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Persistent Organic Pollutants (POPs): Health Hazards and Challenges for their
Bioremediation in Environment

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BIOREMEDIATION OF INDUSTRIAL POLLUTANTS
About the Editors
Dr. Ram Naresh Bharagava earned B.Sc. (1998) in Zoology,
Botany and Chemistry from University of Lucknow, Lucknow, Uttar
Pradesh (U.P.), India and M.Sc. (2004) in Molecular Biology and
Biotechnology from Govind Ballabh Pant University of Agriculture
& Technology (GBPUAT), Pantnagar, Uttarakhand (U.K.), India.
Subsequently, he earned Ph.D (2010) in Microbiology jointly from
Indian Institute of Toxicology Research (CSIR-IITR), Lucknow and
Pt. Ravishankar Shukla University, Raipur, Chhattisgarh, India. He
has authored one book and published many research and review
papers in national and international journal of repute. He also published many book chap-
ters and popular science articles in national and international edited books and science
magazines, respectively. He is a reviewer for various national and international journals
of his field. Currently, Dr. R. N. Bharagava is working as Assistant Professor and actively
engaged in teaching and research activities at Department of Environmental Microbiology
(DEM), Babasaheb Bhimrao Ambedkar Central University, Lucknow (U.P.), India. His ma-
jor thrust areas of research are the Biodegradation and Bioremediation of Environmental
Pollutants, Metagenomics and Wastewater Microbiology. He is life member of the Indian
Science Congress Association (ISCA), India, Association of Microbiologists of India (AMI),
Biotech Research Society (BRSI), and Academy of Environmental Biology (AEB).

Mr. Gaurav Saxena earned B.Sc. (2010) in Industrial Microbiology,


Zoology, Botany and Chemistry from Hemwati Nandan Bahuguna
Garhwal (Central) University (HNBGU), Srinagar (Garhwal), Ut-
tarakhand (U.K.), India and M.Sc. (2013) in Environmental Micro-
biology from Babasaheb Bhimrao Ambedkar University. Currently,
he is earning Ph.D in Environmental Microbiology from Depart-
ment of Environmental Microbiology (DEM), Babasaheb Bhimrao
Ambedkar University (A Central University), Lucknow (U.P.), India.
He has published papers, chapters and popular science articles
in national and international journals, edited books and science
magazines, respectively. His major thrust areas of research are the Biodegradation and
Bioremediation of Environmental Pollutants, Metagenomics and Wastewater Microbiology.
He is the member of the Association of Microbiologists of India (AMI) and Indian Science
Congress Association (ISCA), India.
BIOREMEDIATION OF
INDUSTRIAL POLLUTANTS

Edited by:
Ram Naresh Bharagava
Gaurav Saxena

2016
Educationist Press
an imprint of
Write & Print Publications
New Delhi-110 015
© 2016 Editors
ISBN: 978-93-84649-60-9

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contents of this work are intended to further general scientific research,
understanding and discussion only. Readers should consult with a specialist
where appropriate.
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for any omission brought to their notice for acknowledgement in the future
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Preface

The pollution of our natural environment with various hazardous


pollutants released from industries and agricultural practice is a serious
concern worldwide. However, the degradation and detoxification of
environmental pollutants is a global challenge in recent years for
environmental safety. Waste/pollutants released from various industries and
agricultural practices are widespread in most of the countries, causing the
direct pollution of aquatic resources and soil and indirect pollution of the
surface water and groundwater. In addition, environmental pollutants are
highly toxic in nature and cause serious toxic effects in plants, animals and
humans too. The governments around the globe are strictly advocating for
the mitigation of environmental pollution. Hence, the removal/elimination
of pollutants from the environment is utmost important to promote the
sustainable development of our society with low environmental impact. The
conventional remediation technologies are highly expensive, environmentally
destructive and not aesthetically pleasing. In this regard, „Bioremediation‰
has recently emerged as an eco-friendly and cost-effective sustainable
alternative to degrade and detoxify the environmental pollutants.
Bioremediation is a process that uses microorganisms (bacterial/fungi),
green plants or their enzymes to degrade/detoxify the pollutants such
as phenols, chlorophenols, petroleum hydrocarbons, plastics, azo dyes,
pesticides, toxic metals etc. from polluted soils and wastewaters. Hence,
a detailed knowledge of the environmental pollutants and their toxic
effects as well as their degradation/detoxification is urgently required to
know the fate of metabolic products produced during degradation, which
may otherwise threaten the public health and environment. Though, the
degradation potential of microbes and their interactions with environmental
pollutants has been studied in last yearÊs, but a detailed knowledge in
field of biodegradation and bioremediation is scanty and not available as
a whole to the readers. Therefore, the present book compiled the latest
knowledge on the biodegradation and bioremediation of environmental
pollutants released from different industries, which are one of the major
problems of the current world.
This book showcase the detailed knowledge on the fate and transport
of toxic and hazardous pollutants in the environment, their relation to
vi Bioremediation of Industrial Pollutants

natural attenuation and bioremediation approaches for environmental safety.


A number of experts from colleges, universities and research laboratories
have contributed their valuable knowledge for this book in the areas of
biodegradation and bioremediation of environmental pollutants, which
poses serious threats to the environment. In this book, an extensive focus
has been given on the biodegradation and bioremediation processes of
industrial wastes like discharge of wastewaters containing recalcitrant
organic and inorganic pollutants from industries such as distillery, tannery,
textile, pulp and paper industry and petroleum industry. However, the safe
disposal of solid and liquid waste generated from different industries is also
a major challenge in developing countries. In addition, the persistent organic
pollutants discharged along with industrial wastes and their degradation
and detoxification is one of the real challenges to scientists, researchers,
environmental microbiologists and biotechnologists. The roles of aquatic
macrophytes for phytoremediation of toxic metals with mechanisms have
been described in detail. Further, the role of biosurfactants produced by
microorganisms and genetically engineered microorganism in the remediation
of industrial wastes/pollutants has been discussed. In addition, the potential
role of laccase enzyme in the biodegradation and bioremediation of
industrial wastes has been also described in detail because enzymes are
crucial for the better understanding of biodegradation and bioremediation
processes. Further, the chapter dealing with the role of microbes in the
biodegradation of plastic waste has been also discussed. The book identified
that the biodegradation and bioremediation of industrial wastes/pollutants
is one of the major challenge for sustainable environment.
Therefore, this book will also serve as an invaluable source of basic
knowledge and recent advances in biodegradation and bioremediation of
environmental pollutants that widen its scope for a diverse community
of professionals having interests in bioremediation technologies. All the
chapters compiled in this book cover the different aspects of environmental
problems and their remedies with upto date developments in the field of
biodegradation and bioremediation. We hope that this book will provide
a comprehensive overview on the bioremediation approaches used for
different environmental pollutants causing serious health threats and
environmental problems. Furthermore, this book will also boost up a wide
range of students, scientists and researchers in microbiology, biotechnology,
environmental sciences with the fundamental and advance knowledge
about the environmental challenges and biological processes used for the
remediation of polluted sites. Finally, we gratefully acknowledge the tireless
cooperation and kind support from all the contributing authors for bringing
out this book. Lastly, the editors wish to thank Dr. Ram Chandra, Scientist-F
at CSIR-IITR, Lucknow, UP, India for their encouragement, kind support
and guidance during all the times.
Ram Naresh Bharagava
Gaurav Saxena
List of Contributors

Akash Mishra, Laboratory of Bioremediation and Metagenomics Research


(LBMR), Department of Environmental Microbiology (DEM), School for
Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar University
(A Central University), Vidya Vihar, Raebareli Road, Lucknow 226 025,
Uttar Pradesh, India
Amar Jyoti Das, Rhizosphere Biology Laboratory, Department of
Environmental Microbiology (DEM), School for Environmental Sciences
(SES), Babasaheb Bhimrao Ambedkar University (A Central University),
Vidya Vihar, Raebareli Road, Lucknow 226 025, Uttar Pradesh, India
Anita Sharma, Department of Microbiology, College of Basic Sciences and
Humanities (CBHS), G. B. Pant University of Agriculture & Technology
(GBPUA&T), Pantnagar, Udham Singh (U.S.) Nagar 263 145, Uttarakhand
(U.K.), India
Ashutosh Yadav, Laboratory of Bioremediation and Metagenomics Research
(LBMR), Department of Environmental Microbiology (DEM), School for
Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar University
(A Central University), Vidya Vihar, Raebareli Road, Lucknow 226 025,
Uttar Pradesh, India
Beenu Shastri, Rhizosphere Biology Laboratory, Department of
Environmental Microbiology (DEM), School for Environmental Sciences
(SES), Babasaheb Bhimrao Ambedkar University (A Central University),
Vidya Vihar, Raebareli Road, Lucknow 226 025, Uttar Pradesh, India
Bhawna Vyas, Council of Scientific and Industrial Research (CSIR)-Institute
of Microbial Technology (IMTECH), Sector 39 A, Chandigarh 160 036,
India
Chhaya Verma, Rhizosphere Biology Laboratory, Department of
Environmental Microbiology (DEM), School for Environmental Sciences
(SES), Babasaheb Bhimrao Ambedkar University (A Central University),
Vidya Vihar, Raebareli Road, Lucknow 226 025, Uttar Pradesh, India
viii Bioremediation of Industrial Pollutants

Deepika Rajwar, Department of Environmental Sciences, College of Basic


Sciences and Humanities (CBHS), G. B. Pant University of Agriculture
& Technology (GBPUA&T), Pantnagar, Udham Singh (U.S.) Nagar 263
145, Uttarakhand (U.K.), India
Devendra Mani Tripathi, Department of Environment and Developmental
Studies, Bundelkhand University, Kanpur Road, Jhansi 284 128 Uttar
Pradesh, India
Dhananjay Kumar, Department of Environmental Science (DES), School for
Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar University
(A Central University), Raebareli Road, Lucknow 226 025, Uttar Pradesh,
India
Garima Kaushik, Department of Environmental Science, School of Earth
Sciences, Central University of Rajasthan, Kishangarh, NH 8, Bandar
Sindri, Ajmer 305 817, Rajasthan, India
Gaurav Saxena, Laboratory of Bioremediation and Metagenomics Research
(LBMR), Department of Environmental Microbiology (DEM), School for
Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar University
(A Central University), Vidya Vihar, Raebareli Road, Lucknow 226 025,
Uttar Pradesh, India
Geeta Dhania, Department of Environmental Science, Maharshi Dayanand
(MD) University, Rohtak 124 001, Haryana, India
Govind Kumar, Department of Microbiology, College of Basic Sciences and
Humanities (CBHS), G. B. Pant University of Agriculture & Technology
(GBPUA&T), Pantnagar, Udham Singh (U.S.) Nagar 263 145, Uttarakhand
(U.K.), India
Jai Prakash Narayan Rai, Department of Environmental Sciences, College
of Basic Sciences and Humanities (CBHS), G. B. Pant University of
Agriculture & Technology (GBPUA&T), Pantnagar, Udham Singh (U.S.)
Nagar 263 145, Uttarakhand (U.K.), India
Narendra Kumar, Department of Environmental Science (DES), School for
Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar University
(A Central University), Raebareli Road, Lucknow 226 025, Uttar Pradesh,
India
Pankaj, Department of Microbiology, College of Basic Sciences and
Humanities (CBHS), G. B. Pant University of Agriculture & Technology
(GBPUA&T), Pantnagar, Udham Singh (U.S.) Nagar 263 145, Uttarakhand
(U.K.), India
List of Contributors ix

Pankaj Chowdhary, Laboratory of Bioremediation and Metagenomics


Research (LBMR), Department of Environmental Microbiology (DEM),
School for Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar
University (A Central University), Vidya Vihar, Raebareli Road, Lucknow
226 025, Uttar Pradesh, India
Priyanka Khati, Department of Microbiology, College of Basic Sciences and
Humanities (CBHS), G. B. Pant University of Agriculture & Technology
(GBPUA&T), Pantnagar, Udham Singh (U.S.) Nagar 263 145, Uttarakhand
(U.K.), India
Rajesh Kumar, Rhizosphere Biology Laboratory, Department of
Environmental Microbiology (DEM), School for Environmental Sciences
(SES), Babasaheb Bhimrao Ambedkar University (A Central University),
Vidya Vihar, Raebareli Road, Lucknow 226 025, Uttar Pradesh, India
Ram Chandra, Environmental Microbiology Division, Environmental
Toxicology Group, Council for Scientific and Industrial Research (CSIR)-
Indian Institute of Toxicology Research (IITR), Lucknow, M.G. Marg,
Lucknow 226 000 Uttar Pradesh, India
Ram Naresh Bharagava, Laboratory of Bioremediation and Metagenomics
Research (LBMR), Department of Environmental Microbiology (DEM),
School for Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar
University (A Central University), Vidya Vihar, Raebareli Road, Lucknow
226 025, Uttar Pradesh, India
Sadhana Singh Sagar, Rhizosphere Biology Laboratory, Department of
Environmental Microbiology (DEM), School for Environmental Sciences
(SES), Babasaheb Bhimrao Ambedkar University (A Central University),
Vidya Vihar, Raebareli Road, Lucknow 226 025, Uttar Pradesh, India
Saurabh Gangola, Department of Microbiology, College of Basic Sciences
and Humanities (CBHS), G. B. Pant University of Agriculture &
Technology (GBPUA&T), Pantnagar, Udham Singh (U.S.) Nagar 263
145, Uttarakhand (U.K.), India
Shattrohan Lal, Rhizosphere Biology Laboratory, Department of
Environmental Microbiology (DEM), School for Environmental Sciences
(SES), Babasaheb Bhimrao Ambedkar University (A Central University),
Vidya Vihar, Raebareli Road, Lucknow 226 025, Uttar Pradesh, India
Smriti Tripathi, Department of Environment and Developmental Studies,
Bundelkhand University, Kanpur Road, Jhansi 284 128 Uttar Pradesh,
India
x Bioremediation of Industrial Pollutants

Sujata, Laboratory of Bioremediation and Metagenomics Research (LBMR),


Department of Environmental Microbiology (DEM), School for
Environmental Sciences (SES), Babasaheb Bhimrao Ambedkar University
(A Central University), Vidya Vihar, Raebareli Road, Lucknow 226 025,
Uttar Pradesh, India
Sushila Saini, Department of Botany, Janta Vidya Mandir Ganpat Rai
Rasiwasia (JVMGRR) College, Charkhi Dadri 127 306, Haryana, India
Swaranjeet Singh Cameotra, Council of Scientific and Industrial Research
(CSIR)-Institute of Microbial Technology (IMTECH), Sector 39 A,
Chandigarh 160 036, India
Vineet Kumar, Environmental Microbiology Division, Environmental
Toxicology Group, Council for Scientific and Industrial Research (CSIR)-
Indian Institute of Toxicology Research (IITR), Lucknow, M.G. Marg,
Lucknow 226 000 Uttar Pradesh, India.
Contents

Preface v

List of Contributors ix

1. Persistent Organic Pollutants (POPs): Health Hazards and


Challenges for their Bioremediation in Environment 1
Ram Chandra and Vineet Kumar

2. Microbial Degradation and Decolorization of Dyes from


Textile Industry Wastewater 53
Sujata and Ram Naresh Bharagava

3. Bioremediation of Petroleum Hydrocarbons and Heavy Metal


Contaminated Sites by Biosurfactants: An Eco-friendly and
Sustainable Technology 91
Amar Jyoti Das, Beenu Shastri, Shattrohan Lal and
Rajesh Kumar

4. Organic Pollutants in Tannery Wastewater and Bioremediation


Approaches for Environmental Safety 119
Gaurav Saxena and Ram Naresh Bharagava

5. Plastic Waste: Environmental Pollution, Health Hazards and


Biodegradation Strategies 152
Smriti Tripathi, Ashutosh Yadav and Devendra Mani Tripathi

6. Microbial Degradation of Pesticides for Environmental


Cleanup 178
Anita Sharma, Pankaj, Priyanka Khati, Saurabh Gangola
and Govind Kumar

7. Genetically Modified Organisms (GMOs): Utility, Prospects and


Challenges in Bioremediation of Environmental Pollutants 206
Chhaya Verma, Sadhana Singh Sagar and Rajesh Kumar
xii Bioremediation of Industrial Pollutants

8. Bioremediation Approaches for Pulp and Paper Industry


Wastewater: Advances and Challenges 227
Deepika Rajwar and Jai Prakash Narayan Rai

9. Microbial Degradation and Decolorization of Melanoidins from


Distillery Wastewater for Environmental Safety 250
Garima Kaushik

10. Biodegradation and Bioremediation of Pesticides from


Contaminated Sites 280
Sushila Saini and Geeta Dhania

11. Role of Laccase Enzyme in Bioremediation of Industrial


Wastes and its Biotechnological Application 307
Pankaj Chowdhary, Gaurav Saxena and
Ram Naresh Bharagava

12. Phytoremediation of Heavy Metal Pollutants from Wastewater


Environment using Aquatic Macrophytes 332
Dhananjay Kumar and Narendra Kumar

13. Xenobiotics: Environmental Pollution, Health Hazards, its


Biodegradation and Future Challenges 352
Gaurav Saxena, Pankaj Chowdhary, Akash Mishra
and Ram Naresh Bharagava

14. Bioremediation: A Boon for Pesticides Degradation 379


Bhawna Vyas and Swaranjeet Singh Cameotra
Chapter 1

Persistent Organic Pollutants


(POPs): Health Hazards and
Challenges for their Bioremediation
in Environment

RAM CHANDRA1 AND VINEET KUMAR

SUMMARY
Persistent organic pollutants (POPs) have become a
great concern due to their toxicity, transformation and
bioaccumulation property. Therefore, this book chapter
highlights the types, sources, classification, health hazards and
mobility of organochlorine pesticides, industrial chemicals
and their by-products. Moreover, with the signing of Aarhus
Protocol and Stockholm Convention on POPs, there is an
increased demand to identify and characterise such chemicals
from industrial wastes and environment, which are toxic in
nature or to existing biota. Due to their long life and persistent
nature, they enter into body through food chain and transfer
to all tropic levels of ecological unit. In addition, POPs are
lipophilic in nature and accumulate in lipid containing tissues
and organs, which further indicates the adverse symptoms
after the threshold limit. Though, several potential enzymes
are reported from various categories of microorganisms and

1. Environmental Microbiology Division, Environmental Toxicology Group, Council of


Scientific and Industrial Research-Indian Institute of Toxicology Research (CSIR-
IITR), M.G. Marg, Lucknow 226 000, Uttar Pradesh, India.
2 Bioremediation of Industrial Pollutants

their interaction with POPs may break down the complex


compounds by various microbial technologies, however
technological advancement and human activities has also
insisted to explore the possible role of genetically modified
organisms and metagenomics and metabolomics. Due to
insufficient knowledge and non-feasibility of technique, the
appropriate treatment management of POPs is still a global
challenge for environmental sustainability.
Keywords: Organochlorine, Polychlorinated biphenyls,
Metagenomics, Health hazards and Bioremediation.

Introduction
Due to industrialization and urbanization, it is very difficult for modern
society to imagine their life without chemicals. Many industries like distillery
industry, pulp and paper industry, leather industry, pharmaceutical industry
etc. all are contributing to our modern standard of living. However,
increase in consumption of chemicals lead to the increase in pollution of
the environment. Pollution in terms of chemicals refers to the harmful
effects caused by the hazardous chemicals. Source of pollution can be both
natural and anthropogenic. The natural activities includes volcanic activity,
vegetation fires etc. whereas, the extensive use of chemical substances
pesticides, heavy metals and persistent organic pollutants (POPs) and
rapid industrialization the anthropogenic sources have also risen. Out of
a large number of above mentioned anthropogenic sources, toxicological
manifestation caused by them are highly damaging.
Organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons
(PAHs), poly chlorinated biphenyls (PCB), dioxins and dibenzofurans are the
major pollutants that bring about the POPs contamination (Érseková et al.,
2014). These compounds remain intact with the environment exceptionally
for a long period of time due to non-biodegradable nature because they
are resisting to photolytic, chemical and biological degradation. In addition,
these compounds are of great concern because of long range transport,
persistence nature and bioaccumulation propensity, once they enter into
the food chain they get accumulated in the fatty tissue of human body
and poses a risk to cause adverse effects to the environment and human
health (Kallenborn et al., 2012, Venkatesan and Halden, 2014).
Traditional established treatment methods like incineration, solvent
extraction, and gas phase chemical reduction, alkali metal reduction, land
filling and stabilization/solidification are used for the eradication/removal
of POPs from soil and sediments (Perelo, 2010). However, they suffer from
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 3

major drawback of being expensive owing to the necessity of sophisticated


infrastructure. In addition, these methods might not completely remove the
toxic organic compounds and requires experienced manpower to handle
the instrument properly. Bioremediation technology is one such treatment
method, which uses the microorganisms for the degradation of hazardous
contaminants. Researchers define the bioremediation as it is a sustainable,
eco-friendly and effective way to remove organic pollutants from soil and
water by using microorganisms (Megharaj et al., 2011). In addition, microbes
utilise these pollutants by changing its physical and chemical state for their
nutrition, growth and metabolism, (Joutey et al., 2013, Gadd, 2010). This
chapter provides details about the persistent organic pollutants, their fate
and toxic effects in environment and bioremediation and challenges in the
degradation and detoxification of persistent organic pollutants.

Persistent organic pollutants (POPs) in environment and their health


hazards
POPs are toxic organic compounds that are highly resistant to
degradation by biological, photolytic or chemical means. They are often
halogenated and most often chlorinated and characterised by hydrophobic
(low water solubility) and lipophilic (high lipid solubility) nature, leading
to their bioaccumulation in fatty tissues through food chain, and poses a
risk of causing adverse effect to human health and the environment around
the world. POPs are typically semi-volatile compounds; a characteristic that
favours the long-range transport of these compounds to occur either in the
vapour phase or adsorbed on atmospheric particles, thereby facilitating their
long-range transport through the atmosphere. To address this global concern,
the United States joined forces with other 90 counties and the European
community to sign a global treaty under United Nations Environmental
Program (UNEP) in Stockholm, Swedan in May 2001. This global treaty
is known as Stockholm Convention (Tang, 2013). The aim of this treaty to
protect human health and the environment from hazardous, long lasting
chemicals through a series of activities to reduce and ultimately to eliminate
the release of 12 key POPs, also called the „dirty dozen‰. Currently, there
are 22 chemicals or groups of chemicals that are listed in Annexes A, B, and
C as POPs under the convention and another five chemicals are currently
under review by the POP Review Committee (POPRC) of the convention
as shown in Table 1.
Chemicals listed in Annex A are subject to elimination of production
and use. Those listed in Annex B are restricted in production and use,
with specific and limited exemptions to allow their uses. Unintentionally-
produced POPs are listed in Annex C. The chemical structures of these
POPs are also shown in Fig. 1.
4

Table 1: POPs mentioned in different annexure regulated under the Stockholm Convention (2001).
Persistent organic pollutants (POPs) Half-life (yrs) Partition Uses/sources
Coefficient
Aldrin >5 5.17-7.4 Soil pests control
Chlordane 1 6.00 Agricultural insecticide and fungicide
Dieldrin 5 3.692-6.2 Soil pest control
Endrin Up to 12 Yrs 3.209-5.339 Insect and rodent control
Annex A:
Substances for Heptachlor Up to 2 4.40-5.5 Kill termites and insects
elimination of HCB 2.7-22.9 3.03-6.42 Wood preservative and fungicide
production and use
Mirex Up to 10 N/A Control fire ants and other ants
Polychloronated biphenyls 10days-1.5yr 4.3-8.26 In electrical industry, additives in paints and
(PCBs) carbon less copy paper
Toxaphene 100days- 3.23-5.50 Insect control
12yrs
Lindane 14 days insecticide on fruit and vegetable crops
Hexa and penta --- --- ---
bromodiphenyl ethers
Tetra- and penta --- --- ---
bromodiphenyl ethers
α-and βHCCH 1-7Yrs Kill insects
Annex B: DDT, perluorooctane 10-20 Yrs Kill insects
Substances sulfonic acid and
scheduled for Perfluorooctane sulfonyl
restriction on use fluoride (PFOSF)
Bioremediation of Industrial Pollutants
Dioxins 10-12 4.75-8.20 Formed during manufacture of certain
Annex C: pesticides , paper bleaching and waste
Furans 10-12 5.44-8.0
Substances for incineration
For which emission
Polychloronated biphenyls 10days-1.5yr 4.3-8.26 In electrical industry, additives in paints and
must be reduced
(PCBs) carbon less copy paper
Pentachlorobenzene (PCB) 10days-1.5yr 4.3-8.26 In electrical industry, additives in paints and
carbon less copy paper
Hexachlorobenzene (HCB) 2- 4.2 Yrs -- Used as a fungicide for seed treatment
Chemicals currently Hexabromocyclododecane -- --- used as thermal insulation in the building
under review (HBCD), short-chained industry. Other uses are upholstered furniture,
chlorinated paraffins, automobile interior textiles, car cushions and
chlorinated naphthalenes, insulation blocks in trucks, packaging material
hexachlorobutadiene, etc.
pentachlorophenol

Adapted from (UNEP, 2000; Adeola, 2004).


Persistent Organic Pollutants (POPs): Health Hazards and Challenges....
5
6 Bioremediation of Industrial Pollutants

Fig. 1: Chemical structure of some persistent organic pollutants


(Adapted from Tang, 2013)

In general, POPs can be divided into two main categories: 1. Intentionally


POPs and 2. Unintentionally POPs (Fig.2).

Intentionally Produced POPs


These compounds are produced intentionally as commercial product by
different chemical reactions including chlorine. Moreover, these compounds
show high lipophilicity, high neurotoxicity and are called as organochlorine
compounds (OCs). On the basis of their uses these can be further divided into
two types: organochlorine pesticides and industrial chemicals (El-Shahawi
et al., 2010). The organochlorine pesticides (DDT, mirex, endrin, dieldrin,
heptachlor, chlordane, aldrin and hexachlorobenzene) are the compounds,
which are used to kill pesticides. These pesticides comes into three major
classes: insecticides, fungicides and herbicides (Chopra et al., 2011). Apart
from these classes, the pesticides come under synthetic group that includes
rodenticides, molluscicides and acaricides. Industrial chemicals constitute
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 7

Fig. 2: Classification of POPs.

the important class of specific wastes i.e. polychlorinated biphenyls (PCBs)


that were first discovered as a pollutant in 1966. Additionally, it was found
in water, sediments, birds and fish tissue throughout the world.

Unintentionally Produced POPs


The unwanted products produced as a by-product of chlorine compounds
during combustion or burning are known as unintended by-products. This
category of compounds includes polycyclic aromatic hydrocarbons (PAHs),
dioxins and furans. PAHs are formed during the thermal degradation and
8 Bioremediation of Industrial Pollutants

subsequent recombination of organic molecules. These are produced during


the incomplete combustion at high temperature (500-800ÀC) or subjection of
organic material at low temperature between 100-300ÀC for long period of
time. They are insoluble in water with increase in their molecular weight,
boiling point and melting point while their vapour pressure decreases (El-
Shahawi et al., 2010). Natural (oil seeps, forest and rangeland fires, exudates
from trees) and anthropogenic (burning of fossil fuels, municipal soil waste
incineration and petroleum spills and discharge) activities are the main
sources of PAHs production (Ladygina and Rineau, 2013).
Dioxins and furans are abbreviated name of polychlorinated dibenzo-
p-dioxins and polychlorinated dibenzo- furans respectively. These are
produced during the production of herbicides, bleaching of wood pulp and
when products of some industries are burned. The classification of various
POPs is shown in Table 2. The organophosphorus pesticides (OPs) are
cholinesterase inhibiting chemicals, which are characterized in to four groups
depending upon their molecular structure: phosphates, phosphorothioates,
phosphorodithioates, and phosphorothiolates. OPs can be absorbed via
skin, cornea, and respiratory epithelium and gut either through ingestion
of contaminated food or vapours as these compounds are liquid at room
temperature. Upon exposure, it affects many organs like skeletal muscle,
nervous system, gastro-intestinal tract, secretary glands and respiratory
system. The nervous system is the most sensitive target compared to the OPs
induced toxicity (Rahimi and Abdollahi, 2007; Pehkonen and Zhang, 2002).
High exposure of OPs induced toxicity may cause fatal consequences like
weakness, glandular secretion, fasciculation, acute pancreatitis, convulsion
and respiratory failure. The major mechanism of OPs induced toxicity is the
induction of oxidative stress. It is a phenomenon in which the imbalance
occurs between the ratio of pro-oxidant and anti-oxidant (Rahimi and
Abdollahi, 2007).

Persistent Organic Pollutants (POPs) in Environment


By definition, POPs are likely to be more persistent, mobile, and
bioavailable than other substances cause adverse effects on the surrounding.
POPs behave dynamically in the environment according to their nature of
action as they volatilize in the air and cause pollution (Fig. 3). However,
atmosphere plays a major role in transport and fate of POPs and also
interaction of POPs with environmental compartments and most POPs are
believed to enter the Arctic through air. The scale of atmospheric transport of
POPs depends on the meteorological conditions, POPs physical and chemical
properties etc. therefore volatile and semi-volatile POPs also contaminate
from their sources because they can be transported for thousand of kilometre
through air current and as contaminate in wild life. Several studies have
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 9

revealed that distribution of POPs in northern hemisphere requires days to


weeks while in ocean currents it requires years and decades. POPs migrate
on air current from warmer region of the globe towards the colder polar
region. Once they reach temperature, they condense, precipitate out, and
are deposited again on the earthÊs surface. Thus, POPs found all over the
world.
Table 2: Organic pollutants other than Stockholm convention.
Persistent organic pollutants (POPs)
Intentionally Pesticides Chlorpyrifos, Fenthion, Diazinon, Fonofos, Dicrotophos,
(OPs) Methamidophos, Dimethoate, Monocrotophos,
Disulfoton, Parathion, Famphur, Phorate, Fenamiphos,
Phosphamidon, Fensulfothion , Terbufos
Unintentionally PAHs 1-Methylnaphthalene, 2-Methylnaphthalene,
Dimethylnaphthalenes, Trimethylnaphthalenes,
Fluorenes, Phenanthrene, 1-Methylphenanthrene,
2-Methylphenanthrene, Fluoranthene, Pyrene, Benz[α]
anthracene, Chrysene, Triphenylene, Benzo[g,h,i]
fluoranthene, Benzo[b]fluoranthene, Benzo[j]fluoranthene,
Benzo[k]fluoranthene, Benzo[a]pyrene, Benzo[e]pyrene,
Perylene, Benzo[g,h,i]perylene

Fig. 3: Fate of POPs in environment.

In soil and water, the mobility is administered by their half-life, aqueous


solubility and sorption or retardation factors such as Kd, Koc, Kow. When
hydrophobic organic compounds such as PAH are comes in contact with
10 Bioremediation of Industrial Pollutants

soil, through hydrogen bond and Vander Waals forces some of its portion
is rapidly sorbed by the soil components while the remaining one are
slowly sorbed. Similarly, when the organic contaminants are desorbed,
it follows the same pathway i.e. it first rapidly (weak surface chemical
interaction) desorbed and then slowly (strongly bound) and very slowly
(covalently or physically trapped) (Lohmann et al., 2007). In a similar manner
to soil, the organic pollutant from natural (forest fires, volcanic activities)
and anthropogenic source (pesticides, hydrocarbons, industrial waste)
contaminate the surface and ground water. Due to the presence of hydrogen
bond its various properties, it absorbs and binds many pollutants.
As described above, POPs are semi-volatile in nature, this property may
permit these compounds to occur either in the vapour phase or adsorbed
on atmosphere particles. It is a two step process by which chemicals are
transferred from land to atmosphere (Toose et al., 2004): 1) Change from
liquid or solid state to vapours and 2) Turbulent mixing for subsequent
dispersion. Besides this, there are different pathways through which
POPs are transported in the atmosphere: single hop pathway and multi
hop pathway or grasshopper effect. Both the pathways are temperature
dependent in former one the pollutant never returns to the atmosphere
after deposition while in latter one the deposited pollutant re-enters into
the environment for further transport via subsequent multiple atmospheric
hopes. The organic pollutants are exchanged through volatilization between
air and terrestrial surfaces under high temperature, which results in the
deposition and re-emission of POPs before reaching to final destination (Fig.
4) (Smaranda and Gavrilescu, 2008). As soon as the organic contaminants
comes in contact with soil surface, various phenomena happens, which
includes leaching of contaminants in groundwater, photodecomposition
or/and volatilization, uptake of contaminants by roots and physical and
chemical interaction organic contaminants to the soil components (Loffredo
and Senesi, 2006). Humic substances are the main components, which are
present in soil and help in the adsorption of organic pollutants in the
soil through specific physical and chemical binding mechanism, nature,
properties and forces with varying degree and strengths of organic pollutants
and humic substances. These properties include size, shape, molecular
structure, hydrogen and covalent bonding, ionic strength, redox potential,
dipole-dipole and Vander Waals forces of POPs (Loffredo and Senesi,
2006).

The Grasshoppers Syndrome


The POPs are also known for „Grasshoppers syndrome‰ due to their
highly mobile, travelling long distance even to the remote corner of the earth.
In the grasshopper effect, the POPs undergo through cycle of volatilisation
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 11

Fig. 4: Migration and transport of POPs in environment.

and condensation i.e. evaporation and atmospheric cycling in warmer


climates, condensation and deposition in colder climates. Thus, moving
these chemicals to remote region where they have never been produced or
used. These POPs tend to reach their highest level of concentration in the
cooler region of the globe. The indigenous people of the Arctic who depend
on traditional diet composed of foods with high fat content are especially
at risk of POPs contamination and the resultant adverse heath effect.

Occupational Exposure Limit and Health Hazards of various known Pops


„Silent spring‰, an environmental science documented book, which
tells about the detrimental effects of pesticides and it was written by
Rachel Carson and published in 1962. After the publication, this book
spurred a nationwide ban on DDT (1,1,1-Trichloro-2,2-di (p-chlorophenyl
ethane) for agriculture use (Hill, 2013). POPs are one or more cyclic ring
structures of either aromatic or aliphatic nature that are lack of polar
functional group and having variable amount of halogen usually chlorine.
According to The Aarhus protocol and The Stockholm Convention some
compounds various POPs such as DDT, PCBs, dioxins and furans are well
known for showing toxicity upon exposure (Harmens et al., 2013). The
ecotoxicological effect of POPs has been identified as hormones disrupters,
which can alter normal function of endocrine and reproduction systems
in humans and wild life. In humans, it causes hormone disrupters, which
can alter the normal function of endocrine and reproductive system. These
are able to stay in the environment for decades causing problems such as
cancer, birth defects, and learning disabilities, immunological, behavioural,
neurological and reproductive discrepancies in human (Sweetman et al.,
2005). The occupational exposure limits and lethal dose of POPs according
to occupational safety and health administration (OSHA), National Institute
12 Bioremediation of Industrial Pollutants

of Occupational Safety and Health (NIOSH) and The American Conference


of Governmental Industrial Hygienist (ACGIH) as shown in Table 3.
Table 3: Occupational exposure limits, lethal dose (LD50) and health hazards of
POPs.

POPs Exposure limit (mg/m3) LD50 (mg/ Health Hazards


Kg)
OSHA NIOSH ACGIH
PEL REL TLV
TWA TWA TWA
(Skin) (Ca)
Aldrin 0.25 0.15 0.25 83 Carcinogenic , malaise,
dizziness, nausea
Chlordane 0.5 - - 2 9 - 4 0 Carcinogenic
(oral),
4 2 8
(dermal )
Dieldrin 0.25 0.15 0.25 70 Liver and biliary cancer
Endrin 0.1 - - 171 Carcinogenic
Heptachlor 0.5 - - 90 Cancer, mutation, stillbirth,
birth defects and liver
disease
HCB - - .002 <5-40 Photosensitive skin
lesions, hirsutism,
hyperpigmentations,
porphyrinuria and
debilitation
Mirex - - - - Acute toxicity, termiticide
possible cancer
PCBs 0.5 1 - - Dermal & ocular lesions,
irregular menstrual cycle,
lowered immune response
PAHs 0.2 0.1 1 - Carcinogenic, , liver
(toxaphene) and kidney problems
chromosome aberrations
Lindane - - - -
DDT 1 0.5 1 500 Liver cancer and immune
system suppression
Dioxins - - - - Peripheral neuropathis,
fatigue, liver disease,
depression, embryo toxicity
Furans - - - - Peripheral neuropathis,
Liver problem, embryo
toxicity
Key: TWA: time weighted average, REL: recommended exposure limit, PEL: permissible
exposure limit and TLV: thresh hold limit value.
Table 4: Top 10 foods contaminated with POPs.
Persistent Organic Pollutants
S. Food Items Chlordane Dieldrin Endrin Heptachlor HCB Toxaphene DDT Dioxin
No.
1. Butter + + - + + - + +
2. Cantaloupe + - + - + - +
3. Cucumbers/Pickles + + + + - + - -
4. Meatloaf - + - + + - - +
5. Peanuts - + - - + + - -
6. Popcorn + + + - - + - -
7. Radishes + + - + - + + -
8. Spinach + - + - + + -
9. Summer Squash + + + - + + - -
10. Winter Squash + + + - + + - -
Adapted from Adeola (2004), Key: (+): Contaminated, (-): Not contaminated
Persistent Organic Pollutants (POPs): Health Hazards and Challenges....
13
14 Bioremediation of Industrial Pollutants

An evaluation of POPs residue monitoring data conducted by U.S. Food


and Drug Administration (FDA) in 1999 was showed the POPs contamination
in several food items grown and consumed locally as well those imported
from abroad in the U.S. The top ten foods mostly contaminated by specific
POPs residues were found in virtually all food categories including baked
goods, fruits, vegetables, meat, poultry, and dairy products as shown in
Table 4. The exposure per day was highest in the southeast of the U.S.
and lowest in the mid-west. The number of food items analyzed in the
Total Diet Study conducted by the USFDA and the findings of POPs and
pesticides residues in terms of number and percentage of occurrence as
shown in Table 5.
Table 5: POPs pesticides found in total diet study in 1999
S. No. POPs Frequency occurrence of POPs
pesticides residues
Total no. of finding % Occurrence
1. DDT 225 22
2. Chlorpyrifos-methyl 188 18
3. Malathion 175 17
4. Endosufan 151 15
5. Dieldrin 145 14
6. Chlorpyrifos 93 9
7. Chlorpropham 70 7
8. Permethrin 54 5
9. Iprodione 48 5
10. Chlordane 36 3
11. Heptachlor 36 3
12. Lindane 33 3
13. Thiabendazole 33 3
14. BHC (alpha, beta & delta) 32 3
15. HCB 32 3
(Adapted from USFDA 2000).

Exposure of POP in humans is carried out through the food chain


and the developing child is serving caused by POP because they are more
susceptible to infected by these POP. The developing cells are sensitive to
contamination and are more likely to be affected by exposure of POP. Some
studies have shown that children exposed to POPs during infancy had
remarkably lower scores in assessment determining intelligence (Bouwman,
2003). However, the toxicity mechanism of POPs in vertebrates is not clear
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 15

but several studies showed that the most of the organic pollutants binds to
aryl hydrocarbon receptor and induce harmful effects by forming reactive
oxygen species (ROS) and induce apoptosis (Selvakumar et al., 2013, Zhao
et al., 2012). The mechanism of AhR and ROS induced apoptosis by the
influence of POPs as shown in Fig. 5.

Fig. 5: Mechanism of AhR and ROS induced apoptosis


by the influence of POPs.

Pervasive harms of POPs to both wildlife and humans have been


documented extensively in the literature. In FloridaÊs Lake Apoka, stunted
penis, hormone disruption, and reproductive failure have been found among
alligators-disrupted reproductive development, deformity, immuno-toxicity,
hormonal deficiencies, to overall population decimation have been reported
(Adeola, 2004). In humans, the litany of health problems related to POPs
contamination is quite extensive including allergies, birth defects, cancers,
embryo toxicity, endocrine (hormone) disruptions, decreased sperm count,
diabetes, hypersensitivity, kidney and liver dysfunctions, learning and
behavioural problems (especially among children), mutations, nervous
disorders, premature births, and still births (Bolt and Degen, 2002; Hauser
et al., 2002; Adeola, 2004; Sweetman et al., 2005). Some studies showed that
16 Bioremediation of Industrial Pollutants

children exposed to POPs during infancy have remarkably lower scores


in assessment determining intelligence (Bouwman, 2003). Researchers from
numerous countries through the world has demonstrated that measurable
quantities of POPs are present in human adipose tissue, blood and breast
milk, because they are soluble in fats and are not easily broken down in
the body. The non-biodegradable nature of these organic pollutants and
its prolonged persistence in the environment makes it hazardous to life
present on earth. At young stage of human, POP can have following serious
consequence side effect such as birth defects, certain cancer and tumor at
multiple sites, immune system disorder, and reproductive problems reduced
ability towards off diseases, stunted growth and permanent impairment
of brain function. POP are a suspected carcinogen, causes endometriosis,
increase incidence of diabetes and neurobehavioral impairment including
learning disorder, reduced performance on standard test and changes in
temperament (Bolt and Degen, 2002).

Organochlorine Pesticides
Organochlorine pesticides (OCPs) are of greatest concern as they
are composed of carbon, hydrogen and chlorine. These compounds are
hydrophobic in nature and having high octanol-water partition coefficient
(Kow), long half-life, high bioaccumulation propensity and strong tendency
to sorb to soil (Koc). OCPs not only show their harmful effects on human
beings but also on animals, birds and fishes. As hydrophobic in nature,
OCPs accumulates in the brains, adipose tissue, liver and human milk
because of rich lipid content. OCPs primarily affect the central nervous
system in humans and interfere the fertility and reproduction directly or
indirectly in animals (Yang, 2007).

Aldrin
It is produced by the Diels-Alder reaction of hexachlorocyclopentadiene
with excess of bi-cycloheptadiene at 100■C. It was first synthesised in 1948
and manufactured as a pesticide (corn rootworm, wireworms, rice water
weevils and grasshoppers) in 1950. Aldrin residues are rarely present in
animals because aldrin is readily metabolised to dieldrin in both plants
and animals (Ritter et al., 1995).
No level of aldrin has been considered to be harmless or useful to
the human being. In addition, the lethal dose of aldrin for an adult has
been estimated to be about 83mg/kg of the body weight. Upon exposure,
it affects the adipose tissue of different sites or organs. Exposure of aldrin
to humans may cause fatal consequences like headache, dizziness, nausea,
vomiting, convulsions, myoclonic jerks and general malaise. Aldrin has
showed the low phytotoxicity towards some plants like tomato, cucumber.
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 17

Many studies were done on cauliflower, tomato plant and cabbage seedlings,
the inhibited growth rate, root development was found in these plants.
In all these plants, the dose was given at the rate of 16kg/ha (Edwards,
1965, Hagley, 1965).

Chlordane
It is a two-step reaction; first chlordane is produced by reacting
hexachlorocyclopentadiene with cycloheptadiene and second is chlorination
step in which chlordane is formed. It is semi-volatile in nature and high
partition coefficient and readily binds to the aquatic sediments and
accumulates in the fat of the organisms. In 1945, it was first introduce as an
insecticide that has been used on agricultural crops (Ritter et al., 1995).
It may cause many adverse health effects by suppression of antibody
and humoral immune responses, effect endocrine function and reproductive
system. Upon exposure, various symptoms include: ataxia, cough, abdominal
pain, nausea, vomiting, convulsions and confusion. Phytotoxicity of chlordane
is not available but it showed toxicity towards earthworm (Holsapple et
al., 1991).

DDT
It is given credit for saving millions of lives from malaria, typhus and
other vector born disease, but its stability, persistent nature, accumulation
in the adipose tissue and its estrogenic properties elevate concern about its
possible long term unpleasant consequence (Turusov et al., 2002). No living
organism is considered to be free from DDT, which stored in all tissue with
higher concentration present in fat. DDT residues persist in the environment
predominantly in the form of DDT; 1,1,1-trichloro-2-o-chlorophenyl-2-
pchloro-phenylethane (o,p-DDT); 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane
(o,p-DDD);1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (p,p-DDE).
The half-life of DDT is 10 to 20 year provided that its consumption is
totally ceased while its main metabolite 1,1-dichloro-2,2-bis(4-chloropehnyl)
ethane (DDD) and 1,1-dichloro-2,2-bis(4-chloropehnyl)ethylene (DDE) would
persist throughout the life span as they are more persistent than parent
compound. After 1945, it was used a pesticide in agriculture (70-80%) and
forest. The absorptive capacity of DDT in all soil is very strong (Ritter et
al., 1995). DDT affects the lifeÊs present in fresh and marine water, humans
and wildlife. In birds, such as falcons, an eggs of fish eating bird, causes
a considerable thinning of eggshell, which results in severe decline in
population due to difficulties in hatching. DDT also induces feminism and
altered sex ratio in western Gull population off the coast of southern California
and Herring Gull population in the Great Lakes (Marion et al., 2011).
18 Bioremediation of Industrial Pollutants

In humans, it acts as an endocrine disruptor, as evidence showed that


the DDE is an androgen receptor antagonist. Recent studied showed that
the accumulation of DDE at high concentration in human causes mammary
cancer. Several studies showed that the ancestral exposure of array of
environmental factors and contaminants have been revealed to support
the epigenetic trans-generational inheritance of adult onset disease. Skinner
et al. (2013) examined the impending trans-generational actions of DDT on
obesity and related disease and it was found that the ancestral exposure
to DDT can promote obesity and related disease.

Dieldrin
It was manufactured in 1948 and commercialized in 1950 by the
epoxidation of aldrin with per-acid (e.g. per-acetic acid). It may be
synthesized through condensation of hexacholorocyclopentadiene with the
epoxide of bicycloheptadiene. Due to its volatile and persistent nature, its
residues have been detected in air, water, soil, fish, birds and mammals
(including breast milk). Moreover, it is resistant to leach out into ground
water as it strongly binds to the soil, which shows its hydrophobic property
(Ritter et al., 1995). Initially, it was used an insecticide in agriculture (control
termites, textile pests and wood borer) but latter it has been banned in
many countries due to its environmental concerns. It is toxic to humans
like aldrin and showed the same sign and symptoms upon exposure. In
addition, it may show lethal effect at 10mg/kg of body weight. By varying
the dose of dieldrin, it shows the variable effect on different plants such
as when dose >22kg/ha, it showed the greater phytotoxicity in tomato and
cucumber while dose <11kg/ha no effect on soybean emergence, growth,
yield and chemical composition.

Endrin
It is an endostereoisomer and foliar insecticide, which was used mainly
on the field of cotton and grains. It is produced by reaction of vinyl chloride
and hexachlorocyclopentadiene and the product (dehydrochlorinated)
obtained is then condensed with cycloheptadiene to produce isodrin. This
isodrin is epoxidized with peracetic to yield endrin (Ritter et al., 1995).
The acute exposure of endrin leads to dizziness, weakness of the
legs, abdominal discomforts and nausea while chronic symptoms are
semi-consciousness, coma and repeated, violent epileptiform convulsions
lasting several minutes. Unlike other persistent organic pollutants, it is less
accumulated in fats but it is rapidly metabolise in animals. In addition, it
is highly toxic to fish (Dikshith, 2010).
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 19

Mirex
It is first synthesised in 1946, in the presence of aluminium chloride
by the dimerization of hexachlorcyclopentadiene with half-life of up to 10
years. It is resistant to breakdown and insoluble in water, which makes it
to strongly bind to the aquatic sediments. It is a stomach insecticide and
used as a fire retardant in plastic, rubber, paint, paper and electrical goods
(Ritter et al., 1995).
Its harmful effects were observed on plants, which showed several
symptoms like reduction in seed and emergence. As lipophilic in nature,
mirex is not taken up by plants, so it deposited on the aerial parts on
the plants through volatilization from the surface of soil. Mirex affects the
larval and juvenile stages of crustaceans in aquatic organisms. Moreover,
it also affects the fish by changing the fish behaviour.

Heptachlor
It is prepared by chlorination of chlordane with half-life of up to 2
year in temperate soil having high partition coefficient. In addition, it is
volatile in nature and readily metabolises in animals to heptachlor epoxide
and stored in animal fats. Similar to other organic compounds, it is readily
binds to the aquatic sediments (Ritter et al., 1995).
Heptachlor is banned in many countries as it is a non-systemic and
contact insecticide, chiefly used against soil insects and termites and after
that is has been used to kill grasshoppers and insects present on cotton
plants. Moreover, it also has been accustomed combat malaria. There is
no data on accidental or unsafe intoxication of heptachlor in humans. The
heptachlor induced toxicity leads to symptoms like tumour and convulsions
in animals. In 1992, Brown et al observed that heptachlor and endrin
production plant significantly increase the bladder cancer, which leads to
death small number of death and makes interpretation of those finding
tough. No deaths from liver or biliary tract cancer were determined, though
mortality from cerebrovascular disease was on top of expected (Pohanish,
2011). Studies on wild birds showed the decline in population of several
birds (Canada geese and the American kestrel) in the Columbia Basin in
the USA as it is transferred through the food chain. Heptachlor reduces
the reproductive success and adult mortality in the Canada geese (Li et
al., 2011).

Hexachlorobenzene
Hexachlorobenzene (HCB) a ubiquitous organic pollutant that is having
low water solubility, high stability and semi volatility with estimated half
life in soil from aerobic and anaerobic degradation range from 2.7 to 22.9
20 Bioremediation of Industrial Pollutants

years. It is used as a fungicide to control bunt of wheat and formed at


temperature greater than 150■ C during liquid phase substitution reaction
of chlorine and benzene in the presence of ferric oxide which act as a
catalyst (Ritter et al., 1995).
HCB induced toxicity leads to developed porphyria turcica (disorder
of heme biosynthesis) in human. In childrenÊs, it may cause „pembeyara‰
or pink sore at early stage due to the ingestion of infected breast milk or
grains (Gocmen et al., 1989). The symptoms of HCB induced toxicity includes
photosensitive skin lesions, hyperpigmentation, hirsutism, porphyrinuria
(presence of porphyrin in urine) and debilitation.

Lindane
The gamma isomer of hexachlorocyclohexane (HCH) is known as
lindane. Lindane is used as an insecticide on fruit and vegetable crops. The
use of lindane had been banned in more than 50 countries and restricted in
33 countries (Humphreys et al., 2008). Further, in 2006, the US EPA cancelled
agricultural uses of lindane (ATSDR, 2005). Lindane has a half-life of about
two weeks in soil and water. Once in the soil, lindane adsorbs strongly to
organic matter and is therefore relatively immobile in the soil.
It is quite toxic to humans. The acute (short-term) effects of lindane
through inhalation exposure in humans consist of irritation of the nose and
throat and effects on the blood. Chronic (long-term) exposure to lindane by
inhalation in humans has been associated with effects on the liver, blood,
and nervous, cardiovascular, and immune systems. Animal studies indicate
that lindane causes reproductive effects, while developmental effects have
not been noted. Oral animal studies have shown lindane to be a liver
carcinogen.

Industrial Chemicals
Polychlorinated Biphenyls
Polychlorinated biphenyls (PCBs) are a class of compounds where the
aromatic biphenyl rings carry one to ten chlorine atoms. Due to their non-
flammability, chemical stability, high boiling point and electrical insulating
properties, PCBs have been used for hundreds of industrial and commercial
purposes (Pieper, 2005). Commercial PCB mixtures contain between 20 and
70 of the 209 theoretically possible congeners. The half life of PCB is from
10 days to 1.5 years depending upon the increase in chlorination (Borja
et al., 2005).
The sources of PCB in the environment are poorly released of hazardous
waste that contains PCB, illegal dumping of waste, burning of waste that
contains PCB and accidental spills or leakage during transport (Gioia et
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 21

al., 2013). The PCB can enter into the body through various means, which
could be inhalation, ingestion and dermal contact. Once it enters the body,
it changed into different metabolites in the body itself. In addition, some
of its metabolites have the potential to be as harmful or some may remain
unchanged, which remains in the body and stored in the fat and liver or
other part of the organs (Mackova et al., 2010). PCB induced toxicity affects
the nervous system, reproductive system and immune system. Moreover,
it also shows some systemic effects on human beings, which include
respiratory, cardiovascular, haematological (decreased polymorphonuclear
neutrophil (PMN) and increased lymphocytes, monocytes and eosinophils),
renal and endocrine effects (Borja et al., 2005).

By-products
Dioxins & Furans
These are produced as by-products of various industrial and all
combustion processes. The term „dioxin‰ and „furans‰ are frequently used
to refer the 75 congeners of polychlorinated dibenzo-p-dioxins (PCDDs)
and 135 congeners of polychlorinated dibenzofurans (PCDFs) respectively.
PCDD/Fs are formed unintentionally from human activities. One of the main
sources of PCDD/Fs is municipal waste incinerators. PCDD/PCDFs formed
are absorbed on the fly ash, and then enter into the environment. Therefore,
the fly ash has been considered as a harmful waste causing environmental
pollution. In northern hemisphere during the summer, in vapour phase the
lower congeners of PCDD/PCDF are found. While those are in vapour phase
undergo photochemical transformation with dechlorination process leading
to more toxic congeners (Fiedler and Borja-Aburto, 2003). The PCDD/PCDF
can be deposited on plants by different ways in terrestrial food chain via wet
deposition or via dry or diffusive transport. Dry particle bound deposition
and dry gaseous deposition plays an important role for accumulation of
lower chlorinated PCDD/PCDF and uptake of PCDD/PCDF with six and
more chlorine atoms respectively.
The most toxic of the PCDD/PCDF congeners are 2,3,7,8-
tetrachlorodibenzo-para-dioxin (2,3,7,8-Cl4DD) classified as carcinogenic to
human. These organic compounds have low vapour pressure, extremely
low solubility in water, high solubility in organic/fatty matrices and
strongly bind to the organic matter in soil and sediments. Because of these
properties these compounds gets concentrated into fatty tissue, exists in both
gaseous phase and bound to particles. The congenerÊs vapour pressure and
ambient air temperature are the two key parameters, which administers the
partitioning between gaseous phase and particles. Clinical manifestation of
dioxins induced toxicity are increased risk of hyperpigmentation, altered
liver function and liver metabolism, general weakness related with severe
22 Bioremediation of Industrial Pollutants

weight loss, change in the activity of various liver enzymes, suppression


of immune system, endocrine and nervous system abnormalities. 2,3,7,8-
Cl4DD is the potent fetotoxic and teratogenic chemical, which causes cancer
in animals. It binds to the aryl hydrocarbon receptor (AhR), which occurs
in rodant and human tissues. When AhR lingand binds to the AhR, it
induces CYP1A1 (Cytochrome P450 1A1) and CYP1A2 (Cytochrome P450 1A2)
gene expression. While when PADD/PCDF binds to the AhR, it inhibits
transcription.

Polycyclic Aromatic Hydrocarbons


Polycyclic aromatic hydrocarbons (PAHs) constitute a large and diverse
class of organic compounds and are generally described as molecules,
which consist of three or more fused aromatic rings in various structural
configurations. They are colourless, white or pale yellow-green solid and
formed by the incomplete combustion of fossil fuels or material that contains
C and H. PAHs are used to make pesticides, dyes, plastics and medicines.
As persisting nature, they can stay in the environment for long period of
time. Different PAHs has different property such as some of them turn
into vapour very easily in air while some do not break down easily in
water (Baek et al., 1991).
There are different routes through, which humans can be exposed to
PAHS such as through respiratory tract (by inhalation of PAHs contaminated
air, cigarette smoke, vehicle exhaust and burning of wood), digestive tract
(intake of PAHs contaminated food) and dermal contact (soot, pitch and
tar). Upon exposure, it may form tumour in several organs like lungs, skin,
oesophagus, colon, pancreas, bladder and breast in women (Boström et al.,
2002). In addition to increases in environmental persistence with increasing
PAHs molecule size, evidence suggests that in some cases, PAHs genotoxicity
also increases with size, up to at least four or five fused benzene rings.

Microbial Degradation of Persistent Organic Pollutants (POPs)


As compared to other traditional technologies (incineration, solvent
extraction, and gas phase chemical reduction, alkali metal reduction, land
filling), biodegradation is a viable bioremediation technology that involves
the application of selected living microorganisms to degrade, metabolise or
immobilised the undesirable substances like pesticides, organic pollutants
and hydrocarbons from soil and water to improve its quality (Singh and
Ward, 2004). A large number of bacterial and fungal species possess the
capability to degrade persistent organic pollutants. The degradation process
occurs either under aerobic (requires molecular oxygen such as mono- and
dioxygenase, which not only act as a terminal electron acceptor but also as a
co-substrate) and anaerobic (requires presence of electron withdrawing group
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 23

for initial reductive attack) conditions with the help of microorganisms,


which either alter the functional groups or degrade the basic structure of the
compound leading to the formation of carbon dioxide, water and inorganic
salts. The general pathways of xenobiotic biotransformation and their major
sub-cellular location are presented in Table 6. In addition, anaerobic process
is favoured during degradation because highly chlorinated compounds are
difficult to degrade under aerobic condition (Mehboob, 2010, Kot-Wasik
et al., 2004) Biodegradation process generally depends on many factors.
These factors include the structure of the compound, substituentÊs position
in the molecule, and solubility of the compound and concentration of the
pollutant. Environmental and soil conditions like organic carbon content
influence the degradation rate of POPs.
Adapted from (Parkinson, 2001) The microbial strain is not only
composed of single strain but it is composed of diverse, synergistic
or antagonist communities in soil or aquatic environment. Metabolic
cooperation is a process that occurs within a well-coordinated microbial
community and biodegradation involves transferring the substrates and
products. Microorganisms either change the structure or completely
degrade the target molecule during interaction, which could be chemical
or physical. Among microbial community, bacteria, algae and fungi have
the ability to biotransform the POPs, rendering it non-toxic compounds.
But, few indigenous or engineered microorganisms are used broadly to
remove pollutants efficiently such as Bacillus, Pseudomonas, Corynebacterium,
Staphylococcus, Streptococcus, Shigella, Alcaligenes, Acinetobacter, Escherichia,
Klebsiella and Enterobacter and among them Bacillus species found to be best
for bioremediation/biodegradation of organic pollutants. Microorganisms
have very large enzymatic facilities due to their genetic flexibility, short
reproduction cycle and high adaptive potential. However, bioremediation
technology applied in perspective to POPs takes into consideration by
following techniques (Fig. 6).
Biosparging: It is an in-situ remediation technology that involves the
injection of air under pressure below the water table to increase groundwater
oxygen concentrations and to enhance the rate of the biological degradation
of contaminants by naturally occurring bacteria (Chandra and Vineet,
2015).
Bioventing: It is an in-situ remediation technology deliver air from the
atmosphere into the soil above the water table through injection wells placed
in the ground where the contamination exists. It employs low air flow rates
and provides only the amount of oxygen necessary for biodegradation while
minimizing volatilization and release of contaminants to the atmosphere
(Chandra and Vineet, 2015)
24 Bioremediation of Industrial Pollutants

Table 6: General pathways of xenobiotic biotransformation and their major sub-


cellular location.
Reaction Enzyme Localization
Phase I
Hydrolysis Esterase Microsomes, cytosol, Lysosomes,
blood
Peptidase Blood, lysosomes
Epoxide hydrolase Microsomes, cytosol
Reduction Azo- and nitro-reduction Microflora, microsomes, cytosol
Carbonyl reduction Cytosol, blood, microsomes
Disulfide reduction Cytosol
Sulfoxide reduction Cytosol
Quinone reduction Cytosol, microsomes
Reductive dehalogenation Microsomes
Oxidation Alcohol dehydrogenase Cytosol
Aldehyde dehydrogenase Mitochondria, cytosol
Aldehyde oxidase Cytosol
Xanthine oxidase Cytosol
Monoamine oxidase Mitochondria
Diamine oxidase Cytosol
Prostaglandin H synthase Microsomes
Flavin-monooxygenases Microsomes
Cytochrome P450 Microsomes
Phase II
Glucuronide conjugation Microsomes
Sulfate conjugation Cytosol
Glutathione conjugation Cytosol, microsomes
Amino acid conjugation Mitochondria, microsomes
Acylation Mitochondria, cytosol
Methylation Cytosol, microsomes, blood

Biopiling: It is an ex-situ full-scale remediation technology, where


contaminated soil is constructed into engineered piles or cells with the aim
of enhancing conditions required for biodegradation through greater control
of oxygen, with nutrients such as phosphorus and nitrogen and water.
Biostimulation: It involves the modification of contaminated media to
provide the nutrition to soil microbiota by adjusting pH, addition of limiting
nutrient to improve C: N: P ratio (Singh et al., 2011).
Persistent Organic Pollutants (POPs): Health Hazards and Challenges....

Fig 6: Different mechanisms of microbial degradation of persistent organic pollutants (POPs).


25
26 Bioremediation of Industrial Pollutants

Bioaugmentation: It is the applications of indigenous or allochthonous


wide type or genetically modified microorganisms to polluted hazardous
waste sites in order to accelerate the removal of undesired compounds.
It is thought that the bioaugmentation approach should be applied when
the biostimulation and bioattenuation have failed. (Chandra and Vineet,
2015)

Pollutants and Microbial Interaction


The fractions of pollutant in soil that can be taken up or altered by
living organisms are termed as bioavailability. There are two important
factors that determine the amount of bioavailable pollutant: mass transfer
and intrinsic activity of cell. Bioavailability is differs between species and
organisms so it can be define in terms of specific organism as the extent
to which pollutant is free to move into or on to organism (Semple et al.,
2003). The in-situ microbial degradation of organic pollutant is a function of
bioavailability of contaminant and catabolic activity of microbes. Chemotaxis
is a process that plays a vital role in biodegradation of environmental
pollutants by increasing the bioavailability of pollutants to microbes. It is
a phenomenon in which the bacteria/fungi move under the influence of
chemical gradient. The xenobiotics present in the environment could be
chemoattractant or chemorepellent (Jain et al., 2005). In a guided, non-
random manner bacteria swims toward or away from a chemical stimulant
at a flagella speed of 1800 rpm, powered by proton motive force.
The reversible nature of bacterial flagella helps it to move in clockwise
and anticlockwise direction. On the basis of signal transduction strategies
chemotaxis is divided into two categories: metabolism dependent and
metabolism independent. Former one shares the signalling pathways with
other bacterial behavioural responses. This phenomenon is also known as
energy taxis and aerotaxis (requires molecular oxygen and help bacteria
to move in oxygen concentration niches as it plays an important role in
biodegradation of xenobiotics by using oxygenases) and phototaxis are the
examples. The signal of this type of tactic movement initiates within the
electron transport chain (ETC) and through signal transduction the rate of
change of electron transport is detected. In this process, the metabolizable
substrates can be excite a behavioural response as long as receptor sensing
the change in cellular level is present (Pandey and Jain, 2002). The latter one
occurs through transmembrane chemoreceptorÊs that transmit information
via two component regulatory system to flagella that directs the cell to
move in preferential direction. The similar phenomenon has been seen in
fungi also but the fungal chemotactic is differ from bacteria as the bacterial
efficiency for bioremediation is strongly depends upon its mobility within
the system because for swimming it requires high soil matric potential or
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 27

at least continuous liquid films. In contrast to bacteria, fungi enlarge their


surface to develop the mycelia as it can easily breach through air water
interfaces (Furuno et al., 2010)

Degradation/Biotransformation Mechanisms of POPs

DDT
Microorganisms play an important role in the fate of DDT (1,1,1-Trichloro-
2,2-di(p-chlorophenyl)-ethane) in natural and controlled environments. A
range of bacteria and white rot fungi, such as Eubacterium limosum (Yim et
al., 2008), Alcaligenes eutrophus A5 (Nadeau et al., 1994), Boletus edulis (Huang
et al., 2007), Fusarium solani (Mitra et al., 2001) and Phanerochaete chrysosporium
(Bumpus and Aust, 1987) have been demonstrated to degrade DDT in
both pure culture and natural soil. Fungus uses lignin peroxidises for the
mineralization of DDT and in some fungal strains the rate of mineralization
is depend upon the carbon source. The rate and extent of mineralization of
DDT is lesser as compared to its analogs (dicofol and methoxychlor). DDT
can be biodegraded by two distinct microbial processes, aerobic oxidative
degradation and anaerobic reductive dechlorination.

Fig. 7: Biotransformation of DDT under aerobic condition by Alcaligenes


eutrophus A5. (a) DDT (b)2,3-dihydrodiol-DDT (c) 2,3-dihydroxy-DDT (d) Ring
fission product (e) 4-chlorobenzoic acid.
Aerobic Degradation
The aerobic transformation pathway of DDT by A. eutrophus A5 has
been studied in detail as shown in Fig. 7 (Nadeau et al., 1994). A. eutrophus
A5 initially oxidizes DDT (compound a) at the ortho and meta positions to
form a 2,3-dihydrodiol-DDT intermediate (compound b). It is proposed that
this is a dioxygenase type of attack resulting in the transient production of
a DDT dihydrodiol (compound b). The dihydrodiol compound is unstable
and easily dehydrates into two hydroxylated compounds under weak acidic
conditions (pH < 7.0). The dihydrodiol-DDT would be further degraded to
2,3-dihydroxy-DDT (compound c) by a dehydrogenase. 2,3-Dihydroxy-DDT
28 Bioremediation of Industrial Pollutants

would be further metabolized through meta cleavage to form the yellow


ring-fission product (compound d) which would then be catabolized to
4-chlorobenzoic acid (4-CBA) (compound e). 4-CBA appears to be a terminal
product formed from DDT by A. eutrophus A5 because it has lost the ability
to further degrade 4-CBA.

Anaerobic Degradation
In anaerobic conditions, DDT transformation commonly follows
a pathway of reductive dechlorination (You et al., 1996). Reductive
dechlorination is the major mechanism for the microbial conversion of
both the o,p -DDT and p,p -DDT isomers of DDT to DDD. Proteus vulgaris
was one of the first pure cultures of bacteria observed to reduce DDT to
DDD under reducing conditions. The anaerobic transformation pathway
of DDT in bacteria is shown in Fig. 8. In this pathway DDD undergoes
reductive dechlorination to 2,2-bis (4-chlorophenyl) ethylene (DDNU), which
is successively oxidized to 2,2-bis (4-chlorophenyl) ethanol (DDOH) and
2,2-bis (4-chlorophenyl) acetic acid (DDA). DDA is decarboxylated to 2,2-
bis (4-chlorophenyl) methane (DDM), which is oxidized to DBP, which is
not further metabolized under anaerobic conditions. Recent studies have
shown that 4-chlorobiphenyl- Degrading Gram-negative bacteria primarily
transform DDT to DDD, which is then dehydrogenated to DDE, followed
by dechlorination to DDMU under aerobic conditions.

Polychlorinated Biphenyls
The ability to degrade polychlorinated biphenyls (PCB) in found in
several genera of Gram-positive and Gram-negative aerobic and anaerobic
bacteria. Since the pioneering studies of Lunt and Evans (1970), Catelani
et al. (1971) and Ahmed and Focht (1973), several bacterial strains such as
Pseudomonas, Burkholderia, Comamonas, Cupriavidus, Sphingomonas, Acidovorax,
Rhodococcus and Bacillus able to use biphenyl as a sole source of carbon and
energy have been isolated and their capability to transform PCB congeners
has been evaluated. Burkolderia xenovorans LB400 is able to degrade a broad
range of PCBs (Seeger et al., 2001) and is a model bacterium for PCB
degradation. The degradation of biphenyl and transformation of PCBs is
usually catalyzed by enzymes encoded by the so-called biphenyl upper
(bph) pathway.

The Biphenyl Upper (bph) Pathway


A major interest for analyzing aerobic biphenyl degrading bacteria
is because of their capability to transform PCB congeners. Based on the
analysis of various biphenyl degrading isolates, it could be deduced that, in
general, lower chlorinated congeners are more easily transformed compared
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 29

Fig. 8: Bacterial transformation of DDT via reductive dechlorination.


30 Bioremediation of Industrial Pollutants

to higher chlorinated congeners and that PCB congeners with chlorines


only on one aromatic ring are more easily degraded, when compared
with those bearing chlorine substituents on both aromatic rings. The first
step of the PCB catabolic pathway is the formation of cis-2,3-dihydro-2,3-
dihydroxybiphenyl. This reaction is catalysed by biphenyl 2,3 dioxygenase
(BphA). Biphenyl 2,3 dioxygenase is a Rieske non-heme iron oxygenase,
multi-component enzyme complex which catalyzes the incorporation of
two oxygen atoms into the aromatic ring to form arene cis-diols where a
ferredoxin and a ferredoxin reductase act as an electron transport system to
transfer electrons from NADH to the terminal oxygenase. The biphenyl 2,3-
dioxygenases are of crucial importance for the successful metabolism of PCBs.
The next step of PCB catabolism is the formation of 2,3 dihydroxybiphenyl
which is catalysed by a cis-2,3 dihydro-2,3-dihydroxybiphenyl dehydrogenase
(BphB) and regenerate NADH. Cis-dihydrodiol dehydrogenases are involved
in various aromatic degradation pathways and exhibit common features
such as an absolute requirement for NAD+. 2, 3-dihydroxybiphenyl is
attacked by meta-clevaing 2, 3-Dihydroxybiphenyl 1, 2-dioxygenases (BphC),
and 2-hydroxy-6-oxo-phenylhexa-2, 2-dienoic acid is formed. The fourth
step of the bph pathway is catalyzed by 2-hydroxy-6-phenyl-6-oxohexa-2,
4-dieneoate (HOPDA) hydrolase BphD, which hydrolyzes HOPDA to yield
2-hydroxypenta-2, 4-dienoate and benzoate. The last step in PCB catabolism,
leading to the formation of chlorinated benzoic acid, is catalysed by
hydrolase. The complete degradation pathway of PCB is shown in Fig. 9.

Polycyclic Aromatic Hydrocarbons


PAHs compounds have low bioavailability and low water solubility that
are resistant to biological, chemical and photolytic breakdown. The larger
the molecular weight of the PAHs, the lower its solubility, which in turn
reduces the accessibility of the PAHs metabolism by the microorganisms.
PAHs degrading microorganisms such as bacteria, filamentous fungi, and
yeasts are ubiquitously distributed in environment and utilised PAHs as
a sole carbon source for their growth and metabolism (van Beilen and
Funhoff 2007; Wentzel et al., 2007). There are three fundamental different
mechanisms in the aerobic metabolism of PAH by bacteria and fungi.

Aerobic Degradation by Bacteria


Enzymatic degradation of hydrocarbons by bacteria has been widely
studied in the past decades (van Beilen and Funhoff, 2007; Boll and Heider,
2010). Microorganisms including Pseudomonas putida GPo1, Acinetobacter
sp. ADP1 and Mycobacterium tuberculosis H37Rv are involved in aerobic
degradation of PAHs. The principal mechanism for the aerobic bacterial
metabolism of PAHs is the initial oxidation of benzene ring by the action
of dioxygenase enzymes to form cis-dihydrodiols. These dihydrodiols are
Fig. 9: Pathway for biphenyl degradation BphA: Biphenyl 2,3-dioxygenase; BphB: cis-2,3-dihydro-2,3-dihydroxybiphenyl
dehydrogenase; BphC: 2,3-dihydroxybiphenyl 1,2-dioxygenase; BphD: 2-hydroxy-6-phenyl-6-oxohexa- 2,4-dieneoate
Persistent Organic Pollutants (POPs): Health Hazards and Challenges....

(HOPDA) hydrolase; BphH(E): 2-hydroxypenta-2,4-dienoate hydratase; BphI: acylating acetaldehyde dehydrogenase;


BphJ: 4-hydroxy-2-oxovalerate aldolase. BCL: benzoate-CoA ligase; BenABCD: benzoate 1,2-dioxygenase and benzoate
dihydrodiol dehydrogenase.
31
32 Bioremediation of Industrial Pollutants

dehydrogenated to form dihydroxylated intermediates, which can then be


further metabolised via catechols to carbon dioxide (CO2) and water (H2O)
as shown in Fig. 10. A few bacteria (i.e. Mycobacterium sp.) are also capable
of oxidising PAHs by the action of cytochrome P450 monooxygenase enzyme
to form trans-dihydrodiols. However, the bi-and tri-cyclic PAH substrates
are oxidised by bacterial naphthalene dioxygenase system which is a multi-
component enzyme, includes an NADH oxidoreductase, a ferredoxin and
an oxygenase component (contains active site). Unlike Bph dioxygenase,
naphthalene dioxygenase system (NDO) contains the catalytic portion
composed of large (đ) and small ( ) subunits in đ3 3 configuration. The
large subunit (đ) of catalytic portion contains the Rieske [2Fe-2S] centre
and mononuclear non-heme iron. The NDO is a large family of oxygenases
whose substrate specificity is determined by the alpha (đ) subunit.

Fig. 10: The workflow of “Omics”.

Aerobic Degradation by Fungi


A large number of fungal species have been involved in the degradation of
the PAHs. There are two main mechanisms through which PAH are degraded
by fungi: lignolytic enzymes and Cytochrome P450 monooxygenases (Peng
et al., 2008; Simarro et al., 2013). The term ligninolytic enzymes constitute
mainly three oxidative enzymes; Manganese peroxidase (MnP), lignin
Peroxidase (LiP) and laccases. These enzymes secreted extracellularly and
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 33

act on their substrate in normal to diverse condition. It is well known


that several white rot fungi are able to degrade PAHs from soils and
sediments by the action of ligninolytic enzymes. Recent studies have been
uncertain on PAHs degradation in low-oxygen and microaerobic conditions
by fungal ligninolytic enzymes (Silva et al., 2009). The maximum degradation
of naphthalene (69%) by strain 984 was observed having Mn-peroxidase
activity, followed by strain 870 (17%) showing lignin peroxidase and laccase
activities. Some fungi such as Aspergillus sp., Trichocladium canadense, and
Fusarium oxysporum efficiently degrade low molecular weight PAHs (2ă3
rings) by their ligninolytic enyzmes. Under ligninolytic conditions, fungi can
oxidise PAHs by generating free radicals (i.e. hydroxyl radicals) by donation
of one which oxidise the PAH ring. This generates a selection of PAH-
quinones rather than dihydrodiol, which can then be further metabolised
via ring fission to carbon dioxide (CO2).
Besides, the second major pathway in the metabolism of PAHs by non-
ligninolytic fungi is to oxidation of aromatic ring of PAH by cytochrome
P450 monooxygenase to produce an arene oxide. Arene oxide is subsequently
hydrated via epoxide hydrolase to form forms trans-dihydrodiols (Cerniglia,
1997). In addition, phenol derivatives may be produced from arene oxide
by the non-enzymatic rearrangement of the compound, which can act
as substrate for subsequent sulfation or methylation or conjugation with
glucose, xylose, or glucuronic acid. However, fungal cytrochrome P450
monooxygenase are a super-family of hemethiolate protein bound to the
membrane of endoplamic reticulum. Metabolites that are formed by fungal
degradation of PAHs are similar to those formed by mammalian cells.
Studies had been done on Phanerochaete chrysosporium that has the capability
to produce P450 monooxygenase. The two genes pc-1(CYP63A1) and pc-2
(CYP63A2) of P450 monooxygenase were regulated under nutrient rice and
limited medium to check its response against environmental pollutants like
PAHs, DDT and lignin derivatives. The results showed that these two genes
show the positive response against the mentioned pollutants (Doddapaneni
and Yadav, 2004). In another similar studied showed that benzo(đ) pyrene
was degraded by Phanerochaete chrysosporium using P450 monooxygenase in
both ligninolytic and non-ligninolytic phase. In non-ligninolytic phase, the
P450ăhydroxylated metabolites were formed along with the up regulation
in pc-2 (CYP63A2) and pah4 (CYP5136A3) while in ligninolytic phase the
degradation rate gets higher (91.6%) (Bhattacharya et al., 2013).

Anaerobic Degradation by Bacteria


Anaerobic degradation of PAHs has been gaining importance in
recent years as anaerobic conditions are widespread in numerous polluted
environments and oil reserves. Still some of the bacterial strains that
34 Bioremediation of Industrial Pollutants

use alkanes as a source of carbon under anaerobic conditions have been


characterized in the recent past (Rojo et al., 2009). In the aerobic process of
PAHs degradation, molecular oxygen is incorporated into the aromatic ring
prior to the dehydrogenation and subsequent PAHs ring cleavage. But, in
anaerobic process (the absence of oxygen), alternative electron acceptor such
as nitrate, ferrous iron, and sulphate are necessary to oxidation of PAHs.

Recent Advancement in Microbial Degradation of POPs


Recently, new approach for the process of biodegradation has been
revealed. Scientists have shown the application of genetically modified
microbes and metagenomics for the degradation of POPs from different
sources.

Genetically Modified Microorganism


The main aim of biomolecular engineering in the field of bioremediation
is to enhance the biocatalytic capability of microbes to degrade POPs. It is a
new field that exploits engineering biomolecules and biomolecular processes
for development of genetically engineered enzymes or microorganisms
for bioremediation purpose (Ang et al., 2005). Studies had been done on
functional expression of fungal laccase in Saccharomyces cerevisiae, which
was from Myceliophthora thermophila (MtL) and previously expressed only
in Aspergillus oryzae was subjected to directed evolution. It was found that
directed evolution increased the laccase expression eight fold and 22 fold
increased in Kcat together with 170 fold increase in total activity. Due to high
thermal stability of MtL enzyme it holds the great potential to remediated
PAHs (Bulter et al., 2003).
Out of large number of aforementioned enzymes that help in degradation
of PAHs, CYPs are one of the largest super families that degrade PAHs by
forming catechols which is then further degraded by catechol dioxygenase to
form various TCA cycle products in microorganisms. Wild type cytochrome
P450 enzyme from Bacillus megaterium has been shown to have an inherently
low activity towards naphthalene, fluorine, acenaphthene, acenaphtylene
and 9-methlyanthracene. Therefore, several mutations has been done based
on their crystal structure to obtain a cytochrome P450 BM-3, which showed
the high activity towards PAHs and found to have a great potential in
degradation of PAHs in environment. P450cam (CYP101) has been mutated
to get the high oxidation activity towards PAHs. The wild type CYP101
from Pseudomonas putida had low activity (<0.01 min-1) but after mutation
in the active site residues F87 and Y96 greatly enhanced the activity of
CYP101. Recently first time the eukaryotic P450 CYP5136A3 enzyme from
Phenerochaete chrysosporium has been mutated two times and the enzyme
formed were expressed in Pichia pastoris. It was found that L324F and
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 35

W129F/L324F showed the enhanced oxidation activity towards pyrene and


phenanthrene (Syed et al., 2013).
PCBs that are degraded by biphenyl dioxygenase present in the
microorganisms via meta- cleavage pathway to yield TCA intermediates
and chlorobenzoate (CBA). To reduce the accumulation of CBAs, the upper
pathway enzyme genes for PCB degradation of RHA1 were introduced into
Burkholderia sp. NK8 which is a CBA degrading bacteria. However, this
recombinant strain exhibit no BpA activity so to retain BpA activity of RHA1
in NK8, the BpA genes were constructed by combining the bphAaAbAcAd
genes of RHA1 and bph3A4 of Pseudomonas pseudoalcaligenes KF707 and
the constructed plasmid were introduced into NK8 that efficiently degrade
PCBs and reduce the accumulation of CBA (Ohmori et al., 2011).
Apart from these advantages there are several limitations. Construction
of enzyme with new function represents a vast challenge in genetic
engineering. It is very difficult to apply bimolecular engineering to the
bioremediation of novel pollutants because research is usually focused on
altering the enzymes that can perform the desired function (Ang et al.,
2005). Genetically engineered microorganisms may not survive with the
extra energy demand imposed by the presence of foreign genetic material
when released into the environment.

Role of Metagenomics and Metaproteomics for the Assessment of Organic


Pollutants Bioremediation
POPs contaminated site is influenced by the indigenous microbial
community in environment, which establish a complex ecological niche.
But, these microbial communities are not easily culturable therefore to
understand the detail structure of community composition and role of
their product for bioremediation of various organic compounds through
direct DNA isolation from bacterial community will help to understand the
degradation mechanism of specific ecosystem. Simultaneously, the study
of primary and secondary metabolites/ protein produced by them which
will facilitate to reveal to understand the pollutant-microbe interaction,
its function at molecular level and organism response to environmental
factors such as abiotic stress due to pollution, temperature etc (Bundy
et al., 2009, Lacerda and Reardon, 2009). The organic pollutant exposure
(especially high dose or repeated exposure) can elicit detrimental effects on
life present on earth through diverse mechanism, which leads to formation
of toxic reactive metabolites and also disrupt endogenous metabolism
due to change in their environment. Moreover, due to recalcitrant nature
of pollutants there may be possibility of incomplete mineralization by
microbes or accumulation of sister metabolites in environment. Therefore,
there is a need for prevention and treatment by more accurate method as
36 Bioremediation of Industrial Pollutants

compared to the traditional one because these methods lack the capacity to
define global changes and unexpected events during metabolism and also
exploring or engineering new catabolic pathway to study the primary and
secondary metabolites for production of effective bioremediation reaction
(Chen and Kim, 2013). Metagenomics and proteo-metabolomics would
create a system wide approach to studying site specific microorganisms
during active mineralization process. In addition, the new generation
sequencing technology i.e. next generation sequencing with its ability to
sequence thousands of sequences concurrently and reduce the cost and
time as compared to conventional sequencing method. The workflow of
metagenomics, metaproteomics and metabolomics approach expression
profiling experiment as shown in Fig. 11.

Fig. 11: Proposed pathway of microbial catabolism of PAHs


in bacteria and fungi.

Research has been done to identify the metabolic pathway of bacterial


community from the environment and establish a link between taxonomic
composition and the relative abundances of these metabolic pathways. On
the basis of 16S rRNA the bacterial community were identified, some of them
showed the greater degradability of xenobiotics while some bacterial genes
are associated with metabolic pathways (Debroas et al., 2009). However,
studies had been done where metagenomic approach were used to identify
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 37

the bacterial community by cultivation, metagenomics and stable isotope


probing that has the capability to degrade PAH (Gutierrez, 2011)stable
isotope probing and pyrosequencing</title><secondary-title>Reviews in
Environmental Science and Bio/Technology</secondary-title><alt-title>Rev
Environ Sci Biotechnol</alt-title></titles><periodical><full-title>Reviews in
Environmental Science and Bio/Technology</full-title><abbr-1>Rev Environ
Sci Biotechnol</abbr-1></periodical><alt-periodical><full-title>Reviews
in Environmental Science and Bio/Technology</full-title><abbr-1>Rev
Environ Sci Biotechnol</abbr-1></alt-periodical><pages>301-305</
pages><volume>10</volume><number>4</number><keywords><keywor
d>Polycyclic aromatic hydrocarbons (PAHs. In another study, functional
screening of metagenomic library for genes involved in microbial
degradation of aromatic compounds had been done. In addition, various
extradiol dioxygenases were retrieved, sequenced and characterised and
also the evolution of these genes was discussed (Suenaga et al., 2007).
Recent investigation on potential biodegradation pathways of persistent
pesticides in fresh water and marine sediments through metagenomic
approach has been done. It was found that Plesiocystis, Anaerolinea, Jannaschia
and Mycobacterium were found to be effective population present in all
sediments out of 69 genera identified which help in biodegradation. In
addition, complete degradation pathway of DDT and atrazine (ATZ) and
partial degradation pathway of hexachlorocyclohexane (HCH) were detected
in all sediments (Fang et al., 2014).

Biotransformation Mechanism of Xenobiotics in Mammals


In mammals, biotransformation of xenobiotics and other foreign
chemicals catalyzed by enzymes are widely distributed throughout the
body. However, the liver is the primary biotransforming organ due to
its large size and high concentration of biotransforming enzymes. The
kidneys and lungs are next with 10%ă30% of the liverÊs capacity. Since,
the liver is the primary site for biotransformation, it is also potentially quite
vulnerable to the toxic action of a xenobiotic that is activated to a more
toxic compound in the liver and to a lesser extent also in the lung and
intestine. An important consequence of mammalian biotransformation is that
the physical properties of a xenobiotic are generally changed from those
favouring absorption (lipophilicity) to those favouring excretion in urine
or faeces (hydrophilicity). Without biotransformation, lipophilic xenobiotics
would be excreted from the body so slowly that they would eventually
overwhelm and kill an organism. There are many different processes occurs
during xenobiotics transformation and the pathways of POPs transformation
can be divided into two phases: phase I and phase II.
38 Bioremediation of Industrial Pollutants

Phase-I
Phase I reactions involve hydrolysis, reduction, and oxidation of POPs.
These reactions expose or introduce a functional group (ăOH, ăNH2, ăSH,
or ăCOOH) and usually result in only a small increase in the hydrophilicity
of xenobiotics. In general, phase I biotransformation is often required for
subsequent phase II biotransformation as shown in Fig. 12.

Fig. 12: Biotransformation of xenobiotic in mammalian system.

Although several enzyme systems participate in phase I metabolism


of xenobiotics, perhaps the most notable enzyme in the xenobiotic
transformation pathway is cytochrome P450 (Cyt P450). The highest
concentration of Cyt P450 is found in liver endoplasmic reticulum
(microsomes), but this enzyme is present in virtually all tissues. All Cyt
P450 are heme-containing proteins. The heme iron in Cyt P450 is usually
in the ferric (Fe3+) state. When (Fe3+) reduced to the ferrous (Fe2+) state,
Cyt P450 bind to ligands such as O2 and carbon monoxide (CO). The Cyt
P450 detoxify and/or bioactivate a vast number of xenobiotic chemicals
and conduct functionalization reactions that include N- and O-dealkylation,
aliphatic and aromatic hydroxylation, N- and S-oxidation, and deamination.
It catalyzes several types of oxidation reactions, such as hydroxylation of
an aliphatic or aromatic carbon, epoxidation of a double bond, heteroatom
(S-, N-, and I-), oxygenation and N-hydroxylation, heteroatom (O-, S-, N-,
and Si-) dealkylation, oxidative group transfer, cleavage of esters, and
dehydrogenation.

Phase-II
Phase II biotransformation is catalyzed often by the „transferase‰
enzymes that perform conjugating reactions. Included in the phase II
reaction schemes are glucuronidation, sulfonation (more commonly called
sulfation), methylation, acetylation, glutathione conjugation, and amino acid
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 39

conjugation (such as glycine, taurine, and glutamic acid). The products


of phase II conjugations are typically more hydrophilic than the parent
compounds and therefore usually more readily excretable. Phase II
biotransformation of POPs or xenobiotics may or may not be preceded
by phase I biotransformation. Specific families of phase II xenobiotic-
metabolizing enzymes include the UDP glucuronosyltransferases (UGTs),
sulfotransferases (STs), N-acetyltransferases (arylamine N-acetytransferase;
NATs), glutathione S-transferases (GSTs) and various methyltransferases,
such as thiopurine S-methyl transferase and catechol O-methyl transferase.
The GSTs function as cytosolic dimeric isoenzymes of 45ă55 kDa size
that have been assigned to at least four classes: alpha, mu, pi, theta, and
zeta; humans possess >20 distinct GST family members. The conjugation
of certain xenobiotics with glutathione is catalysed by all class of GSTs.
For example, the alpha, mu, and pi classes of human GSTs all catalyse
the conjugation of 1-chloro-2,4-dinitrobenzene. In concert with the phase-I
enzymatic machinery, the phase-II enzymes metabolize, detoxify, and at
times bioactivate xenobiotic substrates in coordination.

Biotransformation Mechanism of Xenobiotics in Algae


In ecosystem, many microalgae and protozoa are present, which are
involved in the various activities but only few of them are reported in the
degradation of hydrocarbons, pesticides and PCBs (Jain and Bajpai, 2012).
Some microorganisms utilise the non-chlorinated aliphatic and aromatic
hydrocarbons as a carbon source in their metabolic pathway. Algae are
capable of degrading petroleum hydrocarbons in less toxic with the help
of certain enzymes produced by them (Chekroun et al., 2014). Many algal
species like Rhodococcus genus, Desmarestia sp., Focus sp. and Ascophyllum
nodosum are found to be effective in efficiently degradation of hydrocarbons
(Chekroun et al., 2014). Some algae are degraded not only hydrocarbons
but also pesticides. Recent investigation has been done which showed
that the Scenedesmus obliquus and Scenedesmus quadricauda were capable of
removing dimethomorph, pyrimethanil and isoproturon from their medium
(Dosnon-Olette et al., 2010). The schematic representation in the Fig. 13
shows the main pathway leading to xenobiotic metabolism in algae. The
biotransformation mechanism of xenobiotics in algae (photosynethetic
organisms) bear similarities to those of the mammalian liver but in algae
an additional phase III is also occur.

Phase I
In this phase, the addition of reactive functional groups like oxidations,
reductions, or hydrolysis occurs. These groups are catalysed by membrane
bound protein MFO i.e. Cyt P450 and Cyt b5, which transforms the lipophilic
xenobiotics into water soluble compounds and NADPH cytochrome P450
40 Bioremediation of Industrial Pollutants

reductase. The phase one is further divided into various steps: (1) Binding
of substrate to the prosthetic heme ferric iron group of the enzyme. (2)
Reduction of iron by flavoprotein P450 reductase. (3) The release of product
by the formation of substrate radical after the addition of second electron
by Cyt b5. Subsequently the peroxides are formed and O-O bond get
cleaved.

Fig. 13: The metabolism/biotransformation of xenobiotics in photosynthesized


organisms cell (algae). By pass reactions are represented by dot lines. ER:
Endoplasmic reticulum.
Phase II
In Phase II to facilitate the excretion, the large and polar groups such as
GSH and glucuronic acid (GA) are covalently added to xenobiotics. Several
xenobiotics are metabolise by an integrative process involving previous
exploit of the phase I enzymes while others posse the essential functional
groups like ăCOOH, -OH or ăNH2 by conjugative phase II enzymes such
as GST and UDP-glucoronyltransferases (UDPGTs) in direct metabolism.

Phase III
In photosynthetic organisms phase III, is often characterised by
compartmentation of the exported xenobiotics in the cell wall fraction or
in vacuole (Torres et al., 2008).
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 41

Phytoremediation of POPs
Phytoremediation is an eco-sustainable, non-invasive, green technology
for In-situ remediation of environmental pollutants, accomplished by the
use of plants and their associated microbiota for the uptake, sequestration,
detoxi cation, or volatilization of pollutants from soils, water, sediments,
and possibly air. These techniques use plants to extract, degrade, contain or
immobilise pollutants in soil, groundwater, surface water and other polluted
media. Although information on the phytoremediation of POPs rather scanty,
very recent literature has indicated that some plants (primarily those belong
to the Cucurbitaceae family) are capable for taking up significant amount
of POPs and accumulate them in their tissue. However, there are several
mechanisms used to treat contaminated sites that take place outside, inside,
or through plant systems.
Ć Phytovolatilization: In this process, water-soluble pollutants are
taken up by the plant roots, pass through the plant or are modified
by the plant, are transported to the leaves, and volatised into the
atmosphere through the stomata.
Ć Phytostabilization: It is In-situ inactivation or immobilisation of
pollutants by plant roots and is primarily used for the remediation
of soil, sediment and sludge.
Ć Phytodegradation: It is the degradation or transformation of highly
toxic organic pollutants into less toxic forms via the action of plant
enzymes.
Ć Phytoextraction: This is also known as phytoaccumulation,
phytoabsorption and phytosequestration process. Pollutant
accumulating plants to remove pollutants from soil via root
absorption and concentrates them in aboveground harvestable plant
parts.
Ć Rhizofiltration: Rhizofiltration or phytofiltration, is a subset
technique of phytoremediation which refers to the approach of using
plant biomass for removing contaminants from polluted water. It
is a root-zone technology of terrestrial and aquatic plants, which
interact with the pollutants, present in wastewater.
Ć Rhizodegradation: It is also known as phytostimulation. In this
process, it is the contaminants are degraded in the rhizosphere by
means of microbial activity, which is enhanced by the presence of
plant roots.
42 Bioremediation of Industrial Pollutants

Regulation and Guideline for Control of POPs in Environment


To protect the environment from the adverse effects of POPs, many
nations worldwide have enacted legislation to regulate various types of POPs
as well as to mitigate the adverse effects of pollution. There are three main
POPs initiatives exist i.e. the Aarhus Protocol and the Stockholm Convention
and Persistent Organic Pollutants Review Committee. The aim of these
initiatives is to control, reduce or eliminate POPs into the environment.

The Aarhus Protocol


The Protocol on persistent organic pollutants (POPs) was adopted by
the Executive Body for the Convention on Long-range Transboundary Air
Pollution (LRTAP) on 24 June 1998 in Aarhus (Denmark). The objectives of
this protocol are to eliminate discharges, emissions and losses of POPs. The
protocol bans the production and use of some products (aldrin, chlordane,
chlordecone, dieldrin, endrin, hexabromobiphenyl, mirex and toxaphene).
Others are scheduled for elimination at a later stage (DDT, heptachlor,
hexaclorobenzene, PCBs). This protocol severely restricts the use of DDT,
HCH (including lindane) and PCBs. It includes provisions for dealing with
the wastes containing POPs and to reducing POPs emissions (dioxins, furans,
PAHs and HCB). There are about 42 members of this protocol, which covers
both Eastern and Western Europe, besides Canada and the US. The protocol
was amended on 18 December 2009, but the amended version has not yet
come into force.

The Stockholm Convention


As described previously, in 2001, the Stockholm Convention on
POPs was adopted, a treaty negotiated under the auspices of the UNEP.
Building on the 1998 Aarhus Protocol, the Stockholm Convention raised
the profile of POPs to the global level. The Stockholm Convention focuses
on eliminating or reducing releases of POPs. It recognizes that a special
effort may sometimes be needed to phase out certain chemicals for certain
uses and seeks to ensure that this effort is made. It also channels resources
into cleaning up the existing stockpiles and dumps of POPs that litter the
worldÊs landscape. Ultimately, the Convention points the way to a future
free of dangerous POPs and promises to reshape our economyÊs reliance
on toxic chemicals. The Stockholm Convention is perhaps best understood
as having five essential aims:
Ć Eliminate dangerous POPs, starting with the 12 worst
Ć Support the transition to safer alternatives
Ć Target additional POPs for action
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 43

Ć Cleanup old stockpiles and equipment containing POPs


Ć Work together for a POPs-free future

POPs Review Committee


The POPs Review Committee (POPRC) is a subsidiary body to the
Stockholm Convention. The objective of the POPRC is to review proposals
submitted by Parties to the Convention for listing new chemicals in
Annex A, B, and/or C. Article 8 of the Stockholm Convention entails the
reviewing process of new chemicals and Annex D, Annex E and Annex
F specify the information required for the review as shown in Table 7.
However, there are many chemicals with POP-like characteristics that are
currently not listed in the Stockholm Convention or Arhus protocol. In
2005, five candidate chemicals are nominated to the POPRC for inclusion
in the Convention. Norway nominated pentabromodiphenyl ether (a
brominated flame retardant); the European Union nominated chlordecone
(pesticide) and hexabromobiphenyl (flame retardant); Sweden nominated
perfluorooctansulfonate (PFOS); and Mexico nominated Lindane. In
November 2005, the Committee concluded that all chemicals are classifiable
as POPs.

Fig. 14: Schematic diagram of major regulatory authorities for control of POPs
in environment.
Table 7: Detail of annexure D, E & F of Stockholm Convention (2001) regarding POPs screening and monitoring.
44

Annexure Parameter Details


Chemsical identity The detail chemical nature and properties of compound has to be
investigated.
Annex D: Persistence/half life Investigate the half life of chemical in water/soil/sediment
Information requirement &
screening criteria Bioaccumulation Investigate the bioconcentration/bioaccumulation factor properties in
aquatic and other species as well its high ecotoxicity
Potential for long range Measured levels of the chemicals in location distant from the sources of
transport its release that are of potential concern
Toxicity/adverse effect Find out the adverse effect of chemicals to human health or to the
environment
Sources The detail use, releases such as discharge, losses and emission of
chemicals has to be investigated.
Annex E: Hazard assessment Hazard assessment including a consideration of toxicological interaction
Information requirement involving multiple chemicals
for the risk profile
Environmental fate The environmental fate including chemical and physical properties of
chemical as well as it persistence its environmental transport within
environmental compartments, degradation and transformation to other
chemicals has been investigated.
Monitoring data The detail monitoring of data has been find out
Exposure The chemical exposure in local area and bioavailability has been
investigated,
National & International National & international risk evaluation, assessment of profile and hazard
risk evaluation classification has been investigated.
Status of chemical Status of the chemical under international conventions
Bioremediation of Industrial Pollutants
Control measures Efficacy and efficiency of possible control measures in meeting risk
reduction goal
Alternatives Technical feasibility, efficacy, risk, availability and accessibility of compound
Annex F: have been found out.
Information on socio-
economic consideration Positive/negative impact The positive/negative impact of chemical on society of implementing
possible control measure has been investigated.
Waste & disposal In particular, obsolete stocks of pesticides and clean-up of contaminated
implication site
Access information Access to information and public education
Status of control and Status of control and monitoring capacity of chemicals has been
monitoring investigated
National & Regional Any national or regional control actions taken, including information on
control alternatives and other relevant management
Persistent Organic Pollutants (POPs): Health Hazards and Challenges....
45
46 Bioremediation of Industrial Pollutants

Challenges in the Degradation of Persistent Organic Pollutants


POPs are becoming a great concern due to increased industrial usage
causing their accumulation, persistence in living beings and environment.
Through, several mechanisms its exposure causes several fatal consequences
to organs and tissues such as oxidative stress and finally leading to
cell death. Several international strategies have been made to overcome
the usage and complete elimination of POPs but still many developing
countries across the world are not following the guidelines comes under
Aarhus Protocol and Stockholm Convention. Presently, traditional treatment
methods like incineration, solvent extraction and landfilling are used for
the removal of POPs. But, these methods are sufficient to eradicate the
problem moreover the entire existing methods include high cost, incomplete
degradation of POPs and production of more toxic compounds during
degradation. So, there is a need to develop the effective technique for
bioremediation capable to detoxify them completely. In recent past, the
upcoming technology that uses plants, microbes and their enzymes for the
degradation of POPs in an environmental friendly manner. Bioremediation
involves microbial degradation approach which uses the microbes that have
the capability to accumulate and degrade organic pollutants leading to
upgrading the quality of soil and water. However, depending upon the
type of contaminants (PAHs, PCBs or OCPs) different mechanism of POP
degradation (production of specific enzyme) has been implemented by
microbes. The latest addition has opened a broad perspective for the removal
of different organic pollutants which are recalcitrant in nature. However,
due to generation of several unknown pollutants from industrial process
is challenge for safe disposal. These are causing mutagenic, carcinogenic
and endocrine disrupting effect on human and aquatic life. Conclusively, it
can be said that microbial degradation technology has given us a platform
that could direct us towards the elimination of POPs contamination in an
eco-friendly manner. Moreover, there is no detail data or any adequate
screening of chemical nature and toxicity profile for their monitoring as
per POPRC recommendation as Annex D, E & F.

Conclusion
POPs are becoming a great concern due to increased industrial usage
causing their accumulation, persistence in living beings and environment.
Through, its exposure causes several fatal consequences to organs and
tissues such as oxidative stress and finally leading to cell death. Several
international treaties have been made to overcome the usage and complete
elimination of POPs but still many developing countries across the world are
not following the guidelines comes under Aarhus convection and Stockholm
convection.
Persistent Organic Pollutants (POPs): Health Hazards and Challenges.... 47

Presently, the traditional treatment methods like incineration, solvent


extraction and landfilling are used for the removal of POPs. But, these
methods are sufficient to eradicate the problem moreover; the entire
existing methods include high cost, incomplete degradation of POPs and
production of more toxic compounds during degradation. Hence, there is a
need to develop the eco-friendly and low cost technique for the treatment
of POPs from contaminated sites. In recent past, the upcoming technology
that uses plants, microbes and their enzymes for the degradation of POPs
in an environmental friendly manner. Bioremediation involves microbial
degradation approaches, which uses the microbes that have the capability to
accumulate and degrade organic pollutants leading to restore the quality of
soil and water. However, depending upon the type of contaminants (PAH,
PCB or OCPs) different mechanism of POP degradation (production of
specific enzyme) has been implemented by microbes. The latest addition has
opened a broad perspective for the removal of different organic pollutants,
which are recalcitrant in nature. However, due to generation of several
unknown pollutants from industrial process is challenge for safe disposal.
These are causing mutagenic, carcinogenic and endocrine disrupting effect
on human and aquatic life. Conclusively, it can be said that microbial
degradation technology has given us a platform that could direct us towards
the elimination of POPs contamination in an eco-friendly manner.

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