching the Earth’s surface [47]. An increase in animal stocking rates and
intensive gazing results in the deposition of huge amounts of N via animal excreta (urine +
dung); farm management practices that enhance soil organic N mineralization also lead to N2O
production [1, 48, 49].
3.2.2.1. Mechanism of nitrous oxide production
The emission of N2O from manure occurs directly by both nitrification and denitrification of
nitrogen contained in the manure. This emission mainly depends on the N and C content of
the manure during various types storage and treatment. The nitrification process strictly needs
oxygen, while subsequent denitrification is an anaerobic process.
Manure from livestock mixes with the soil or in the tank, lagoons, etc., where the microbes
break down organic N to inorganic NH4+ through mineralization. In this step, the organic N
becomes available for plants and microorganisms. Microorganisms (Nitrosomonas genus) can
take up NH4+ and oxidize it to nitrite (NO2-). In the next step, Nitrobacter and Nitrococcus oxidize
NO2- to nitrate (NO3-) by nitrification. This process of oxidation of NH4+ to NO3- is known as
nitrification, which is also done by other genera like Nitrosococus and Nitrosospira and subge‐
nera Nitrosobolus and Nitrosovibrio [50, 51].
Studies show that N2O was emitted from animal houses at the rate of 4–5 mg N m-2 d-1, with
straw as bedding material, whereas when no bedding material was used, little or no N2O was
emitted from slurry-based cattle or pig building as complete anaerobic condition would have
maintained [52]. Deep litter system with fattening pigs showed much higher emission
compared to slurry based pig houses, while mechanical mixing still further increased N2O
emission [53]. In cattle collection yards, there had been very less or no N2O emission as the
anaerobic condition prevents conversion of NH4+ to NO3-.
Stored solid manures acts as a source of N2O production/consumption and emission. Covering
heaped manure shows reduction in NH3 emissions but has no effect on N2O emission, while
other studies showed that both were reduced. The addition of chopped straw reduced N2O
emission by 32% from the small scale of cattle manure. [54]. Slurry or liquid manure with no
cover showed negligible N2O release, while slurry with straw cover might act as a source of
emission [55]. N2O emission occurs following manure application to soil [56]. Various factors
that affect N2O release from soil include (i) type of manure, (ii) soil type, (iii) manure compo‐
sition, (iv) measurement period, (v) timing of manure application, (vi) amount of manure
applied, and (vii) method of application.
3.3. Other sources of GHGs from livestock farm
If all parts of the livestock production lifecycle are included, livestock are estimated to account
for 18% of global anthropogenic emissions [57]. According to Gill and coworkers [57], apart
from enteric fermentation and manure management, the other sources of GHG emission from
livestock and related activities are fossil fuels used during feed and fertilizer production and
transport of processed animal products.
4. Models for forecasting the greenhouse gas emission in livestock farms
Agricultural production is recognized as a significant contributor to GHG production.

Intensive dairy production, in particular, contributes to significant quantities of CH4 and
several forms of nitrogen (N), which can contribute to N2O production. Over the past 10 years,
research studies have attempted to address various sources of GHG emissions within the dairy
production system. These sources have included housing [58], manure removal, storage, and
treatment systems [59]. Others have compared GHG emissions from conventional farming
practices to those employed in organic production. Many of these studies have looked at one
section of the production chain in isolation. However, dairy production is a complex system
involving inputs such as feed and fertilizer, animals with inherent physiological structures for
fermentation of feedstuffs, and the production of manure, storage systems, cropping systems,
and export of meat and milk.
It is very easy to understand that attempting to design and conduct research trials to ascertain
the effect of one or multiple changes on production, economics, and GHG emissions from a
dairy production system would be expensive and time consuming. Therefore, the use of whole
farm models, with short-term studies for validation, is an attractive alternative. The integrated
www.ebook3000.com
http://dx.doi.org/10.5772/62135
farm system model (IFSM) apart from evaluating alternate agronomic feeding, manure
storage, and disposal strategies, also accounts for fossil fuel used in farming activities. In real
sense, these models do not predict production of GHG but assist in generating some basic
information required to predict GHG based on published data.
The development of whole-farm approaches for the mitigation of GHG emissions has been
taken up recently by several research groups. A common feature of whole farm models is the
ability to calculate CH4 and N2O emissions from all farm activities. Furthermore, the models
vary considerably on many other aspects. General characteristics of whole farm models include
model type, CH4 and N2O emissions, CO2 emissions, C sequestration, NH3 and NO3 emissions,
P cycling, pre chain emissions, animal welfare, economics, biodiversity, product quality, soil
quality, and landscape aesthetics [60]. Whole farm model (WFM) uses pasture growth and cow
metabolism for predicting CH4 emissions in dairy farms. Also included in the WFM is climate
and management information. However, recent reports also suggests that WFMs may
incorrectly estimate CH4 emission levels as they do not take into account the DMI and diet
composition while predicting the enteric CH4 emission. This low prediction efficiency of WFMs
may lead to substantial error in GHG inventories [10, 11].
The integrated farm system model (IFSM) is a simulation model that integrates the major
biological and physical processes of a crop, beef, or dairy farm and evaluating the overall
impact of management strategies used to reduce CH4 emissions [61, 62]. The IFSM is a process-
based whole farm simulation including major components for soil processes, crop growth,
tillage, planting and harvest operations, feed storage, feeding, herd production, manure
storage, and economics [63]. IFSM predicts the effect of management scenarios on farm
performance, profitability, and environmental pollutants such as nitrate leaching, ammonia
volatilization, and phosphorus runoff loss. The dairy greenhouse gas model (DairyGHG) is a
type of IFSM that was developed to provide an easy to use software tool for estimating GHG
emissions and the carbon footprint of dairy production systems [64]. Recently, FAO developed
a global livestock environmental assessment model (GLEAM), which reported that livestock-
related activities contributed around 7.1 gigatonnes CO2-eq per annum, indicating the
prominent contribution of livestock to climate change [65].
A whole-farm approach is a powerful tool for the development of cost-effective GHG mitiga‐
tion option. The modeling technology can be used to assess the technical, environmental, and
financial implications of alternative farm management strategies, under changing external
conditions. Whole farm models (WFMs) can reveal relevant interactions between farm
components and is useful for integrated scenario development and evaluation. Further, the
whole-farm approach ensures that the potential negative trade-offs are taken into account and
that positive synergies are identified. In addition, the whole farm models are also used to
explore future farm strategies, and since it is operated on farming level, it also provides
opportunity for farmers to learn and understand the underlying processes on their own farm.
Hence, the whole-farm approach is also helpful in communicating the mitigation option to the
farmers, and this could be more beneficial if the models additionally evaluate costs and benefits
associating with farming activities.
5. Conclusion
Livestock undoubtedly need to be a priority focus of attention as the global community seeks
to address the challenge of climate change. Livestock contribute directly as well as indirectly
to global GHG pool. The two primary sources of GHG from livestock are enteric fermentation
and manure management. There are several techniques available to quantify CH4 emission,
and the application of appropriate technique depends on objectives of the study. Further,
simulation models offer a great scope to predict accurately the GHG emission in farm as a
whole. This information will be very valuable in understanding the role of livestock to climate
change in depth, and this understanding will help in designing suitable mitigation strategies
to reduce livestock-related GHGs.
Author details
Veerasamy Sejian1,2*, Raghavendra Bhatta1, Pradeep Kumar Malik1, Bagath Madiajagan1,

Yaqoub Ali Saif Al-Hosni2, Megan Sullivan2 and John B. Gaughan2
*Address all correspondence to: drsejian@gmail.com
1 ICAR-National Institute of Animal Nutrition and Physiology, Adugodi, Bangalore,

Karnataka, India
2 School of Agriculture and Food Sciences (Animal Science) The University of Queensland,
Gatton, QLD, Australia
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Chapter 12
Life Cycle Assessment Method –

Tool for Evaluation of Greenhouse Gases
Emissions from Agriculture and Food Processing
Zuzana Jelínková, Jan Moudrý Jr, Jan Moudrý, Marek Kopecký and
Jaroslav Bernas
http://dx.doi.org/10.5772/62300
Abstract
The chapter focuses on the use of the Life Cycle Assessment method to monitor the emis‐
sion load of foods from different systems of farming production. The products of the con‐
ventional and organic farming production intended for public catering are compared
within the SUKI and UMBESA international projects. Conventional farming is mainly
characterized by high inputs of mineral fertilizers, chemical pesticides, the use of hor‐
mones and stimulants in animal husbandry. It is a system based on the highest possible
yields without respecting the natural principles of nature. Conversely, organic farming is
a system of production established by the legislation that respects fundamental natural
cycles, such as crop rotation, ensures welfare of animals, prohibits the use of fertilizers,
pesticides, and other substances of synthetic origin. However, lower yields are a big dis‐
advantage. In the Czech Republic, only about one tenth of the agricultural fund is cur‐
rently used for organic farming. Arable land constitutes only about 10% of the total area
of agricultural land, other areas are mainly grasslands and orchards. The work primarily
aims to answer to the question whether the selection of foods may contribute to decrease
in greenhouse gas emissions, which is a part of the objectives of many policies. Besides
the comparison of agricultural production, processed and unprocessed foods, local and
imported foods and fresh and stored foods were compared as well. The Life Cycle As‐
sessment (LCA), which is used to assess environmental impacts of products and services
throughout their entire life cycle, was used to quantify the emission load. This method
may be briefly characterized as a gathering of all inputs and outputs that take place dur‐
ing the production in the interaction with the environment. These inputs and outputs
then also determine the impact on the environment. The LCA consists of four successive
and iterative phases: This concerns the definition of objectives and scope, inventory anal‐
ysis, impact assessment and interpretation of the results. The LCA was originally devel‐
oped for the assessment of impacts of especially industrial products. Certain
methodological problems and deficiency, which bring a level of uncertainty of the results,
have been caused by its adaptation to agricultural product assessment, but this method is
still recommended for comprehensive assessment of environmental impacts of agricul‐

tural production and the comparison of different agricultural products. In this study, a
Cradle-to-Gate assessment was performed, which means that the impacts of products (in
this case the emission formation) were evaluated only to the delivery of foods to public
facilities, further treatment and waste management was not assessed. About 20 most fre‐
quently used foods for school catering facilities were compared. The results of the project
confirm the general assumption about the less emission load of unprocessed, fresh and
local products. It may not clearly state that products from organic farming produce less
emissions when comparing agricultural systems. It always depends on the particular
crop. The absence of synthetic substances such as fertilizers and pesticides reduces the
emission load of organic farming, on the other hand, a higher number of mechanical op‐
erations and especially the lower income clearly increase the emission burden, therefore,
in several cases, lower emission loads of crops were achieved using the conventional
farming system. However, less emission may be achieved within the organic farming sys‐
tem. Among 11 evaluated agricultural products, 8 organic products and only 3 conven‐
tional ones go better. The situation is different regarding the following phases of food
production, processing and transport. The transport phase significantly worsens the envi‐
ronmental profile of organic foods, because transport distances are too far due to insuffi‐
cient processing capacity and underdeveloped market networks, and often exceed the
emission savings from the agricultural phase. On the contrary, conventional foods are
carried within relatively short distances, therefore the final emission load of conventional
foods is in many cases fewer than the load of organic foods. This fact is also confirmed by
the result of the study, because among 22 evaluated foods, organic food goes better in 11
cases and conventional food in 11 cases as well.
Keywords: LCA, conventional farming, organic farming, greenhouse gases, food
1. Introduction
Currently, agriculture is one of the largest anthropogenic activities with global impact. The
area of agroecosystem that covers about one third of the landmass [1] is directly related to the
need of humans to survive and it follows the population growth to a large extent. With the
growing population curve, the pressure on natural habitats and their conversion to agricultural
land and intensification of farming on existing agricultural land also increases. Since the
population growth continues very rapidly and also the consumption of meat, respectively
animal products, and the energy consumption in agriculture increase, we cannot expect that
in the foreseeable future, a spontaneous reversion of the trend of increasing environmental
load will come [2].
The environmental load increase impacts the soil, water, biodiversity and, last but not least,
the atmosphere. Climate changes and anthropogenic contribution to them have become a
frequently discussed issue in recent years. It is not clear yet to what extent these changes are
natural and to what extent they are influenced by human activities. Many questions have not
been answered yet and the discussion on whether the climate change is determined by natural
evolution or negative consequences of human activity is still held [3]. Just the anthropogenic
share of changes, especially in terms of GHG (Greenhouse gases) emission production, may
be regulated while this activity is one of the priorities of sustainability.
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http://dx.doi.org/10.5772/62300
Climate changes have a significant impact on agricultural systems in the world and can be a
crucial factor in ensuring sustainable food production. [4] states that, within the European
Union, the largest polluters are energetics, which releases 27.8% of anthropogenic greenhouse
gas emissions, transport with 19.5% and industry with 12.7%. Agriculture is with 9.2% in fourth
place. Current agricultural trends tending to sustainability should establish more environ‐
mentally friendly ways while maintaining the ability of the population food assurance. In order
to take steps in this direction, it is necessary to understand agricultural impacts and be able to
quantify them. In the case of greenhouse gases, the accurate quantification is quite difficult.
However, there are some methods that can help to implement it. One of the methodological
tools is the Life Cycle Assessment - LCA. It can be used to quantify GHG emissions, respec‐
tively emission saving options. It is a transparent scientific tool [5] which evaluates the
environmental impact on the basis of inputs and outputs within the production system [6].
Additionally, LCA analysis currently offers (as one of the few tools) a comprehensive approach
to assess the environmental effects [7]. A very valuable tool is LCA analysis thanks to its ability
to incorporate and compare different farming systems, their individual processes and products
and most of their environmental impacts [8].
Considering the choice of farming system, respectively changes within particular farming
systems, as a tool for mitigation, we need to quantify their total impact first and to find the
most problematic areas in terms of emissions that can provide space for an effective change.
The choice of farming system could be one of the ways to reduce the anthropogenic share of
GHG emissions while organic farming seems to be one of the ways. In the last decade, organic
farming has become an important element in the environmental friendliness policy and the
policy of quality of food in Europe because, inter alia, it reduces the use of synthetic fertilizers
and other chemicals such as pesticides [9]. However, mitigation can be achieved also within
conventional and integrated farming systems and within food production in general. Reduc‐
tion of emissions and environmental load in general is a necessary way to long-term sustain‐
ability within current population conditions.
2. Literature search
2.1. Climate change and agriculture activities
Anthropogenic activities have a very strong impact also on the environment. With increasing
population curve, globalization, technological progress and higher consumer demands, also
environmental pressure and environmental impacts grow. There are many impacts from
impacts on water, soil, biodiversity to the impacts on the air. Just the anthropogenic air
pollution and its relation to climate changes is a big current issue.
Agriculture is ranked among the five major anthropogenic activities contributing most to the
production of greenhouse gases. Global GHG emissions from agriculture reach values from
5,1 to 6,1 billions tons of CO2 equivalent [10]. [11] sets out the share of emissions of greenhouse
gases (CO2, N2O and CH4) from particular fields of human activities, while his findings indicate
that agriculture in 2000 contributed to the anthropogenic emissions with 13.5%. More than one
third of agricultural emissions are field emissions (especially N2O), methane (CH4) makes up
about one third. Also [12] states that agriculture contributes to the worldwide emission
production with the share of 10-12%, while until 2030, we can expect an increase of even half
these values [13]. Agriculture is a significant emission producer in the EU also according to
[14]. The total share of GHG emissions from agriculture within the EU-27 was 10.1% in 2011
[15]. We can find similar values also in the paper by [16] who states that this share within the
EU-15 was 10.2% in 2009. In the Czech Republic, the share of agricultural emissions in total
greenhouse gas emissions is calculated at 6.42% [17].
According to [18], 29% of emissions produced within the EU is related to the food production.
However, these emissions arising within food production are related not only to the field cycle
but also to the production of fertilizers and agrochemicals, processing or all process transport.
[18] sets the share of food production to anthropogenic emissions to 22-31% while the most
significant proportion (15%) is related to transport.
[19] also stated the high dependence of agriculture on non-renewable materials and to a great
extent, the resulting increased GHG emissions production. Agriculture produces emissions
in many ways. For example, CO2 is released during the consumption of fossil fuels or within
reduction of organic matter content in the soil. N20 is released as a result of fertilizer
application, CH4 from the digestive tract of some livestock species. We can conclude that the
amount and composition of our diet reflect the specific features of particular technological
processes in agriculture and thus the different GHG emission production. Therefore, the
change in the way of nutrition in industrialized countries can be extremely important to
ensure sustainable development (admittedly conditional on the stabilization of anthropogen‐
ic GHG emissions) [20].
2.2. Farming systems
Production systems have their own characteristics and can be categorized into groups e.g.
according to density and the resulting impact on the environment. Conventional farming
systems are commonly widespread, alternatively, there are integrated and organic farming
systems.
2.2.1. Conventional farming
Conventional farming is the most common way of farming in agriculturally advanced

countries. Its main objective is to maximize production. Other farming aspects are secondary.
Conventional farming is implemented in various intensity degrees. Environmentally friendly
processes beyond the ordinary laws are not enforced and monitored. Still, conventional
farmers can implement these processes and farm in accordance with environmental protection.
However, the European Union introduces a number of rules and legislative provisions for
conventional farming leading to limiting inputs in order to protect the environment. On the
contrary, in its extremely intensive forms, the conventional farming often leads to excessive
environmental damage. The precision farming is a technologically advanced form of conven‐
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tional farming that reduces environmental load to some extend through more efficient and
optimized inputs.
2.2.2. Integrated farming
Integrated farming is a kind of an intermediate step between conventional and organic farming
systems, originally based on integrated plant protection and extended to other agrotechnical
processes. Its objective is the sustainability of farming system and it is largely focused on
procedures friendly to the environment. However, unlike organic farming, it is not strictly
limited by legislation and it is possible, if necessary, to apply procedures that are forbidden
within organic farming (e.g. the use of some agrochemicals).
2.2.3. Organic farming
Organic farming is a special kind of farming that cares about the environment and its particular
components through restrictions or bans on the use of substances and procedures that burden
the environment or increase the risk of contamination of the food chain. Within livestock
breeding, it ensures their behavioural and physiological needs in accordance with the require‐
ments of specific legislation. It becomes an environmentally friendly alternative to other
farming systems [21]. The main goals of organic farming include:
• Maintenance and improvement of soil fertility.
• Genetic resources protection and biodiversity maintenance.
• Preservation of landscape features and their harmonization.
• Water management, keeping water in landscape and the protection of surface and ground‐
water against contamination.
• Efficient use of energy, focusing on renewable resources.
• The pursuit for maximum nutrients recirculation and a prevention of the entry of extraneous
substance into agroecosystem.
• Production of quality food and raw materials.
• Optimization of life for all organisms, including humans.

Organic farming systems create more potential to reduce greenhouse gas emissions than
conventional. The biggest difference is due to the absence of chemical fertilizers. The Farming
Systems Trial at Rodale Institute, an American long-term research comparing organic and
conventional agriculture, states that the introduction of organic farming nationwide in the
USA would manage to reduce CO2 emissions by up to a quarter due to increased carbon
sequestration in soils [22]. The disadvantage of organic farming is less production per the area
unit that increases the unit emission load. [23] states that yields of organic farms are on average
17% lower than within conventional farming systems. The impact of organic system on the
mitigation is usually measured per the area unit in order to enhance the objectivity. However,
it is important to convert it also to the production unit.
2.3. A Life Cycle Assessment
The aim of the assessment of the effects of agricultural products on the environment is to
evaluate their impact on environment sustainability [24], especially in terms of food consump‐
tion patterns [25]. As stated by [26], the system sustainability can be evaluated on the basis of
inputs and outputs and their conversion to CO2e. [27] states that the measurement of GHG
emissions suffers from certain inaccuracy. The reason for this error is that emissions in
agriculture are influenced by complex biological processes with a wide range of variables.
There are some suitable methods to assess environmental impacts of agricultural activities [28]
such as Life Cycle Assessment (LCA), Ecological Footprint or Emergy Analysis. [29]. The LCA
method may be briefly characterized as an assessment of all inputs, outputs and possible
impacts on the environment during the entire life cycle [30]. LCA analysis is a tool that enables
to assess environmental impacts within the product life cycle. Social or economic aspects may
be included as well, however, the calculation of their impacts has only just begun [31] and the
main focus is on the environmental component which evaluates, according to [32], the
environmental impact of a product based on the assessment of the material and energy flows,
that the monitored system shares with its surrounding space (environment).
[33] states that the LCA is an appropriate instrument because it enables to express the rela‐
tionships between the food production, transport and production of CO2.
With the LCA analysis, the impact categories - the impact on climate, water pollution and air
pollution - are mostly evaluated. Whereas, impacts such as biodiversity or pesticide toxicity
are seldom evaluated because of methodological problems [34]. The LCA study consists of
four basic stages: Definition of objectives and the scope, Inventory, Impact assessment and
Interpretation [32].
2.3.1. Goal and Scope definition
In the first stage of the LCA analysis, it is necessary to define the objective and the scope of the
paper before the actual start [35]. The study goal and scope definition determine the next
procedure character and the circumstances in which the study outputs are valid [32]. [36]
requires to establish a study goal and scope while the study scope means to determine the
product system, the functional unit and system boundaries, to determine allocation rules, the
assessment methodology, hypothesis and limits and data quality.
In the objectives of the study, there must be clearly specified who it is addressed to, the reasons
for the study and the intended use of the results [36]. This increases the transparency of the
study and the comprehensibility of the context of the results since different recipients empha‐
sise different aspects.
The study scope results form goals and is determined by financial resources of the ordering
authority and the available time of the processor [5]. The study scope describes the most
important methodological choices, hypothesis and limits [35] that are described below.
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2.3.1.1. Function and functional unit
To compare products (systems), it is necessary to define also the functional unit. The functional
unit is described as a quantified performance of a product system which serves as a reference
unit in a study of life cycle assessment [36]. It is an essential element which all study results
are related to. It must be chosen so as to be easily expressible and measurable. The functional
unit is the starting point for searching for alternative ways how to fulfil the function with a
lower negative impact on the environment [5]. [37] states that the determination of functional
units is as a crucial step especially when comparing systems with different levels of production
per hectare such as conventional and organic farming system. [38] sees fit to set the production
unit instead of the area unit as a functional unit. On the contrary, [9] recommends to involve
both functional units into calculations and perform the calculations for both the unit area and
the unit of production. This is confirmed also by [39] who states that LCA analysis outputs are
usually set per the production unit. Some authors, such as [40], state that LCA outputs should
by calculated in relation to the area unit allowing the better expression of environmental load
carrying capacity. With the LCA analysis, we cannot perform both calculation methods and
use the production unit as well as the area unit as a functional unit [2].
2.3.1.2. System boundaries
Each product system consists of a variable number of processes involved in the product life
cycle. However, the product under consideration is often related to other processes that may
no longer be important for the LCA study. The system boundary serves to the separation of
essential and non-essential processes of the product life cycle. Since the choice of system
boundaries significantly affects LCA study outcomes and in addition, its intensity and
complexity, system boundaries should always be well considered and clearly defined. The
choice of system boundaries is carried out with regard to the studied processes, studied
environmental impacts and selected complexity of the study. Not-including any life cycle
stages, processes or data must be logically reasoned and clearly explained [32].
Determination of system boundaries is always a very important step, especially in the area of
food production and agriculture, where the clearly identifiable technological processes and
systems meet the natural processes and procedures influenced by a number of factors [41]. The
system boundary defines which unit processes will be included in the monitored system [36].
The system boundary definition virtually defines which life-cycle stages will be analysed (in
the case the whole life cycle was not included) or what unit processes and elementary flows
will or will not be considered. The system boundaries can be restricted to the processes within
the farm [42], or can extend into other phases from pre-farming processes, through transport
and storage, to the end user, respectively consumption. [43] states that although it would be
desirable to include the entire product cycle, most studies of food production omit some
phases, usually trade and other related sections. Their impact is mostly negligible in relation
to e.g. the agricultural phase [44]. When comparing conventional and organic farming systems,
we can also omit the calculation of load from buildings and infrastructure because there are
only small differences between farming systems while slightly more noticeable difference is
apparent within animal production [45].
System boundaries determine not only which processes will be incorporated into the product
scheme, but also define the geographic and temporal scope of the study to determine its
purview. Defining the geographical scope (local, regional, national, continental or global) or
determination of the exact study location is important for the environmental aspects of various
material and energy flows because their impacts may be different in different geographical
conditions. E.g. due to different ways of development of power in each country, the environ‐
mental impact of power development and hence of energy consuming processes is different.
Using unsuitable system boundaries or oversight of important factors such as the place and
method of energy development can lead to false results.
2.3.1.3. Allocation principles
During the life cycle assessment, the study authors are very often confronted with the fact that
the product system has at its end more than one output. In these cases, we use the allocation.
Allocation means the assignment of the share of total environmental burden to particular
outputs [32]. The Standard recommends to avoid the allocation whenever possible, e.g. by
extending systems or sub-division processes [36].
In the case we cannot avoid the allocation using the above mentioned methods, the Standard
proposes to use the allocation based on the physical principle such as weight or energy content
of final products.
2.3.1.4. Data quality
The quality of data entering the LCA study is to be determined in view of temporal, spatial,
technological, data sources (it must be determined whether primary data required or secon‐
dary data can be used), their accuracy etc. It concerns the determination of all requirements
for the input data [5].
2.3.2. Life Cycle Inventory
The inventory tasks is to collect environmentally important information about relevant

processes involved in the product system. Inventory collects information about unit processes
at first and subsequently, an inventory of inputs and outputs of the system and its surround‐
ings is carried out. The goal is the identification and quantification of all elementary flows
associated with product system. Inventory analysis is the nature of the technical implemen‐
tation of LCA studies. It is an essential part of a study, has high demands for data availability,
practical experience in modelling product systems and, in the case of using database tools, it
is necessary to master them perfectly and to understand their function [46]. The inventory
phase principle is data collection that is used to quantify values of the elementary flows. This
phase represents a major practical part of the LCA study, time consuming and with demands
for data availability and author's experience with modelling product system studies [47].
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2.3.3. Life Cycle Inventory Assessment
The inventory results should be presented in clear form, how much and what substances from
the environment enter the system and how much get out. These results serve for subsequent
life cycle impact assessment [48]. The aim of the life cycle impact assessment is to measurably
compare the environmental impacts of product systems and to compare their severity with
new quantifiable variables identified as impact category. The impact categories are areas of
specific environmental problems such as global warming, climate changes, acidification,
eutrophication, ecotoxicity and others. Already in the phase of definition of the LCA study
scope, it is necessary to describe what impact category will be applied and which of their
environmental mechanisms will serve as a basis for impact assessment [46].
2.3.4. Interpretation
The outcome of the LCA study is a large amount of different values from the inventory as well
as from the life cycle assessment. An important task for the study author is to sort the data and
their appropriate and understandable interpretation [32]. The need for proper interpretation
is also stated by [49] who states that on the basis of LCA outcomes, there are often taking steps
with significant economic, environmental and other impacts, while there is the risk that
incorrect and misleading interpretation of outputs can lead to a deepening of existing or
creating new problems. Since the form of presentation of data often affects their meaning, the
life cycle interpretation has become an integral part of LCA studies and gained some rules. On
the general, interpretation of LCA consists of structuring data with regard to the most
important processes or process groups and the most important substances, performing
sensitivity analyses and evaluation of the uncertainties of the study, discussion of the data
meaningfulness in relation to the study completeness and the input data quality, and the final
summary and formulation of realistic recommendations.
3. Goal of the study
The main objective of the Czech - Austrian SUKI (Sustainable Kitchen) project was to assess
the total amount of GHG emissions produced by public catering facilities.
These emissions originate both within energy consumption for the kitchen operation (ie.
lighting, heating, ventilation, cooling, operating kitchen appliances, cooking process), but
mainly in the food production, processing and transport to catering facilities. While direct
energy consumption in the kitchen can be determined relatively easily, emissions from food
production are unexplored areas in the Czech Republic. The project set the target to answer
following questions using the emission quantification:
• What is the influence of the production method (conventional, organic) on the GHG
emission production?
• What is the influence of the place of the food origin (region / outside the region) on the GHG
emission production?
• What is the influence of the food processing method (raw, processed, fresh, frozen) on the
GHG emission production?
By answering these questions, we can deduce the possibilities and limits of greenhouse gas
emission savings without compromising the food quality which is also subject to the actual
selection of foods, meals and a preparation process. The aim is to promote catering facilities
on the path to sustainable production and at the same time to the food nutritional quality
improvement. Through targeted food selection, they can take a step towards sustainable
development and a healthy diet, contribute indirectly to the global reduction of greenhouse
gas emissions while promoting regional organic farming.
4. Methodological procedure
In the first project stage, it is necessary to identify the most widely used ingredients heading
for school catering facilities. For this purpose, we used annual lists of purchased raw materials
from partner catering facilities that were processed by tabulating and from them, all the
ingredients that made up at least 80% of the raw materials used kitchens during the year were
selected. These lists also provide a good comparison between Czech and Austrian cuisines.
The second step and the focus of this chapter was to evaluate the emission load of individual
foods from the list of most common foods. There was used the simplified Life Cycle Assess‐
ment method in which only the Climate change Impact category was assessed. Detailed
description of the LCA methodology is shown in the literature review, the following text
describes practical method implementation.Food emission load evaluation using the LCA
method
4.1. Goal and Scope definition
On the basis of evaluation of consumption of involved catering facilities, 11 most commonly

used products were selected. When work them into other raw materials, we can expand the
list to final 22 products that heading for school kitchens. For each product, a comparative study
focused on the comparison of organic and conventional versions, imports and regional variants
was elaborated, if possible, the also a comparison of the fresh and stored product was made,
as well as a comparison of different stages of processing. The results should serve as an answer
to the question whether the selection of the food contributes to reducing greenhouse gas
emissions. The target group are the chiefs of kitchens, school principals, cooks, diners, farmers,
suppliers, as well as actors at the regional and national political level.
Evaluated systems were modelled with the cradle to gate principle, thus the product system
of particular foods was terminated at the point of entry into the school canteen. The following
presentation of food and related activities, as well as waste management of the product and
its packaging materials were not included in the LCA. One kg of the final food was selected
as a functional unit. In the case the allocation was necessary, the weight-economic allocation
was used.
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4.2. Life Cycle Inventory

At this stage, it was necessary to collect the relevant data relating to the entire product system.
The product system was divided into sub-processes: agriculture, processing and trade. For
agriculture, inputs relating to the consumption of seeds, fertilizers, pesticides and fuel within
agricultural operations for crop production, feed consumption, energy and fuel within the
livestock sector were surveyed. Emissions from nitrogen fertilizer application within crop
production calculated according to the methodology [50] and emissions from manure man‐
agement in the livestock production, calculated according to the methodology [51], were
integrated into agriculture. A general framework for crop and livestock products is shown in
Figure 1 and Figure 2.
Figure 1. Framework of plant food product LCA
For processing, the data on energy consumption were collected, within the trade, it was travel
distance, information on cargo and storage time of various foods. All data was obtained
primarily from farmers, processors and traders, absent sufficient data, it was supplemented
by data from available databases, especially the Ecoinvent database.
From a geographical point of view, regarding the data quality, the data corresponds primarily
to the Czech Republic, secondarily to Central Europe. In terms of time, data corresponding to
the term 2000 - 2012 were obtained, from a technological point of view, data corresponds to
the widely used average technologies.
Figure 2. Framework of animal food product LCA
4.3. Life cycle inventory assessment
The results were calculated using the SIMA Pro software. To obtain the necessary results, the
Recipe Midpoint (H) Europe method has been chosen as a characterization model. Results
come from the climate change impact category and they are expressed in kg of a carbon dioxide
equivalent (CO2e).
4.4. Interpretation
Result interpretation and discussion is given below.
5. Results
Based on the analysis of the annual consumption of foods of participating catering facilities,
there were 22 of the final products which constitute the largest food consumption selected.
5.1. Emission load in food production
5.1.1. Agricultural phase
A basic emission load resulting from agriculture involves the calculation of greenhouse gases
in the field phase. In the context of comparing the formation of greenhouse gas emissions in
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the cultivation of selected crops and breeding of selected species within conventional and
organic farming systems, the total greenhouse gas emissions with twelve agricultural products
were observed. This total amount sum was divided into subgroups within crop production:
agricultural engineering, fertilizers, pesticides, seed and field emission, and in the context of
animal production to: feed consumption, manure management, and in the case of cattle on
enteric fermentation.
In the case of crop production, the conventional farming system differs from the organic one
in the total CO2e emissions production as well as in the production within subgroups.
Although the production of GHG emissions differs within particular subgroups, in total with
most studied crops, the production of CO2e is lower in the organic farming system. In the
primary agricultural study, [52] monitored a set of crops including wheat, rye, potatoes,
onions, carrots, tomatoes and cabbage, while the higher greenhouse gas emissions expressed
as CO2e within the conventional farming system in the Czech Republic were found with all
investigated crops except onions. The greatest differences were found with carrots and cabbage
where the ecological variants produced almost 60% lower emissions than the conventional
variant. The extension study [53] complements the study with the comparison of emission load
of organic and conventional apples and rice, where the results showed almost the same burden
for rice and in the case of apples, 33% lower emissions within organic farming. Another
extension study [54] comparing garlic proves again 40% lower emissions when grown in the
organic farming system. In conclusion, it can be summarized that in the context of plant
production, eight of ten evaluated products were better as an organic variant, one raw material
showed the same emissions in both variants and only one crop was better in the conventional
variant. Results and emission savings are summarized in the Table 1.
Group Product Organic* Conventional* save BIO
wheat 0,4218 0,4606 8%
corn products rye 0,2972 0,5364 45%
rice 0,6197 0,6266 1%
potatoes 0,1256 0,1446 13%
cabbage 0,0329 0,0774 58%
carrot 0,0411 0,0987 58%

vegetables products
tomato 0,0671 0,0871 23%
onion 0,0997 0,0828 -20%
garlic 0,2480 0,4306 42%
fruit products apple 0,0568 0,0848 33%
*in kg CO2e/kg of products
Table 1. Emission of GHGs from the plant production (agriculture phase only)
Comparative studies show positive and negative factors of organic farming which are mainly
lower yields and specific agronomic rules. It coincides e.g. with findings by [55]. The organic
farming is more agricultural operations intensive as compared with the conventional one. For
most crops, emissions from production of one kg are higher due to more intensive agricultural
technology (especially mechanical protection against pathogens), while the difference is even
increased by generally lower yields in organic farming. Emission load within the agrotechnical
phase in the organic farming system is increased also by some operations related to pre-seeding
soil preparation. The possibility of reducing GHG emissions by changes in agricultural
technology is highlighted e.g. by [56] who identifies the main potential for reduction within
tillage.
The fundamental difference between the conventional and organic farming system in terms
of GHG emissions is obvious within fertilization. While organic farming uses organic fertilizers
(especially manure or slurry), the use of synthetic fertilizers within the conventional farming
system increases significantly the share of emissions. This is stated also by [57] who gives
synthetic fertilizer decrease as one of the main tools for reducing CO2e emissions. From an
economic perspective, the nitrogen in organic farms is financially much more demanding than
industrially produced nitrogen. This is a powerful incentive to try to prevent losses and learn
how to use recycling technology [58]. Timing and management of nitrogen application are
crucial. Soil mineralization processes should deliver components to plants when the plants are
most in need [10]. In conventional farming, GHG emissions are increased also due to the use
of pesticides. In organic farming, this load is completely eliminated, respectively, transferred
to the agrotechnical phase in the form of mechanical plant protection. However in total, it is a
relatively low proportion of total emissions. [59] can see here another opportunity to save
emissions.
Within plant production, in organic farming, there is space for reducing greenhouse gas
emissions per the production unit and an increase in income, while maintaining the current
input structure.
To compare the emission load of livestock products, several studies were carried out again.
Initial work [61] compared load from conventional and organic cattle breeding without milk
production. One kilogram of organic beef produced twice higher emissions than one kilogram
of conventional meat. Another study [53] compared pork. Organic pork was again worse than
conventional meat in terms of emissions. On the contrary, when comparing variants of milk,
organic milk was a little emission-less burdensome than conventional milk. The latest from
animal studies compared the production of eggs [62], where organic eggs produce almost 40%
lower emissions than conventional eggs. Results and emission savings are summarized in the
Table 2.
The higher emission load in organic farming systems is mainly due to technology of rearing
and fattening when in the organic farming system, young ones are fed with breast milk while
in conventional breeding, they are fed with feed. Production of breast milk causes significantly
more emissions then production of crops for feed mixtures. Additionally, within conventional
breeding, the emission load is divided among several products (meat, milk).
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Product Organic* Conventional* save BIO
milk 1,336 1,420 6%
egg 0.219 0.383 43%
beef 24,10 11,45 -110%
pork 6,643 5,143 -29%
*in kg CO2e/kg of products(in egg study in kg CO2e/egg)
Table 2. Emission of GHGs from the animal production (agriculture phase only)
5.1.2. Manufacturing phase
Environmentally friendly farming systems that utilize anti-erosion measures, advanced

methods of nitrogen management and other measures, have the potential to sequester carbon
and reduce greenhouse gas emissions [63]. This creates a positive environmental potential
which may however be discarded in the following, or vice versa agricultural stage preceding,
parts of the food production process which could result in a significant increase in CO2e
emissions. [64] states that within cereal production, the production of fertilizers in the pre-
farming cycle makes up 35% of total emissions, while the farm stage only 27%.
Importance of pre-farming and post-farming stage can be documented by the example of

potato, where [65] states the production of 0.145 kg of CO2e in the conventional and 0.126 kg
of CO2e in organic farming system per one kilogram of potatoes. However, if we take into
account also other phases (especially the processing and transport), the load resulting from
potato products in relation to potatoes grows significantly. For one kilogram of peeled
potatoes in the Czech Republic, it is 0.262 kg of CO2e in conventional 0.247 kg of CO2e in
organic farming systems. However, for the manufacture of chips, it is already 2.072 kg of
CO2e in conventional and 2.271 kg of CO2 in organic farming systems per one kilogram of
finished product. And in the case of mashed potatoes, even in conventional production, it is
3.201 kg of CO2e and in organic production 3.192 kg of CO2e. These findings suggest that the
differences between the production systems are relatively small if we compare it to the
difference in CO2e emissions between processed and unprocessed products. Another
important factor is also common transport distances. Their importance is higher with the
processed products that are in their life cycle more transported (besides transporting raw
materials, there is still transport of semi-finished products between processing units). The
transport distance is also affected by the density of processing networks and infrastructure.
The results of the finished material (see Table 3) in our study [53] showed that eleven of the
22 evaluated products have better results as a conventional variety and eleven products have
better result as a organic variety. This indicates a lack of potential of a manufacturing and
sale network for organic products.
Group Product Organic* Conventional* save BIO
wheat 0,4593 0,4699 2%
rye 0,3336 0,5495 39%
wheat flour 0,6463 0,5861 -10%
rye flour 0,5080 0,6737 25%

corn products
roll 0,8100 0,7766 -4%
bread 1,0431 1,0632 2%
pasta 0,7336 0,7020 -5%
rice 0,6197 0,6266 1%
potatoes 0,1931 0,1867 -3%
peeled potatoes 0,2475 0,2624 6%
puree 3,1918 3,2009 0%
pommes 2,2714 2,0718 -10%
vegetables products cabbage 0,0851 0,1151 26%
carrot 0,1158 0,1517 24%
tomato 0,1748 0,1802 3%
onion 0,1749 0,1285 -36%
peeled onion 0,2428 0,1789 -36%
fruit products apple 0,1273 0,1189 -7%
milk 1,4870 1,5603 5%

milk products
yoghurt 1,7390 1,8123 4%
beef 24,5313 11,6510 -111%

meat products
pork 6,7452 5,3083 -27%
*in kg CO2e/kg of products
Table 3. Emission of GHGs from the final products
Besides transport distances, also the way of transportation has the influence. E.g. [63] states
that significant energy savings could be achieved by rail preference which can reduce power
consumption by up to half while emissions of greenhouse gases are reduced comparably.
These factors, together with the production technology may, in some cases, eliminate emissions
savings resulting from environmentally friendly management system. The principle of
regionality which reduces unnecessary transport processes is thus superior to the principles
of organic farming, since its failure may to reduce or completely eliminate the environmental
potential, respectively, the emission savings resulting from organic farming,. Reducing the
environmental potential can be demonstrated e.g. by the example of the production of bread
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in conventional and organic farming systems in the Czech Republic. Thanks to the low-volume
technologies in production of bread in organic processing capacities, produced greenhouse
gas emissions are much higher, so the positive effect of previous organic cultivating of wheat
and flour production is eliminated [66]. Post-farming life cycle stages of agricultural products
are very significant in terms of GHG emission production because within them, the emission
savings generally made by organic farming in relation to conventional farming can be
devalued. Assuming that the growing agricultural systems with arable land and permanent
crops and grazing systems worldwide can sequester up to 200 kg C ha-1 year-1, the global
carbon sequestration can reach 2.4 billion tons of CO2e year -1. This minimum idea of conver‐
sion to organic farming would be able to lose 40% of global agricultural GHG emissions [10].
Environmentally friendly and organic farming systems are such an important tool for reducing
greenhouse gas emissions.
Acknowledgements
This research study was supported by the European territorial co-operation Austria-Czech
Republic 2007-2013, the Project EUS M00080– Sustainable kitchen and by the University of
South Bohemia in Ceske Budejovice grant GAJU 063/2013/Z.
Author details
Zuzana Jelínková*, Jan Moudrý Jr, Jan Moudrý, Marek Kopecký and Jaroslav Bernas
*Address all correspondence to: jelinkova@zf.jcu.cz
University of South Bohemia in České Budějovice, Faculty of Agriculture, České Budějovice,

Czech Republic
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ISSN:1459-0255
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Chapter 13
Carbon Footprint as a Tool to Limit Greenhouse Gas

Emissions
Francesco Fantozzi and Pietro Bartocci
http://dx.doi.org/10.5772/62281
Abstract
The Carbon Footprint is the amount of greenhouse gases (GHG) produced during the
life cycle of a product, a process, or a service (expressed in equivalent tons of carbon
dioxide per functional unit of analyzed product/process/service). The patterns of fossil
fuel combustion, carbon capture and sequestration, and conventional and unconven‐
tional fossil fuel production, but also the emissions linked with consumer behavior,
can be analyzed considering their carbon footprint. In this chapter the carbon footprint
tool is introduced, linking it to fossil energy systems and renewable energy systems,
as well as the main products on the market, to provide information on which
technology should be promoted to reduce GHG emissions.
Keywords: Carbon Footprint, ISO 14067, GHG, Life Cycle Assessment
1. Introduction
Carbon footprint, as an indicator of the impact of the emissions of GHG of products and
services, is interesting for enterprises, consumers, and politicians [1]. Investors control the
carbon footprint of their products as it is an indicator of their investment risk. Purchasing
managers are interested in the carbon footprint of the goods that they are dealing with, and
the market is beginning to offer consumers carbon-labeled products. These are the reasons for
the popularity of product carbon footprint. It is defined as the mass of cumulated CO2
emissions that can be measured through a supply chain or through the life cycle of a product
[2]. The average per capita carbon footprint of continents and of the most important nations
is reported in Table 1 (data are expressed in equivalent tons of carbon dioxide per capita per
year). Also the contribution of different sectors is reported (expressed in percentage).
Country Construction Shelter Food Clothing Manufactured Mobility Service Trade

footprint (%) (%) (%) (%) products (%) (%) (%) (%)
[tCO2e/p]
Europe 13 9 21 16 3 12 21 17 6
USA 29 7 25 8 3 12 21 16 8
Canada 20 8 18 8 2 9 30 18 6
South 5 6 8 36 3 8 22 13 5
America
Russian 10 9 40 15 1 3 16 17 1
Federation
Asia 7 11 14 24 4 11 19 16 4
Africa 2 6 13 40 2 6 10 22 3
Australia 16 8 18 18 3 9 19 16 13
and New
Zealand
Table 1. Carbon footprint of continents and most important nations [3]
Carbon footprint is most appropriately calculated using life-cycle assessment or input-output

analysis [3,4]. In this sense it is based on the ISO 14040 [4] and ISO 14043 [5] norms, on life
cycle assessment (LCA). Specific norms for carbon footprint of enterprises and products are
ISO 14064 (part 1,2, and 3) [6-8], ISO 14067 [9], and PAS 2500 [10]. Carbon footprint calculation
process is shown in Figure 1.
Figure 1. Carbon footprint calculation
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Main emissions due to the most important processes are added through the whole life cycle.
Carbon footprint of a purchased good or service can be calculated using Equation 1 [11].
PCF=S1+S2+S3+S4+OE (1)
Where:
• S1 is the sum across purchased goods and services;
• S2 is the sum of emissions due to material inputs;
• S3 is the sum of emissions due to transport of material inputs;
• S4 is the sum of emissions due to waste outputs;
• OE stands for other emissions emitted in provision of the good or service.
In order to calculate carbon footprint, it is very important to consider the boundaries of the
process: which emissions should be considered in calculation of the footprint? This problem
can be solved by considering three definitions: Scope 1, Scope 2, and Scope 3.
Scope 1 indicates direct emissions, for example, on-site emissions; Scope 2 indicates emissions
embodied in the purchased energy; and Scope 3 indicates all the emissions not covered under
Scope 2, such as those associated with transport of goods and waste disposal [12].
Another important aspect is the functional unit, which is defined as a measure of the function
of the studied system, and it provides a reference to which the inputs and outputs can be
related. This enables the comparison of two essential different systems.
2. Carbon footprint of renewable energy systems
2.1. Carbon footprint of transport fuels
The carbon footprint of transport fuels has been analyzed in several studies starting from 1990.
One of the most important is the study realized by Sheehan et al. [13] at National Renewable
Energy Laboratory of the United States.This is an LCA study that includes the impact of CO2
emissions. Most important operations belonging to the petroleum diesel product system
include crude oil extraction, its transport to an oil refinery, crude oil refining to diesel fuel, its
transportation to the user, and its use in a bus engine.
In addition to energy and environmental outputs in each step, energy and environmental
inputs from raw materials use are also included. Generally, life cycle flows include all raw
materials used for extraction. Likewise, life cycle flows from intermediate energy sources such
as electricity, back to the extraction of coal, oil, natural gas, limestone, and other primary
resources should be included.
Life cycle presents a typical allocation case because the refining process is a multiple product
process and the other sub-products obtained during diesel production are shown in Figure 2,
together with the definition of the most important processes involved in the refining step.
Figure 2. Crude oil refining step [13]
The final results show that diesel production and use account for a total emission of CO2 of
633 gCO2eq/bhp-h. The processes that contribute most to the release of CO2 emissions are
refining (which is responsible for 10% of the emissions) and petroleum combustion in the
engine (which is responsible for 87% of the emissions).
2.2. Carbon footprint of electricity generation through fossil fuels
The electricity supply sector is responsible for over 7,700 million tonnes of CO2 emissions
annually (2,100 Mt C/yr); being 37.5% of total CO2 emissions [14]. The annual carbon emissions,
associated with electricity generation, is projected to surpass the 4,000 Mt C level by 2020 [15].
Past and projected electricity production from fossil fuels is shown in Table 2 and also CO2
emissions per kWh.
1995 2000 2010 2020

Coal 4,949 5,758 7,795 10,296
Natural Gas 1,932 2,664 5,063 8,243
Oil 1,315 1,422 1,663 1,941
Average GHG emissions (g CO2/kWh) 158 157 151 147
Table 2. Past and projected global production from the electricity generating sector (TWh/yr) and average CO2
emissions per kWh [14]
The efficiencies of modern thermal power stations using the steam cycle can exceed 40% based
on lower heating value, although the average efficiency of the installed stock worldwide is
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closer to 30%. Recently, efficiencies of 48.5% have been reported and, with further develop‐
ment, by 2020, they could reach 55% at costs only slightly higher than current technology.
Physical carbon sequestration is more useful with the emissions of large point sources of
CO2 such as power plants. It can be captured either before combustion, in an IGCC or in a
reforming process (transforming steam to methane), or after combustion from the flue gas
stream using amine solvents, for example. The volume percentage of CO2 in exhaust flue gases
is between 4% (for gas turbines) and 14% (for a pulverized coal-fired plant), which means that
large volumes of gas have to be treated using efficient solvents, and this will result in high-
energy consumption because of solvent regeneration. These techniques will achieve an
efficiency of 80–90% in carbon capture. Other carbon capture techniques include cryogenics,
membranes, and adsorption. After the CO2 has been captured, it is pressurized, typically up
to 100 bar, before transportation to storage areas. CO2 capture and compression imply a
decrease on the thermal efficiency of a power plant, which has been estimated to be equal to
8–13%. The cost of CO2 capture in power plants comprises between $30 and 50/t CO2 of
emissions; while the cost of CO2 transportation is influenced by the distance and the capacity
of the pipeline and ranges between $1 and 3/t CO2 per 100 km. The cost of underground storage,
which excludes the costs due to compression and transport, is estimated to range between $1
and 2/t CO2 stored. With the development of new technologies, for example the development
of new solvents and system components, the costs of carbon capture and storage would
decrease.
2.3. Carbon footprint of residential heating systems based on fossil fuels
Glaeser and Kahn [16] evaluated the emissions released by American households for heating
purposes. The two primary heating sources for households are fuel oil and natural gas. On the
one hand in the United States, the use of fuel oil is pretty rare, with the exception of the
Northeast, and it is used as a source of home heating in few metropolitan areas; on the other
hand, natural gas is the most common home heating source; and in some areas electricity is
also used. Natural gas consumption is driven primarily by climate.
For fuel oil and natural gas, there are conversion factors that enable to move from energy use
to CO2 emissions. In the case of fuel oil, the factor is 22.38 lb of CO2 per gallon.
It can be considered that about 20,000 kWh/yr are required to heat a typical house in developed
countries. If hard coal, oil, natural gas, and LPG are used, the annual total CO2 emissions are
8,280 kg CO2/yr, 6,280 kgCO2/yr, 4,540 kg CO2/yr, and 5,180 kg CO2/yr, respectively [17]. These
data agree with those reported by Johnson [18], which are shown in Figure 3.
2.4. Life cycle carbon footprint of shale gas
Recent advances in drilling and fracking technologies have made the access to huge deposits
of natural gas in shale deposits technically and economically feasible. These are located across
the United States and elsewhere [19,20], and thus shale gas production has grown about 48%
per year from 2006 to 2010 in the United States. This fact will influence the American and the
world energy outlooks for the near future, together with the variation in the oil price [21]. The
Figure 3. Carbon footprint of different heating fuels [18]
growth of the shale gas industry has brought important benefits, such as significant job growth,
decoupling gas and oil prices, providing an alternative to the more polluting use of oil in
transportation and of coal in power generation [22,23]. The carbon footprint of shale gas can
be calculated evaluating or measuring the direct CO2 emissions from its final use and evalu‐
ating indirect CO2 emissions produced from fossil fuels used to extract, develop, and transport
it. Also methane fugitive emissions and emissions from venting have to be considered.
Literature studies have shown that the indirect CO2 emissions throughout shale oil life cycle
are relatively small than that of the direct combustion of the fuel. In fact indirect emissions
range between 1 and 1.5 g CO2/MJ−1 [24], whereas direct emissions range between 13-15 g
CO2/MJ [25,26]. Indirect emissions from shale gas are comparable with those due to conven‐
tional gas production [26].
Figure 4. Comparison of GHG emissions from shale gas and conventional natural gas with low and high estimates of
fugitive methane emissions, surface-mined coal, deep-mined coal, and diesel oil; time horizon equal to 100 years [27]
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From the most important studies available in literature, it can be inferred that both carbon
footprints of shale gas and of conventional gas are dominated by direct CO2 emissions and
fugitive methane emissions. In Figure 4 direct emissions of CO2 during combustion of shale
gas, conventional gas, coal, and diesel oil are represented with white bars, whereas indirect
emissions occurring during the development and the use of the energy sources are represented
in black bars, and fugitive emissions of methane are represented with grey bars. All the
emissions have been normalized to the quantity of energy released during combustion.
3. Carbon footprint of renewable energy systems
3.1. Carbon footprint of transport biofuels (biodiesel, bioethanol, biomethane)
The GHG emissions released during biodiesel life cycle are about 40–65% of those released
during conventional diesel life cycle. For bioethanol technologies, the GHG emissions are
deeply influenced by the technology. Emissions of the whole life cycle of bioethanol produced
from corn can be about 80–90% of those of competitor fossil fuels. For bioethanol produced
from sugar cane, a reduction of 75-80% in fossil fuels emissions can be achieved. Important
factors that influence the final results are the amounts and type of fossil fuels used in the life
cycle as energy carriers to produce, transport, and process the feedstock. Also non-CO2
emissions, generated during the cultivation phase, such as N2O, have to be considered. Besides,
the efficiency in the conversion process is important too, together with the degree to which
biomass is used to provide the energy required by the process, and feedstock yields during
the cultivation phase. The mass and energy balances are also influenced by the capacity of the
bioenergy plant and the scale of the project. In the case of large-scale projects, there will be
important land use changes that can influence carbon stocks in the soil. Table 3 shows GHG
emissions per kilometer travelled.
Transportation Fuel GHG Emissions (gCO2-eq./km)
Bioethanol from sugar cane 50-75
Bioethanol from other crops (corn, sugar beet, wheat) 100-195
Biogas 25-100
Biodiesel (rapeseed, soy, sunflower) 80-140
Fischer Tropsch diesel from biomass 15-55
Bioethanol from lignocellulose 25-50
Gasoline 210-220
Diesel 185-220
Natural gas 155-185
Table 3. GHG emissions per kilometer travelled using renewable fuels and fossil fuels [28]
3.2. Carbon footprint of electricity generation through renewable energy

The carbon footprint of electricity generation through RES (Renewable Energy Systems) are
described in this section. Hydro-electricity is described first, and then wind power, followed
by bioenergy systems and solar energy.
Hydro-electricity is the most developed renewable resource worldwide, even if it has to face
social and environmental barriers [29]. In fact societal preferences are difficult to predict, while
hydro-sites are often difficult to reach, which results in high transmission and capital invest‐
ment costs. These are difficult to be accepted by private power companies. The global economic
hydropower potential ranges between 7000 and 9000 TWh per year. Particularly rural
communities without electricity appear to be convenient for small (<10 MWe), mini- (<1 MWe),
and micro- (<100 kWe) scale hydro schemes. They have low environmental impacts, and
generation costs are around 6–12 c/kWh. Emissions of GHG linked with hydro-electricity
operation are due to flooding of land upstream of a dam that can imply a loss of biological
carbon stocks and can produce methane emissions due to vegetation decomposition.
Wind power is a technology that has been developed recently. It has an intermittent flow
and produces about 4% of total global electricity. In 2013 the production capacity reached
282,000 MWe, which implies a huge development, respect from year 2000 [30]. Denmark is
producing about 40% of its total electricity consumption from wind power, and it's one of
the main exporters of wind turbine technology. Many wind turbines will be sited off-shore.
On the one hand in this way future demand can be met, the advantage is to increase the rated
output to more than 3 MWe, to decrease costs linked with operation and maintenance, to
have more reliable plants; on the other hand the cost of investment for wind turbines is
decreasing, while the installed capacity increases. So wind power is becoming competitive
with other sources of energy in highly windy areas. The costs of electricity generation in this
case range between 3 and 5 c/kWh. The investment costs will fall from $1000 to $635/kWe
and operating costs will decrease to about 0.01 c/kWh - 0.005 c/kWh [31].
Bioenergy can be produced from agricultural and forestry residues, animal effluents, the
organic fraction of municipal solid wastes, and dedicated energy crops. Since biomass is widely
spread in the territory, it is an interesting source of energy for rural and mountain areas. The
challenge is to optimize the production of biomass, collection and logistics, optimize its
conversion to energy and delivery to the end user, to provide a service that is economically
competitive with that obtainable using other fossil fuels. Residual biomasses, such as bagasse,
rice husks, straw, olive husk, bark, and sawdust often have a corresponding cost for disposal.
Therefore, biomass-to-energy conversion, in the case of residues, can have good economic
performance, especially in rural areas, where there is abundance of them. Denmark produces
about 40% of the electricity it consumes through cogeneration plants, using wood waste and
straw. Also biogas is produced from animal breeding effluents. Energy crops are less prom‐
ising in the short term due to their higher production costs in terms of $/GJ of available energy.
Also the competition for land use with food crops is becoming an issue. Biomass as a fuel is
more reactive than coal if it is used in gasification process, which promotes the use of biomass
in IGCC systems, that are approaching to commercial realization. Besides if coupled with
carbon capture, biomass integrated gasification combined cycle can be a carbon-negative
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technology, because CO2 is absorbed during biomass cultivation and production, and it is not
released in the IGCC plant, due to carbon capture. On the one hand, capital investment for a
biomass gasification–combined cycle plant, working with an high pressure reactor, is decreas‐
ing from $2000/kWe to $1100/kWe by 2020; on the other hand operating costs (fuel supply
included) will decline from 3.98 to 3.12 c/kWh [31]. Actually operation costs for a traditional
plat working with boiler plus steam turbine are about 5.50 c/kWh.
The cost of solar photovoltaic (PV) is slowly decreasing from $5,000/kWe to $4,000/kWe
installed. The increase in the installed capacity corresponds to an increase in scale-up of
manufacturing plants and the use of mass production techniques that are the main reasons
for costs reduction. Also operating costs are quite high, being about 20–40 c/kWh. Promis‐
ing new applications for solar PV are represented by grid connected buildings and by large
installations (up to 1 MWe), which are pushing innovation in inverters and net metering
systems. Other important markets for photovoltaic power systems are off-grid applications
for rural areas, especially in developing countries where there is a need for electrification
projects. The worldwide installed PV capacity is estimated to be about 178 GWe in 2014,
while it will reach about 400 GWe in 2020. Conversion efficiencies of silicon cells are
continuously improving. The efficiency of commercial monocrystalline modules is about 13–
17%, whereas the efficiency of multicrystalline module is about 12–14%. Literature studies
show that a single factory of 400 MWe capacity (obtainable with 5 million panels) can reduce
production costs of 75%, due to economies of scale [32]. Neij [33] calculated that a $100 billion
investment in manufacturing capacity would be needed in order to reach an acceptable
generating level of 5 c/kWh (excluding back-up supply or storage costs). Capital costs for
concentrated solar will fall from $4000/kWe to $2500/kWe by 2030 (Table 4) [34].
Technology PF + fgd, IGCC and CCGT PF + fgd CCGT Nuclear Hydro Wind Biomass PV and
NOx, etc. super- + CO2 +CO2 Turbines IGCC Solar
critical capture capture thermal
Energy source Coal Coal Gas Coal Gas Uranium Water Wind Biofuel Solar
Emissions (gC/ 229 190-198 103-122 40 17 0 0 0 0 0

kWh)
Reduction Baseline 55 103 5-50 N.A. 191 37 128 77 20

potential to
2020 (MtC/yr)
Cost of C Baseline -10-40 0-156 159 71-165 -38-135 -31-127 -82-135 -92-117 175-1400
reduction ($/t C
avoided)
PF, pulverised fuel; fgd, flue gas desulphurization; IGCC, integrated gasification combined cycle
Table 4. Cost estimates of alternative mitigation technologies in the power generation sector compared to baseline
pulverized coal-fired power plant and natural gas Combined Cycle with Gas Turbine (CCGT) power stations and the
potential reductions in CO2 emissions to 2020 [14]
3.3. Carbon footprint of residential heating systems based on renewable energy
Heat production and hot water supply to buildings are essential and important worldwide.
The problem is how to produce them in a sustainable way, replacing fossil fuels. Today, it is
intensively being discussed how to do so in the best way in future energy systems in which
the combustion of fossil fuel should be reduced or completely avoided. One way could be
through the promotion of low energy buildings in which the consumption of energy can be
reduced or even removed (through the use for example of solar thermal heating systems).
Another way could be the one to use excess heat produced from the industrial sector, waste
incineration, power stations based on large-scale exploitation of geothermal energy, solar
thermal energy, and heat pumps powered by excess wind energy. In these cases, a district
heating network becomes essential. Table 5 shows the comparison of GHG emissions for
different household.
Heat Source GHG Emissions (gCO2-eq./MJ)
Biomass (i.e., wood chips, pellets) 520
Geothermal 15
Solar thermal 1030
Coal 110150
Oil 90120
Natural gas 7085
Electricity from natural gas (space heating) 180210
Electricity from oil (space heating) 265295
Electricity from coal (space heating) 290320
Table 5. GHG emissions per unit output in the heating sector (taken from [28])
The development of district heating systems is linked with the development of other systems
such as combined heat and power systems, which generate waste heat, together with power.
These increase the fuel use efficiency [35]. Also heat pumps should be introduced in residential
heating systems [18]. In some countries like Norway, district heating system’s GHG emissions
have been compared with those of individual heating systems and it has been found that the
first have lower CO2 emissions.
4. Carbon footprint of products
4.1. Carbon footprint in the food industry
Food industry sector is one of the major contributors to climate change [36]. In Sweden, it has
been estimated that about 25% of GHG emissions from the private sector are due to the
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consumption of food [37]. In the European Union, food industry contribution to GHG
emissions is estimated to be about 31% [36,38]. GHG emissions in the transport sector are
mainly due to CO2; while in agriculture most emitted GHG are methane (CH4) and nitrous
oxide (N2O). The CO2 emitted from land use change represents also an important source of
emissions of the food production system. Starting from the publication of the Fourth Assess‐
ment Report of the IPCC in 2007 [39], the calculation of food carbon footprint has become more
and more popular. Food carbon footprint is calculated by companies also for marketing
purposes [40-42]. Also research efforts in the calculation of carbon footprint of food and in the
estimate of its uncertainty have increased in recent years [43-46] (see Figure 5). Challenges in
calculating the carbon footprint of food products can be linked with the functional unit, system
boundaries and allocation, land use change, carbon sequestration in soils, uncertainties, and
variation.
Figure 5. Carbon footprint of different types of food products at retail. Average values estimated to be representative
for food products sold on the Swedish market. Error bars show ranges of values found in the literature. Emissions
from land use change and carbon stock changes in soils are not included [47]
Besides marketing purposes, carbon footprint is calculated in the food sector also with the aim
at reducing its value, producing more sustainable food. The main ways to reduce the product
carbon footprint of food are as follows: by reducing emissions of CO2 due to energy use in
agriculture (for example improving energy efficiency and using renewable energy sources)
and reducing CH4 emissions from enteric fermentation and N2O emissions from fertilizer
nitrification in soil. CH4 emissions can be reduced to some extent by altering the diet fed to
ruminants [48], but the risk of pollution swapping is great [49,50]. N2O emissions from soils
can be reduced by optimizing nitrogen use and promoting N2O inhibitors.
Another way to reduce GHG emissions in the food sector is changing the consumption patterns
[51-54]; for example, switching from diets based on meat to diets in which proteins are also
supplied by vegetables.
Being on-farm emissions (from cultivation and animals breeding) the most important source
of GHG in food life cycle, numerous studies have tried to reduce them. Ahlgren [55] has used
LCA to evaluate the use of biofuels in tractors and the substitution of mineral nitrogen
fertilizers. This implied that 3–6% of a farm’s available land was needed to produce the
required biomass (to produce biofuels and fertilizer).
Another issue is represented by dairy production and the carbon footprint of milk [56,50]. An
important area of research is the production of animal feed for the different diets used in
livestock production [57-58].
4.2. Carbon footprint in the textile industry
Many enterprises in the textile and clothing industry are involved in product carbon footprint
calculation. They range from fiber manufacturers (e.g., Lenzing, Advansa, Dupont) to
producers of flooring material (e.g., InterfaceFlor, Desso, Heugaveld), to fashion brands
(united in the Sustainable Apparel Coalition), to other organizations (European Commission
and the Dutch branch organization Modint). They are using LCA to calculate the environ‐
mental impacts of textile-related products. Also educational textile and fashion institutes (e.g.,
the Amsterdam Fashion Institute) are promoting life cycle thinking, picking up the signals
from companies and other organizations. A literature survey [59] shows that Collins and
Aumônier [60] compiled a LCI (Life Cycle Inventory) on textile products upon references
dating from 1978 to 1999. Another research executed by Kalliala and Talvenmaa [61] reports,
for example, spinning energy, which is derived from a study out of 1997. In-depth investigation
on weaving led to the research of Koç and Çinçik [62]. In the recent work of Shen [63], non-
renewable energy use for the production processes of different fabrics is given, based upon a
report from 1997 [64].
Walser et al. [65] have published a LCA study using inventory data for polyester (PET) textile
production. The authors also noticed that the data in the Ecoinvent database [66] on cotton
and bast fibers do not specify the yarn size, which has an important influence on energy use.
Figure 6 presents the carbon footprint of cotton textiles and of synthetic textiles. In the case of
cotton, different yarn thickness are taken into account. They are expressed on decitex (abbre‐
viated dtex). In the case of synthetic textiles, only yarn thickness of 70 dtex is taken into account.
Figure 6. Carbon footprint of cotton textiles with yarn thickness comprised between 70 and 300 dtex (left) and synthet‐
ic textiles - acryl, nylon, PET, elastane-, with yarn thickness of 70 dtex (right) [59]
4.3. Carbon footprint in the cement industry
The cement industry is one of the sectors that contributes most to climate change, accounting
for roughly 5% of the total CO2 emissions worldwide [67]. Therefore reducing these emissions
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is a primary goal in order to comply with the objectives laid down in the Kyoto protocol to
combat climate change. Currently, the cement industry, belonging to the WBSCD (World
Business Council for Sustainable Development), has launched the Cement Sustainable
Initiative program to meet the challenges of sustainable development. The carbon footprint is
the most promising tool to evaluate the impact of carbon emissions of different products and
can be an indicator to be used for eco-labeling. Several efforts have been made to develop it
[68]. The study of Cagiao et al. [69] is based on the MC3 approach, also called organization-
product-based-life-cycle assessment (OP-LCA). Given its top-down approach, this methodol‐
ogy first allows the organization’s footprint to be calculated and then distributing it among
the products that it manufactures. Some of the advantages are as follows:
a. It is a single methodology to be used both for organizations and products.
b. It uses all the financial accounts as input data.
c. The information flows automatically through the value chain.
d. The scope is always the same for all the analyses.
e. It is simple and easy-to-understand and adaptable.
f. Both the carbon footprint and the ecological footprint of the organization can be obtained
[70-72].
The study of Cagiao et al. [69] was carried out with three potential scenarios in mind: case A
pertaining to a conventional integral plant; case B which refers to a grinding plant; and case
C, an integral plant which has been subject to the best available technical improvements. All
the plants have the same productivity of 1,000,000 t/year. A summary of main results is
proposed in Table 6.
Process Emissions Case

1,003,555.2 tCO2/year Case A
Carbon footprint of cement industry 907,384.2 tCO2/year Case B
790,278.3 tCO2/year Case C
1.00 tCO2/tcement Case A
Carbon footprint of one ton of cement 0.91 tCO2/tcement Case B
0.79 tCO2/tcement Case C
Direct emissions (75.33%) and wastes
Case A
(17.98%)
Main parts of the carbon footprint produced Materials (75.07%) and services (14.60%) Case B
Direct emissions (77.06%) and wastes
Case C
(15.18%)
213,276.9 tCO2/year (21.25% of initial
Reduction of total footprint by using BATs
carbon footprint)
Table 6. Carbon footprint of cement production [69]

5. Product Carbon Footprint (PCF) case study
Fantozzi et al. [73] presents the study of the carbon footprint of a typical food product in Central
Italy: truffle sauce. This is a mixture of vegetable oil and truffle in proportions of 33% and 67%
respectively and minor components and spices (garlic, salt, pepper, etc.). Both truffles and
olives are cultivated and harvested in a farm in Umbria (Italy). Olives are crushed in a mill
that is situated few kilometers from the farm. Once it has been produced, the extra virgin oil,
together with the truffle, is transported to another facility to produce bottled truffle sauce. The
carbon footprint calculation is based on ISO 14076 technical standard. Product Category Rules
(PCR) have been developed (see Table 7).
Stage Rule Description
Scope and functional unit Scope Calculate PCF of truffle sauce (expressed in kgCO2eq/kg
product)
System boundary Cultivation, transformation, packaging, and waste

disposal are taken into account, while consumption is
neglected
Allocation Allocation based on system expansion has to be

preferred to allocation based on mass and economic
value
Product definition Truffle sauce Truffle sauce is a mixture of vegetable oil and truffle in
proportions of 33% and 67% respectively and minor
components and spices (garlic, salt, pepper, etc.) that
were not considered in the analysis
LC stages Cultivation; Milling; Truffle production; Transport;

Sauce production
PCF calculation Software Simapro software was used to design process tree, and
calculate PCF, based on the impact method GWP 100
years. Cut-off on processes impact is set to 1% to ease
results view
Data uncertainty Data uncertainty was measured based on used

instruments precision and on the uncertainty of Simapro
datasets
Results communication Label A carbon footprint label was designed for the package
Table 7. Product Category Rules of truffle sauce [73]
The cut-off threshold on life cycle processes is about 1%. This decision is due to the need to
simplify the process tree diagram. All the calculations are referred to the growing season
2011/2012.
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The boundaries of the system analyzed are shown in Figure 7. Truffle sauce life cycle has been
divided in the following product stages:
• cultivation;
• truffle production;
• truffle sauce production;
• packaging.
This is a clear example of a cradle-to-grave study, so GHG fluxes comprise also disposal of the
packaging. The consumption phase is not considered in the study. The functional unit is 1 kg
of truffle sauce.
Figure 7. System boundaries [73]
Results of the analysis are proposed in Table 8. Cultivation gives an important contribution to
the final impact of truffle sauce, while truffle production has a reduced impact, because it is a
very extensive production. Olive trees cultivation uses fertilizers, diesel fuel for field opera‐
tions, electricity for the olives harvest, herbicides and pesticides.
Life Cycle Stage Contribution (kg CO2eq/kg product)
1) Cultivation 0.94
2) Milling 0.28
3) Truffle production 0.09
4) Sauce production 0.06
5) Packaging production & disposal 0.77
6) Transport 0.03
7) Avoided emissionsAvoided fuel 0.18

- Avoided fertilizer 0.02
Total 1.93
Table 8. Carbon footprint of truffle sauce [73]
Author details
Francesco Fantozzi and Pietro Bartocci*
*Address all correspondence to: bartocci@crbnet.it
Department of Engineering, University of Perugia, Perugia, Italy
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Chapter 1 The Changing Landscape of Energy Management in

Chapter 2 The Choice between Economic Policies to Face Greenhouse

Chapter 3 Energy for Sustainable Development: The Energy–Poverty–

Chapter 4 Native Forest and Climate Change — The Role of the

Chapter 5 Greenhouse Gas Emissions – Carbon Capture, Storage and

Chapter 6 Review of Recent Developments in CO2 Capture Using Solid

Chapter 7 Carbon Dioxide Geological Storage (CGS) – Current Status

Chapter 8 Methane Emissions from Rice Production in the United States

Chapter 9 Greenhouse Gases Production from Some Crops Growing

Chapter 10 Mitigating Greenhouse Gas Emissions from Winter

Chapter 11 Livestock as Sources of Greenhouse Gases and Its

Chapter 12 Life Cycle Assessment Method – Tool for Evaluation of

Chapter 13 Carbon Footprint as a Tool to Limit Greenhouse Gas

Sustainability should be a key component of every process,

We offer current technologies and valid methods for a wide range of

The Changing Landscape of Energy Management in

Elliot Woolley, Yingying Seow, Jorge Arinez and Shahin Rahimifard

Additional information is available at the end of the chapter

Keywords: Energy management, Greenhouse gases, business strategy, manufacturing,

The management of energy consumption within the manufacturing sector is particularly

2. Review of Existing EM Techniques

1. Enterprise level – supply chain of materials or components, network of production sites,

2. Facility level – building envelope, heating, ventilation and air-conditioning (HVAC),

3. Production/machine cell level – planning, production engineering and management,

5. Turret or tool-chip level – actual transformation of material.

Figure 2. Energy considerations at different manufacturing levels. Adapted from [10].

2.1. Energy Research on an Enterprise Level

2.2. Energy Research on a Facility Level

2.3. Energy Research at the Machine Cell Level

2.4. Energy Research Associated with Production Machines and Equipment

Cooperative Effort on Modelling Process Emissions in Manufacturing (CO2PE!) is an interna‐

Similarly, Overcash et al. [32] produced an engineering rule-of-practice-based analysis of

In contrast, however, Fleschutz et al. [38] conducted an energy simulation on 12 similar

2.5. Energy Research on the Turret Level (Theoretical Process Energy)

3. An Overview of the Current Scope of EM

3.1. Lifecycle Process System Planning

3.2. Eco-Intelligent Manufacturing and Agile Supply Chains

3.3. Energy Management at the Business Strategy Level

Short-life furniture Long-life furniture

⋅ Energy efficient process ⋅ High quality processes

⋅ Rapid production ⋅ Quality-driven production

⋅ Automated production ⋅ Semi-automated production

⋅ High throughput ⋅ Low throughput

⋅ Low profit margins ⋅ High profit margins

4. A Case Study for EM Method at the Business Strategy Level

Steel sheet production #

Factor Sale PSS Values/Assumptions

Steel sheet production (MJ/m2) Ex,prod Ey,prod Ex,prod=Ey,prod = 178

In addition, as manufacturers consider more radical ways of reducing their environmental

Elliot Woolley1*, Yingying Seow2, Jorge Arinez3 and Shahin Rahimifard1

*Address all correspondence to: e.b.woolley@lboro.ac.uk

1 Centre for Sustainable Manufacturing and Recycling Technologies (SMART), Wolfson

2 Jacobs, New City Court, London, UK