The Fate of Nitrogen in Bioreactor Landfills

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The Fate of Nitrogen in Bioreactor Landﬁlls
Article in Critical Reviews In Environmental Science and Technology · July 2005

DOI: 10.1080/10643380590945003
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Critical Reviews in Environmental Science and Technology, 35:365-399, 2005 ( Taylor & Francis
Copyright © Taylor & Francis Inc. Tay,m,f,r,ncm
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ISSN: 1064-3389 print / 1547-6537 online

DOI: 10.1080/10643380590945003
The Fate of Nitrogen in Bioreactor Landfills
N. D. BERGE and D. R. REINHART

Department of Civil and EnvironmentalEngineering,University of CentralFlorida, Orlando,
Florida, USA
T. G. TOWNSEND
Department of EnvironmentalEngineering and Science, University of Florida, Gainesville,
Florida, USA
Although bioreactor landfills have many advantages associ-

ated with them, challenges remain, including the persistence of
ammonia-nitrogen in the leachate. It has been suggested that
ammonia-nitrogenis one of the most significant long-term pollu-
tion problem in landfills and is likely a parameterthat will de-
termine when landfill postclosure monitoring may end. The fate
of nitrogen in bioreactorlandfills is not well understood.As more
landfills transition operation to bioreactors, more attention must
be paid to how operating the landfill as a bioreactormay affect
the fate of nitrogen. Processessuch as sorption, volatilization, ni-
trification, denitrification,anaerobicammonium oxidation, and
dissimilatory nitratereduction may all occur.
KEY WORDS: aerobic treatment, ammonia-nitrogen, denitrifica-

tion, leachate, nitrification
I. INTRODUCTION
A new and promising trend in solid waste management is to operate the

landfill as a bioreactor. Bioreactor landfills are controlled systems in which
moisture addition (often leachate recirculation) and/or air injection are used
to create a solid waste environment capable of actively degrading the readily
biodegradable organic fraction of the waste. Several researchers have docu-
mented the benefits associated with bioreactor technology.79,90, 98,10,12 6 One
Address correspondence to N. D. Berge, Department of Civil and Environmental Engi-

neering, University of Central Florida, PO Box 162450, Orlando, FL 32816-2450, USA. E-mail:
UCFNickib@cs.com
365
366 N. D. Berge et al.
advantage is that increased waste degradation rates characteristic of bioreac-

tor landfills permit the life of a bioreactor landfill to be expanded beyond that
of conventional landfills through recovery of valuable airspace. As leachate
is recirculated, it is treated in situ, decreasing its organic strength and thus
potential impact to the environment. In situ treatment potentially reduces
the length of the postclosure care period and associated costs. 9 0'99'101 Ad-
ditionally, bioreactor landfills stimulate gas production; the majority of the
methane is produced earlier in the life of the landfill, allowing for more
efficient capture and subsequent use.
Although the organic strength of the leachate is significantly reduced
in bioreactor landfills, ammonia-nitrogen remains an issue. The ammonia-
nitrogen concentrations found in leachate from bioreactor landfills are greater
than those found in leachate from conventional landfills.7' 82 Ammonia-
nitrogen tends to accumulate in both systems because there is no degradation
pathway for ammonia-nitrogen in anaerobic systems. However, in bioreactor
landfills, moisture addition and/or recirculating leachate increases the rate
of ammonification, resulting in accumulation of higher levels of ammonia-7 17 82 93
nitrogen, even after the organic fraction of the waste is degraded.' ' '
The increased ammonia-nitrogen concentrations intensifies the toxicity of
the leachate to aquatic species,' 25 potentially inhibiting the degradation pro-
cess and necessitating leachate treatment before ultimate disposal to protect
receiving waters.' 7 It has been suggested that ammonia-nitrogen is one of
the most significant long-term pollution problem in landfills, 7 and it is likely
that the presence of ammonia-nitrogen will determine when the landfill is
biologically stable and when postclosure monitoring may end. 93 Thus an
understanding of the fate of nitrogen in bioreactor landfills and possible
mechanisms for ammonia-nitrogen removal is critical to both a successful
and economic operation.
As more and more landfills transition operation to bioreactors, more at-
tention must be paid to how operating the landfill in such a manner may affect
the fate of nitrogen. The in situ physical, chemical, and biological processes
in bioreactor landfills differ from those typically observed when operating
a landfill conventionally, potentially resulting in different nitrogen transfor-
mation and removal processes. The fate of nitrogen in bioreactor landfills
is not well understood. Because of the adverse impact ammonia-nitrogen
has on the environment, an understanding of nitrogen transformation pro-
cesses in bioreactor landfills is necessary to ensure adverse environmental
impacts and/or treatment costs are minimized by expanding the current use
of landfills to include in situ leachate treatment.
This article discusses the nitrogen transformation and removal processes
that may occur in bioreactor landfills. Little research has been conducted eval-
uating the fate of nitrogen in bioreactor landfills, or in conventional landfills
for that matter. However, it is suspected that processes that typically occur
in wastewater treatment and in soils will also occur in bioreactor landfills,
Nitrogen in BioreactorLandfills 367
but in a much less controlled fashion, as the inherent variability and hetero-
geneities in bioreactor landfills do not allow for them to be operated with
the high level of control possible in wastewater treatment processes. Using
wastewater and soil literature, as well as landfill-related literature, nitrogen
removal and transformation processes that may occur in bioreactor landfills
are discussed and evaluated in this review.
II. BIOREACTOR LANDFILL OPERATION
Traditionally, landfills have been thought of as storage and containment sys-

tems, functioning primarily to entomb the waste. Recently, however, the focus
of solid waste management has changed to regarding the landfill as a com-
plex biological system capable of managing solid waste in a more proactive
manner, acting to degrade the readily biodegradable material.','100 ,10 1 Be-
cause bioreactor landfill environments are different from conventional land-
fills, there is potential for a greater number of nitrogen transformation and
removal processes to occur and for them to occur to a greater extent than
in conventional landfills. System design of bioreactor landfills provides the
flexibility in the location and duration of liquid and air injection, allowing for
adjustment of pH, oxidation-reduction potential (ORP), and moisture content
to create an environment conducive to microbial degradation and biologi-
cal nitrogen removal. System design is rigid with respect to parameters such
as waste composition and age (i.e., organic carbon content); waste compo-
nents cannot be controlled and vary from landfill to landfill, while waste age
varies from location to location within a landfill. Thus, in a landfill, the active
control of in situ reactions and nitrogen removal/transformation is generally
restricted by the location and volume of injected liquid and air.
Liquid addition to landfills has many advantages associated with it.
Leachate recirculation involves the collection and redistribution of leachate
through the landfill. Moisture addition and movement are important factors
affecting waste biodegradation, resulting in an increase in the moisture con-
tent of the waste and distribution of nutrients throughout the landfill, respec-
tively. Optimal levels of moisture content have been found to be between
40 and 70%, on a wet-weight basis. 6 Much research has been conducted
evaluating the benefits associated with increasing the moisture content of
solid waste and can be found elsewhere.10 1 At times, insufficient leachate
is available and it is necessary to supplement with other liquids such as
groundwater, stormwater, wastewater, or surface water.
Achieving uniform liquid distribution is difficult. Waste heterogeneities
and differences in compaction within landfills create distribution challenges.
Injected liquid will flow around areas with lower hydraulic conductivities
and channel through the waste following preferential flow pathways formed
by areas of higher hydraulic conductivites; the areas of higher hydraulic
conductivity may be due to waste heterogeneity or differences in compaction

ratios.7 3 The nonuniform distribution that occurs results in portions of the
landfill (on both a micro and macro level) having various moisture con-
tents and thus different waste degradation rates; therefore, several microbial
consortiums will be present, potentially in close proximity to one another,
allowing for different types of microbial degradation and thus nitrogen
removal/transformations to occur simultaneously. Differential settlement may
also occur as a result of the changes in waste degradation with respect to
location. There are different methods that can be used to reinject leachate
or add liquid to landfills, including horizontal trenches and vertical injection
98 99
pipes. These recirculation methods have been reviewed elsewhere. ' Rein-
troduction rates, for horizontal trenches, vary from 0.15 to 0.30 gpm/ft trench,
gpm. 10 1
while vertical injection rates in wells are generally from 0.5 to 2.5
Air addition has also been used as an enhancement and has been shown
to enhance degradation processes in landfills at both the field and laboratory
scale. 4,36,68,7479,96,112 Adding air uniformly throughout the waste is also a chal-
lenge. Not only do waste heterogeneities and compaction affect the air distri-
bution, the presence of moisture does as well. Air will take the path of least re-
sistance; thus, there will likely be areas of an aerobic landfill in which air does
not reach, resulting in anoxic or anaerobic pockets within the waste mass.
Generally, bioreactor landfills undergo the same degradation processes
as conventional landfills, just at a faster rate and to a greater extent because of
the optimization of in situ conditions. However, degradation pathways may
vary depending on the operation of the bioreactor landfill. Compared with
conventional landfills, bioreactor landfills have shown a more rapid and com-
plete waste conversion and stabilization process. 46,90,98,126 Increased waste
degradation rates characteristic of bioreactor landfills may allow for the life of
a bioreactor landfill site to be expanded beyond that of a conventional land-
fill, potentially allowing for the reuse of one site rather than construction
of many. Because waste degradation rates increase in bioreactor landfills,
airspace may be created by settlement and filled prior to closure. Moisture
injection increases the rate of initial settlement due to additional unit weight,
and, over time, increases the extent of waste degradation, all resulting in
the recovery of a significant volume of airspace. For example, Reinhart and
A1-Yousfi99 reported that for one landfill 13-15% settlement occurred over
a 4-year period when recirculating leachate; a dry control cell at the same
site settled only 8-12%. Bioreactor landfills also provide a means to store
and/or treat leachate. As leachate is recirculated, it is treated in situ via natu-
rally occurring processes such as adsorption, ion exchange, and mechanical
filtration, 91 significantly decreasing both the organic strength (i.e., chemical
oxygen demand [COD] and biochemical oxygen demand [BOD] by almost
50%) and heavy metal content, thus reducing impact to the environment
90 99
were the leachate to reach the groundwater or surface water. ' Not only
can leachate be treated within bioreactor landfills, but it may also be stored
by adsorption by the waste, rather than stored external to the landfill. Per-
haps the biggest advantage of bioreactor landfills is the reduction of landfill
biological stabilization time.99 This reduction in time has been repeatedly
proven through the reduction of COD half-lives in landfills utilizing leachate
recirculation;10 1 COD half-lives in leachate from conventional landfills have
been calculated to be around 10 years, whereas for bioreactor
99 10 1
landfills, the
COD half-life of the leachate is closer to 230 to 380 days. '
Four types of bioreactor landfills have been explored, each with different
operating schemes to obtain optimal results: anaerobic, aerobic, facultative,
53 48
and hybrid systems. Each bioreactor type is a patented process. 43 , 47' '
A. Anaerobic Bioreactor Landfills

Anaerobic bioreactor landfills are those in which moisture addition is prac-
ticed. Sources of liquid addition may include groundwater, stormwater, infil-
trating rainfall, or leachate. Moisture content adjustment results in enhanced
methane production, which has been repeatedly demonstrated in several lab-
oratory, pilot, and field-scale studies.27,36 ,84 ,88, 98 ,117,11 8 Because waste degra-
dation is enhanced in anaerobic bioreactors and organic material is returned
to the landfill via leachate recirculation, 99 methane is produced at a much
faster rate. The total volume of gas produced also increases, as organics in
the leachate are recycled and then biodegraded within the landfill. The ma-
jority of gas production may be confined to a few years, earlier in the life of
the landfill, than traditionally occurs in conventional landfills, allowing for
more efficient capture and subsequent use. 99 Gas production time frames
are highly dependent on the moisture content of the waste. Modeling of gas
production from bioreactor landfills requires different parameters than used
for conventional landfills. 7' 33 As the parameters are fitted for wet landfills,
the time for 99% of the methane to be produced may decrease by almost 14-
fold. 33 Although the vast majority of the gas will be produced relatively early
after closing the landfill (within 20 years), limited methane production may
continue over long periods of time due to wetting of previously unreached
dry areas.
Anaerobic bioreactor landfills are more effective at degrading the solid
waste than conventional landfills. However, when compared to other types
of bioreactor landfills, anaerobic systems tend to have lower temperatures
and slower degradation rates. 74' 112 A disadvantage to operating the land-
fill as an anaerobic bioreactor is the accumulation of ammonia-nitrogen. In
anaerobic bioreactor landfills, the ammonia-nitrogen present in the leachate
is continually returned to the landfill, where there is no degradation path-
way for ammonia in anaerobic environments. An advantage of operating the
bioreactor anaerobically when compared to other bioreactor landfill types is
that air is not added; therefore the operational costs are less than what would
be incurred aerobically and methane can be captured and reused.
B. Aerobic Bioreactor Landfills

Adding air to landfills has been shown to enhance degradation processes
in landfills, as aerobic processes tend to degrade organic compounds typ-
ically found in municipal solid waste (MSW) in shorter time periods than
anaerobic degradation processes.5, 6 8,79, 96 ,112 Reported advantages of operat-
ing the landfill aerobically rather than anaerobically include increased set-
tlement, decreased metal mobility, reduced ex situ leachate treatment re-
quired, lower leachate management and methane control costs, and reduced
environmental liability. 30 '96 Both laboratory and field-scale studies have
been conducted showing the effectiveness of the aerobic bioreactor landfill
74 110
system.68, ,
Many of the nitrogen transformation/removal process are favored by aer-
obic processes, including nitrification and ammonia air stripping or volatiliza-
tion. Air stripping and volatilization may be favored in aerobic bioreactor
landfills because of higher pH levels and temperatures that are inherent in
an aerobic environment. The additional gas flow associated with air injection
may also induce greater masses of ammonia-nitrogen removal.
During aerobic degradation of MSW, biodegradable materials are con-
verted mostly to carbon dioxide and water. Little, if any, methane is produced,
which may be viewed as either an advantage or disadvantage, depending on
whether methane collection and use as an energy source is desired or re-
quired. Methane is a potent greenhouse gas; thus, if it cannot be efficiently
controlled and collected in anaerobic landfills, its production can be a local
environmental concern. Further, the solid waste environment during aerobic
degradation has a fairly neutral pH,44 '74 '91 12 which decreases metal mo-
bility. Volatile organic acid production is decreased in aerobic bioreactors
because the anaerobic fermentation processes are limited. However, volatile
acid and methane production may still occur in anaerobic pockets within the
landfill.
The aerobic process generates a considerable amount of heat, leading
to elevated in situ temperatures as high as 660C. 4, 74, 112 The elevated tempera-
tures increase evaporation, which results in a significant loss of leachate. As a
consequence, there is less leachate to manage.3 0 The high temperatures may
limit certain biological nitrogen transformation processes from occurring, al-
though no data regarding temperature effects are available. Additionally, the
combination of the high temperatures and presence of air may create a fire
potential. However, by minimizing methane production and ensuring proper
moisture contents, fire potential is lessened.
Odors often associated with anaerobic systems, such as from hydrogen
sulfide and volatile acids, are reduced in aerobic bioreactor landfills. Aerobic
processes do have some odor associated with them; however, it is an earthy
smell. Some odorous compounds emitted by aerobic composting include
77
methanethiol, which has a pungent sulfide odor.
C. Hybrid Bioreactor Landfills

Another, less studied type of bioreactor landfill that shows promise is the
hybrid bioreactor. This type of bioreactor landfill is still in the early stages
of development. Hybrid bioreactor landfills involve the combination of both
aerobic and anaerobic conditions. Two types of these aerobic/anaerobic sys-
tems have been explored: short-term cycling of air injection into the landfill,
and sequencing of aerobic and anaerobic conditions.
Cycling of air injection into the landfill is defined as a pattern of alter-
nating in situ aerobic and anaerobic conditions that is repeated throughout
the life cycle of the landfill, while sequencing of air injection into the landfill
involves an initial aerobic phase, followed by a final anaerobic phase. Be-
cause there are many advantages associated with both aerobic and anaerobic
degradation processes, researchers see combining the processes as a way to
maximize the potential of a bioreactor landfill. There are some components in
both the waste and the leachate that are recalcitrant in anaerobic conditions
but degradable in aerobic environments, such as lignins and aromatic com-
pounds. Utilizing one of these hybrid techniques may allow for the leachate
and/or waste to be treated more completely.1'0 86"10 0 Operating a bioreactor
landfill as a hybrid system may serve to combine several nitrogen trans-
formation and removal processes, such as nitrification and denitrification,
potentially resulting in complete in situ removal of nitrogen from landfills.
A few laboratory studies have been completed evaluating the effect of
cyclic air injection on the performance of bioreactor landfills.10 , 86 1 32 Each
cyclic air injection system evaluated achieved a more biologically stable
leachate with respect to COD in a shorter period of time than that expe-
rienced by purely aerobic systems. Ziehmann and Meier' 32 conducted both
laboratory and pilot-scale studies evaluating this technique. Three bioreactor
systems were operated for 180 days. Anaerobic and aerobic conditions were
cycled based on the methane concentration measured; once the methane
concentration reached 2.5% by volume, air was added. Results from the lab-
oratory study showed that the leachate from the reactor in which aerobic
and anaerobic conditions were alternated had lower concentrations of total
organic carbon and COD than those from either the anaerobic or aerobic
reactors. However, when operating the pilot-scale study, there was little dif-
ference between the cyclic and continuously aerobic reactors, suggesting that
the advantages of the cyclic system seen in the small-scale studies may not
be realized at field scale. Each study was conducted over short time periods,
so additional long-term studies are needed to evaluate this process further.
A few studies have also evaluated the effect of a sequencing air-injection
system.12,111 In this system, waste is placed in lifts. The first lift is aerated
for a period of time; when the second lift is placed, aeration of the first
layer stops and aeration of the second layer commences. Leachate is con-
tinuously recirculated. This process continues until the landfill is filled. 47 It
is hypothesized that this system acts to speed typical anaerobic degrada-

tion processes, specifically the onset of methanogenesis. By initially aero-
bically degrading the waste, the temperature of the waste is increased and
the extent of the acidogenic phase is reduced, thus allowing for the early
onset of methanogenesis. Fletcher et al. 35 conducted a study that demon-
strated the effect of increasing temperatures on methane production. Air was
briefly added to an older landfill using vertical injection wells to promote
aerobic activity. As a result of the air addition, local temperatures increased
by 17°C. Methane production was stimulated as a result of the increase in
temperature.
Stegmann and Spendling"' conducted lysimeter tests evaluating se-
quencing of air addition. In their studies, waste was loosely placed in thin
layers (from 0.4 to 2 m) with no cover to allow natural air diffusion into the
waste; leachate was also recirculated. In the lysimeters with the 0.4-m lifts, a
new loosely placed lift of waste was applied every 6 weeks. Another lysime-
ter was operated with waste placed in 2-m lifts; after 2 years, another 2-m
layer of loose waste was placed. The addition of waste lifts prevented air in-
trusion into the lower layers of waste, resulting in the lower layers becoming
anaerobic. The investigators found that the waste placed in thinner layers
resulted in the production of methane earlier. Because of the initial aero-
bic degradation of the readily biodegradable organics, it was hypothesized
that the organic acid production was reduced and did not reach concentra-
tions inhibitory to methane production. Methane production rates were not
measured.
D. Facultative Bioreactor Landfills

Facultative bioreactor landfills are operated with the intent of actively de-
grading the waste mass and, at the same time, controlling high ammonia-
nitrogen concentrations typically found in the leachate from bioreactor land-
fills. In facultative systems, leachate is removed from the bioreactor landfill
48
and nitrified in an external treatment system prior to recirculation. Thus, the
ammonia-nitrogen concentrations of the treated leachate are low to nonex-
istent, while the nitrate levels are high. As the nitrate-rich leachate is recir-
culated and passes through the landfill, denitrification occurs, since several
microorganisms, including facultative microorganisms, use the nitrate for res-
piration. Although this type of bioreactor has not been evaluated in many
studies, there is laboratory evidence suggesting that implementation of such
9 Price et al. 93 conducted a laboratory-scale study
a system is plausible. 92,93 '11
demonstrating the ability of this process to denitrify nitrified leachate as it
passed through the waste. The Outer Loop Landfill in Louisville, KY, is in the
9
process of using this approach for controlling nitrogen discharges)'1 A disad-
vantage of this technique is that external treatment of leachate for ammonia-
nitrogen removal must occur, which adds an extra step to the bioreactor
landfill process and can be both difficult and costly because of high levels of
ammonia-nitrogen in the leachate. Additionally, while denitrification of the
leachate is occurring, methane production may be halted until the nitrate is
consumed. It has been shown that methane production quickly resumes after
93
nitrate is depleted.
III. AMMONIA-NITROGEN IN LEACHATE

The ammonia-nitrogen in leachate is derived from the nitrogen content of
the waste; the concentration is dependent on the rate of solubilization and/or
leaching from the waste. The nitrogen content of MSW is less than 1%, on a
wet-weight basis,1 13 and is composed primarily of the proteins contained in
yard wastes, food wastes, and biosolids.17 As the proteins are hydrolyzed and
fermented by microorganisms, ammonia-nitrogen is produced. This process
is termed ammonification. Researchers report concentrations range from less
28 39 95 101
than detection levels to over 5000 mg/L. ' , '
Leachate composition is quite variable, depending highly on waste com-
position, moisture content of the waste, and age of the landfill. Table 1
provides ammonia-nitrogen concentration ranges for both conventional and
bioreactor landfills as a function of waste age as summarized by Reinhart and
Townsend.10 '
Removal of ammonia-nitrogen from leachate to low levels is necessary
because of its aquatic toxicity and oxygen demand in receiving waters. Sev-
eral researchers have conducted tests to measure the toxicity of leachate, con-
cluding that ammonia-nitrogen significantly contributed to the toxic nature
of the leachate.7, 6 1,1
2 5 In landfill leachate, the vast majority of the ammonia-
nitrogen species will be in the form of the ammonium ion (NH+-) because pH
levels are generally less than 8.0.96,100,119 Figure 1 provides the distribution of
ammonia and ammonium as a function of pH. Dissolved unionized ammonia
(predominant at pH levels above 10) is more toxic to anaerobic degrada-
tion processes than ammonium ions but should not be present in significant
concentrations in a landfill. Ammonia-nitrogen concentrations greater than
TABLE 1. Ammonia-Nitrogen Concentrations in Both Conventional

Bioreactor Landfills with Respect to Degree of Landfill Biological
01
Stabilization'
Concentration (mg/L as N)
Stabilization phase Conventional landfills Bioreactor landfills
Transition 120-125 76-125

Acid formation 2-1030 0-1800
Methane fermentation 6-430 32-1850
Final maturation 6-430 420-580
:1:: i/ -•
R 60 I-ammonium
6 L-- ammonia J
o40
E
Eo2 /
"2 0 .
4 6 8 10 12 14
solution pH
FIGURE 1. Dominant form of ammoniacal nitrogen in solution at 25°C at various pH levels.
500 mg/L as N are inhibitory to the degradation process.66 Ammonium con-

centrations between 50 and 200 mg/L have been shown to be beneficial to
anaerobic degradation processes in wastewater treatment, while ammonium
concentrations between 200 and 1000 mg/L have been shown to have no
adverse effect. Concentrations ranging from 1500 to 5500 mg/L have been
shown to have inhibitory effects at higher pH levels, and concentrations
66
above 5800 mg/L have been shown to be toxic to some microorganisms.
However, the effect of ammonium concentrations on landfilled waste degra-
dation has not been reported.
IV. NITROGEN TRANSFORMATION AND REMOVAL PROCESSES

Currently, ammonia-nitrogen is treated in leachate ex situ to the
landfill. 21,52,54,70 ,109, 127 Ammonia-nitrogen removal methods often include
complex sequences of physical, chemical, and/or biological processes, in-
cluding chemical precipitation, nanofiltration, air stripping, and biological
nitrification/denitrification via various reactor configurations (i.e., rotating
biological filters, suspended and attached growth reactors). However, op-
erating the landfill as a bioreactor provides opportunities for in situ nitrogen
transformation and removal processes. Little research has been conducted
evaluating the fate of nitrogen in bioreactor landfills; however, understand-
ing the possible nitrogen transformations is important when considering po-
tential leachate management options. When adding air to landfills, biological
processes such as nitrification traditionally found and expected only in land-
fill cover soils as a result of air diffusion may now occur within the waste
mass. Additionally, recirculating nitrified leachate allows for denitrification
processes to occur in anoxic areas found in both anaerobic and aerobic
bioreactor landfills. Figure 2 illustrates the potential nitrogen transformation
and/or removal pathways that may occur in bioreactor landfills.
The heterogeneous nature of solid waste complicates the nitrogen cycle
in bioreactor landfills. Because the waste is heterogeneous, portions of the
0 0
'o0
000
c/z z
o
*0" r
z
000
Sz• -• -z
-z•
0
375
landfill may contain different amounts of nutrients, be at different tempera-

tures, have different moisture levels, and may be at different ORPs. Environ-
mental conditions greatly affect the transformation and removal of nitrogen.
Thus, within one landfill cell, there may be many nitrogen transformation pro-
cesses occurring simultaneously or sequentially. Processes commonly found
in wastewater treatment processes and in soils, such as ammonification, sorp-
tion, volatilization, nitrification, denitrification, anaerobic ammonium oxida-
tion (ANAMMOX), and nitrate reduction, may all occur in bioreactor land-
fills. This section discusses how the nitrogen transformation and removal
processes found in wastewater and/or soils may also occur in bioreactor
landfills based on the current knowledge associated with each process.
A. Ammonification
Proteins present in the waste are the major source of ammonia-nitrogen.
This conversion of organic nitrogen to ammonia-nitrogen by heterotrophic
bacteria is termed ammonification. Ammonification is a two-step process
consisting of the enzymatic hydrolysis of proteins by aerobic and anaer-
obic microorganisms releasing amino acids and the subsequent deamina-
tion or fermentation (depending on aerobic vs. anaerobic conditions) of the
17
acids to carbon dioxide, ammonia-nitrogen, and volatile fatty acids. Dur-
ing deamination, amine groups are liberated to form ammonia or ammo-
7
nium, depending on the pH, and alkalinity is slightly elevated.' The deam-
ination process is illustrated in Figure 3. Once ammonification occurs, the
H
I Amino
H -C -COOH Acid
I
NH2
H
I
H -C - COOH
Deaminating Bacteria
(ex. Citrobacter) NH4+
NH2 - 0 NH 3
H÷
FIGURE 3. The deamination process.

ammonia-nitrogen is dissolved in the leachate and is ready to be transformed

and/or removed via volatilization, sorption, or biological processes when in
an aerobic environment. The pH also increases during ammonification. Any
free ammonia that is present is highly reactive and has been found to combine
with organic matter (i.e., carboxyls, quinine hydroxls), making them more
biodegradable.15 Thus, in landfills, any ammonia that is produced within
the landfill may redissolve and react with organic matter before exiting the
landfill.
Little research has been conducted evaluating the rate of ammonification
in landfills. However, ammonia-nitrogen release from wastes has been eval-
uated in both solid waste digestion and composting studies.2 5,10 7 Ammoni-
fication rates were not quantified, although the generation trends appear to
follow first-order reaction kinetics. Additionally, ammonification occurs dur-
ing the organic hydrolysis phase of landfill stabilization, which is also often
represented by first-order kinetics. 3' 42 In compost, ammonification has been
found to be optimal between 40 and 50°C.104
B. Ammonium Flushing
The mass of ammonia-nitrogen that can be leached from the waste is con-
trolled by the volume of water passed through the landfill, the nitrogen con-
tent of the waste, and the ammonia-nitrogen concentration in the bulk liquid.
Reducing ammonia-nitrogen concentrations by washout and dilution to ac-
ceptable levels within a landfill requires the addition of large volumes of wa-
55
ter. The Institute of Waste Management Sustainable Landfill Working Group
reported that at a solid waste moisture content of 30% (wet weight basis) and
an initial liquid-phase ammonia-nitrogen concentration of 5833 mg/L as N,
a flushing volume of approximately 2.4 m 3/tonne of waste was necessary to
reduce the nitrogen concentration to 2 mg/L as N. It was also noted that other
studies had been conducted suggesting that flushing volumes between 5 and
7.5 m 3/tonne of waste were needed to adequately reduce nitrogen concen-
trations in the landfill. No time frames for this reduction to occur were given.
The effectiveness of flushing will be dependent on hydraulic conductivity of
the waste, as it will be harder to introduce liquid in areas of lower permeabil-
ity. As the hydraulic conductivity decreases, the time required for leaching
to occur increases, as does the ammonification process.
Purcell et al.9 4 conducted a laboratory-scale study evaluating the flush-
ing of ammonia-nitrogen from landfills. It was found that as flushing rates
increased from 435 mm/year to 2195 mm/year, the release of ammonium-
nitrogen from the waste and thus overall removal from the reactors in-
creased. The main mechanisms of ammonia-nitrogen removal were found
to be washout and dilution from the incoming water.
Flushing results in the removal of ammonia-nitrogen from landfills by
adding large volumes of water, which must be treated externally. When
operating the landfill as a bioreactor, leachate is recycled, and hence

ammonia-nitrogen is continually reintroduced to the landfill while additional
ammonia is solubilized into the leachate.
C. Ammonium Sorption
Sorption of ammonia-nitrogen to waste may be significant in bioreactor land-
fills because of the high ammonium concentrations present. Ammonium is
6
known to sorb onto various inorganic and organic compounds. 5 The amount
of ammonium sorbed on some organics has been reported to exceed the
mass found in the bulk liquid.8 ' Sorption of ammonium to the waste will
allow for temporary storage of ammonium prior to it being used in other
processes, such as nitrification and volatilization, and may also result in the
50
slow dissolution of ammonium over time.
Sorption is dependent on pH, temperature, ammonium concentration,
and ionic strength of the bulk liquid. For ammonia to sorb to waste particles,
it must be in the form of ammonium (NH+). At pH levels expected in a land-
75
fill, the dominant form of the ammonia species is the ammonium ion, as
depicted in Figure 1. As ionic strength of the bulk liquid increases, sorption
of ammonium tends to decrease 50'8 1 due to ion-exchange effects. The sorbed
ammonium is released and exchanged with other ions present in the bulk
liquid, especially those with higher selectivity or concentration. A common
procedure used to extract sorbed ammonium from solid particles involves the
addition of a sodium or potassium sulfate solution. The sodium or potassium
ions exchange with the ammonium, allowing for the ammonium to desorb
from the waste. The conductivity of landfill leachate is generally high (ap-
proximately 7000 Amho/cm) 6' and thus may influence ammonium sorption.
The effect of the ionic strength in leachate on the sorption of ammonium
needs to be evaluated.
In marine sediments, sorption of ammonium has been shown to follow a
Langmuir-type isotherm. 65 However, Nielson" conducted a study of ammo-
nium sorption to activated sludge and found the data did not fit well to that
isotherm type. Little work has been conducted evaluating ammonium des-
orption, which is important to predict the amount of ammonium that will be
available for treatment over time.81 Nielson 8 ' found that a portion of sorbed
ammonium on activated sludge flocs was oxidized and used during the nitri-
fication processes; however, a significant portion of the sorbed ammonium
remained unoxidized, even when the ammonium in the bulk water was al-
most completely removed via nitrification. Ammonium desorption kinetics
may be dependent on ammonium removal in the bulk liquid; as the ammo-
nium concentration in the bulk liquid decreases, potentially due to flushing
or other removal processes, ammonium is likely to be desorbed from the
waste to regain equilibrium. 50 Ionic strength affects were not evaluated in
this study; however, they were noted to potentially impact the sorption and
desorption properties of ammonium.
Ammonium sorption in soils has also been measured. Kwok and Loh64
conducted a laboratory-scale study evaluating the cation-exchange capac-
ity of different soil types in Singapore. In each isotherm study, ammonium
sorption followed a Freundlich isotherm; sorption increased with increasing
exchange capacity. Van Raaphorst and Malchaert12 2 conducted ammonium
sorption studies on various sea sediments and found the sorption data to also 22
follow a Freundlich isotherm. Additionally, Van Raaphorst and Malchaert1
conducted a study in which they measured the mass of ammonium that
could be extracted from a sediment using a potassium chloride solution over
a 40-h time period. They found that exchange of ammonium was initially
rapid (during the first 10 h), but declined significantly after 10 h. During the
40-h test, not all of the ammonium was recovered, suggesting that some of
it was tightly bound to the soil particles.
Studies evaluating the sorptive capacity of fresh waste have not been
conducted; however, the sorptive capacity of peat and soil has been studied.
Heavey 5° found that peat (which may simulate well-oxidized waste) could
sorb 18 to 27 mg NH+/g dry peat. It seems probable that more sorption occurs
in older solid waste than in younger waste because older waste has a smaller
particle size and thus a larger surface area, yielding more available reactive
sites for sorption. Additionally, older waste contains more recalcitrant organic
particles (predominantly humic and fulvic acids) to which ammonium may
sorb. Further, as waste ages, there may be changes in the surface charges of
the waste, resulting in higher levels of sorption. The presence of complex
organics has been shown to influence ammonium sorption; the ammonium
ions may fix irreversibly to these molecules. He et al. 49 found that approxi-
mately 15% of the radiolabeled ammonium they added to soil samples was
associated with the humic fractions; however, the ammonium was recover-
97
able using a series of several different types of extraction media. Reinhart
conducted long-term desorption isotherms with various organic pollutants
and MSW and found that as time increased, the mass of sorbed compound
increased. It was suggested that sorption may be time dependent; the com-
pound may sorb deeper into the solid phase over time, ultimately allowing
for sorption of more mass over time. A similar phenomenon of irreversible
sorption in soils has been observed 14 ' 78' 120 and will likely occur with ammo-
nium. More research on the sorption and desorption of ammonia-nitrogen
on MSW is necessary.
D. Volatilization
In conventional landfills, ammonia makes up approximately 0.1 to 1.0% (dry
volume basis) of landfill gas exiting the landfill.'1 3 Ammonia is not a green-
house gas, so its impact on the environment is not as harmful as methane;
however, there are some adverse health effects that may result from exposure
to the gas. Ammonia has a pungent odor and is a respiratory-tract irritant.
Also, ammonia gas can dissolve in the moisture on skin and form 72
ammonium
hydroxide, a corrosive chemical that can cause skin irritation.
Volatilization only occurs when free ammonia is present. At pH levels
above 10.5 to 11.5, the majority of the ammonia-nitrogen present in solution
is in the form of free ammonia gas (NH 3), as depicted in Figure 1. The free
ammonia concentration at a particular pH level may be computed via Eq. (1).
[NH+-N] x 1 0 pH
[NH 3-N] - + 1J0pH
K--,-
4 p (1)
Kw
where NH 3 -N is the free ammonia concentration, (mass/volume), NH+-N the

ammonium concentration (mass/volume), Ka the acid dissociation constant,
and K, the water ionization fraction (10-14).
As temperature increases, more of the ammonia is converted to free am-
monia gas because of the temperature dependence of the acid dissociation
constant. At a pH level of 7, under standard conditions (i.e., temperature is
25°C and pressure is 1 atm), 0.56% of ammonia present is in the form of
free ammonia. When the temperature increases to 60'C, a temperature com-
monly found in aerobic landfills, the percentage of free ammonia present at
pH 7 increases to 4.90%. Ammonia volatilization has been measured in nu-
merous compost studies. Results have shown that as temperature increases,
the dominant ammonia removal mechanism becomes volatilization. Sanchez-
Monedero et al.11 5 found that at temperatures above 40'C, the only ammo-
nia removal mechanism observed in compost was volatilization. Tiquia and
Tami16 also found that at temperatures above 40 0 C and at pH levels of 7 and
above, the majority of nitrogen removed from compost is via volatilization.
Air flow also plays an important role in ammonia-nitrogen volatiliza-
tion. As air is introduced, it begins to agitate the leachate, creating a re-
moval pathway for dissolved free ammonia to volatilize and leave the landfill.
Air flow also dilutes the concentration of gas-phase ammonia-nitrogen above
the leachate, increasing the driving
5 1"'14
force for dissolved ammonia-nitrogen to
partition to the gaseous phase.
Ritzkowski and Stegmann10 3 conducted a laboratory-scale study in which
the mass of ammonia-nitrogen volatilized from the waste mass was mea-
sured. All gas emissions from a simulated aerobic bioreactor landfill exited
through an acid scrubber to capture any ammonia-nitrogen that may have
been volatilized. It was found that at a pH of 7.4 and a temperature of 35°C,
50% of the ammonia-nitrogen initially present in the leachate was volatilized.
The air flow rate was not reported.
E. Nitrification
Nitrification has been successfully used in wastewater treatment processes as
a means to convert ammonium-nitrogen to nitrite and nitrate for decades, and
the mechanisms in which it is conducted and operated have been thoroughly

studied. 1,41,106,121 The purpose of this section is not to thoroughly review
the nitrification process, but rather to discuss how nitrification may occur
in bioreactor landfills. More detailed information about nitrification can be
38 6
found elsewhere. 'io
Nitrification is a two-step aerobic process in which ammonia-nitrogen/
ammonium is microbially oxidized to nitrite and nitrate via obligate aer-
obe, autotrophic, chemolithotrophic microorganisms. Because nitrification is
an aerobic process, it is almost nonexistent in conventional landfills and in
bioreactor landfills in which air is not added. In those systems, nitrification
is restricted to upper portions of the landfill or the cover where air may
infiltrate. 17 In landfills in which air is purposely added, nitrification can be a
significant nitrogen removal pathway.
During the first step of nitrification, Nitrosomonas bacteria oxidize
10 2:
ammonia-nitrogen to nitrite, according to the following reaction
NH+ + 1.502 -+ NO- + 2H+ + H 2 0 (2)
The second step of the nitrification process is the oxidation of nitrite to

nitrate by Nitrobacterbacteria (or the more recently implicated Nitrospira)
10 2
according to the following reaction :
NO 2 + 0.5002 --+ NO3 (3)
Nitrifiers must fix and reduce inorganic carbon to use as their carbon
source,102 resulting in low cell yields and thus small maximum specific growth
rates. Additionally, nitrification results in the consumption of alkalinity as ni-
trous acid is formed. The first step of nitrification is often the limiting step, as
38
the Nitrosomonasbacteria grow more slowly than Nitrobacteror Nitrospira.
Some heterotrophic microorganisms are able to nitrify; however, their spe-
cific nitrifying rates are considered generally three to four orders of magni-
tude lower than that of the autotrophs. 40 ,10 6 Thus, heterotrophic nitrification
is generally considered to be a minor pathway. Some of the heterotrophic
nitrifiers are able to denitrify (reduce nitrate) aerobically as well. 9
Nitrification has also been documented to naturally occur in soils. , 16,124
Nitrification processes in soil generally result from the addition of nitrogen
fertilizers and the diffusion of oxygen.
Nitrification may occur in bioreactor landfills in which air is added. Al-
though the metabolic processes associated with nitrification may be essen-
tially the same in landfills and wastewater treatment processes, the operation,
control, and potential extent of such processes are not the same. Nitrification
in landfill environments is complicated by oxygen and temperature limita-
tions, heterotrophic bacteria competition, and potentially pH inhibition. Oxy-
gen is a required element for nitrification. Adding air to a landfill would be
dual-purpose: to nitrify, removing the ammonia-nitrogen, and to enhance the
382 3N.D. Berge et al.
degradation of solid waste. However, maintaining and controlling sufficient

oxygen levels within the landfill, especially considering the heterogeneous
nature of solid waste and the high temperatures characteristic of aerobic
landfills, may be difficult and may result in oxygen limitations (dissolved
oxygen concentration declines with temperature increases) and thus reduced
nitrification rates. Additionally, oxygen may become limiting to nitrifiers in
areas within the landfill containing large amounts of organic carbon (newly
placed waste) due to competition with heterotrophs. Under oxygen-limiting
conditions, autotrophic ammonia-oxidizing bacteria may produce nitric and
nitrous oxides, which would be a distinct disadvantage of this technique as
they are potent greenhouse gases.1 7 Heterotrophic nitrifiers are also capable
of producing nitrous oxide.
Cheng et al. 20 measured the production of both nitric and nitrous ox-
ides in Chinese agricultural soils in which high levels of fertilizer were added.
Different types of soils were tested to determine which conditions resulted
in higher gas production. Both nitric and nitrous oxide production from ni-
trification was observed. Production could be correlated with the pH of the
system; soils that were more basic (pH > 8) resulted in the highest con-
centrations of nitrous oxide, while the more acidic soils produced the least.
Khalil et al. 6° also conducted a study evaluating the production of nitrous
oxide in soils, paying particular attention to the influence of oxygen on ni-
trous oxide production. They found that as oxygen decreased, the mass of
nitrous oxide from nitrification increased. In landfills, there may be areas in
which oxygen concentrations are limiting; thus, nitrous oxide production via
nitrification may result. However, long residence times are expected, so the
nitrous oxide may be converted to nitrogen gas before exiting the landfill.
When air is added to landfills, in situ temperatures generally increase,
often as high as 55 to 66'C, 4' 74 which is a temperature range potentially
inhibitory to nitrification. 69,80 ,128 Willers et al.128 reported that pure Nitro-
somonas cultures have a thermal death point between 54 and 58°C. In land-
fills, there may be pockets of lower temperatures, allowing for the nitrifiers
to be protected. Additionally, nitrifiers that may be present within biofilms
on waste particles may be temporarily protected from high temperatures.
At these high temperature levels, volatilization may become the predom-5
al.11
inant ammonia-nitrogen removal mechanism. Sanchez-Monedero et
completed studies evaluating the dynamics of nitrogen transformations dur-
ing organic waste composting. They reported that nitrification did not occur
when temperatures rose above 40'C. Several studies evaluating nitrification
69
in thermophilic wastewater processes have been conducted.59' 's° Juteau
et al. 59 found that nitrification did not occur under thermophilic conditions.
2
However, Lubkowitz-Baily and Steide169 and Willers et al." ' found that nitri-
fication was achievable at temperatures as high as 44°C in wastewater and
50'C in veal-calf slurry, respectively, although the rate of nitrification was
decreased significantly at both temperature levels. In higher temperature
environments, other types of bacteria may be responsible for conversion

of ammonium to nitrite.76 Methanotrophs have been shown to oxidize am-
monium to nitrite under thermophilic conditions (53QC); however, nitrifica-
tion by the methanotrophs was highly dependent on oxygen and methane
concentrations; at methane concentrations above 84 1tM, nitrification was
inhibited.76 In hydrothermal vents, thermophilic heterotrophic nitrifiers have
been isolated and found to convert ammonium to nitrite at temperatures
as high as 65°C, thus conversion of ammonium to nitrite at high tempera-
tures is possible. 76 Heterotrophic nitrifiers generally have lower ammonium
conversion rates than autotrophic nitrifiers, but in environments in which
autotrophic processes are inhibited, heterotrophic processes may occur and
be the dominant nitrogen conversion process.
It is suspected that in situ nitrification may be optimized when oper-
ated in landfill cells containing older waste, because, as in composting, as
the age of the waste increases, the temperature of the system decreases due
to reduced biological activity.' 13"12 3 Additionally, since older waste contains
fewer biodegradable organics, less competition with heterotrophs for oxy-
gen will occur. Sanchez-Monedero et al.'1 5 also reported that nitrification did
not occur in compost processes until the majority of the organic matter was
degraded, something also seen in wastewater treatment processes.19, 67 Ad-
ditionally, in older waste, more recalcitrant organics, such as humic acids,
are present. In leachate collected during the methanogenic stage of degra-
dation, almost 60% of the dissolved organics present were in the form of
high molecular weight compounds (i.e., humic and fulvic acids). 61 Humic
acid has been shown to inhibit nitrification, resulting in the buildup of ni-
trite concentrations. Bazin et al. 8 conducted a study in which humic acid
was added to columns containing glass beads and pure cultures of nitrify-
ing microorganisms. At input levels of 100 Ag/cm 3 , the humic acid additions
had no adverse effect on nitrification rates and aided in buffering the pH of
the system. However, when humic acid was added at rates above that level,
nitrification was inhibited. The mechanism of inhibition was not stated. It is
suspected that in landfills humic acids may affect nitrification, although more
work needs to be conducted evaluating the extent of such effects.
pH may also be a complication during nitrification processes in landfills.
The pH of leachate in aerobic landfills is generally near neutral, or slightly
above. 96 ,112 The alkalinity of leachate is generally in the range of 1000 to
10000 mg/L as calcium carbonate." 3 Because nitrification destroys alkalinity,
there may not be sufficient alkalinity present to buffer pH changes that would
result from nitrification of high ammonia-nitrogen leachates. It is possible that
alkalinity may need to be added to the landfill to buffer the leachate.
1. NITRIFICATION CASE STUDIES IN LANDFILLS
Several researchers have evaluated the potential use of in situ, or partially

in situ, nitrification processes in landfills. Youcai et al.' 3 ' conducted a study in
which a biofilter consisting of old waste (8 to 10 years old) was used to treat
leachate. Aerobic portions existed at the top and bottom of the system (air
was not supplied, rather was drawn in from the atmosphere via convection),
while the middle of the system was anaerobic. It is important to note that
these conditions (aerobic and anaerobic) were never shown experimentally,
nor was the ORP measured. A removal of 99.5% of the ammonia-nitrogen
in leachate was observed. Elevated concentrations of nitrate and nitrite were
measured, indicating the ammonia-nitrogen was converted biologically. Ad-
ditionally, 20-30% of total nitrogen in the leachate was removed, suggesting
in situ nitrification and denitrification occurred sequentially in the landfill.
Incidental treatment of nitrogen in aerobic or semiaerobic landfills has
also been observed. Hanashima 44 described lysimeters operated under aer-
obic and semiaerobic conditions over a three to 20-year period. Aerobic
test cells were continuously supplied with air via a feed pipe to the bot-
tom of the cell. The semiaerobic cell was constructed with a large drainage
pipe in contact with the atmosphere to provide aeration to the bottom of
the cell while maintaining the upper portion of the landfill under anaerobic
conditions. Leachate was recycled to both cells. Comparison with the perfor-
mance of conventional anaerobic cells suggested that nitrogen removal under
both semiaerobic and aerobic conditions was significantly greater than under
anaerobic conditions.
The most efficient method evaluated to date is complete in-situ removal
of nitrogen using dedicated zones. Onay and Pohland 82 completed an in-situ
nitrification/denitrification laboratory study in which a three-component sys-
tem was used to facilitate the process. A laboratory study was conducted to
evaluate a conceptual idea of an anoxic denitrification zone located near the
surface of the reactor, an anaerobic zone to simulate methanogenic condi-
tions in the middle, and at the bottom an aerobic nitrification zone. When
utilizing leachate recirculation among the zones, approximately 95% nitro-
gen removal was achieved. Onay and Pohland8 2 completed another study
during which the reactors were connected in series, but with no leachate
recycle, just a single pass. Nitrogen removal was observed with this set of
experiments as well; however, only 30 to 52% removal of nitrogen in the
leachate was achieved. Onay and Pohland 82 suggested application of this
type of system in the field by having different portions of the landfill serving
as treatment zones: The upper portion of the landfill would be anoxic, the
middle anaerobic, and the bottom aerobic (air naturally added via convection
through leachate collection pipes).
2. NITRIFICATION KINETICS
Traditional nitrification kinetics in wastewater systems are derived from the

net growth rates of both Nitrosomonasand Nitrobacter,with the growth rate
of Nitrosomonasconsidered as the rate-limiting step and thus the most critical
from a design perspective. Monod kinetics are often used, as they describe
first-order substrate-limiting growth at low ammonia-nitrogen concentrations

and zero-order at higher concentrations.38 ' 10 2 Because ammonia oxidation is
the rate-limiting step, it is often used as the overall rate of nitrification. Several
environmental factors influence the rate and must be accounted for in the
rate expression, including pH, dissolved oxygen (DO) concentrations, and
temperature. These factors are included in the rate expression of ammonia
oxidation in a multiplicative Monod manner. 26 The Monod relationship can
also be modified to account for substrate inhibition, which could be relevant
at high ammonia-nitrogen concentrations.
The nitrification process in solid waste environments may be better ap-
proximated by fixed-film theory rather than suspended, as the waste may
act as an attachment surface for the microorganisms. 85'10 8 In fact, a bioreac-
tor landfill may contain both suspended and fixed-film populations, but it
seems likely that in most cases the greater portion of the biomass will be
associated with biofilms. This means that diffusion of electron acceptors and
donors and other mass transfer limitations become significant. In landfills,
mass transfer of ammonium and/or oxygen may be a bigger factor than in
wastewater treatment because of the large particle sizes of the waste and
because the liquid to solid ratio is much smaller than in typical wastewater
treatment processes. Mass transfer limitations would likely become apparent
in the value of the half-saturation constant in the Monod model. 89 The half-
saturation constants in wastewater for nitrification are generally 1 to 2 mg/L
as N; a much larger value may indicate mass transfer limitations. In addi-
tion, the presence of biofilms increases the possibility of multiple microen-
vironments (e.g., even an aerobic region may contain biofilms with anoxic
depths and thus possibly simultaneous denitrification). Thus, it is unlikely
the kinetics of in situ nitrification will fit well to strict Monod or biofilm ki-
netic models; rather, an expression including both types of consortia may be
appropriate.
F Denitrification
Denitrification has been applied in many wastewater treatment processes.
The intent of this section is not to review the denitrification process, rather
to discuss how denitrification may occur in bioreactor landfills. Information
regarding denitrification processes may be found elsewhere. 11,29,31,37,38,71,106
In situ denitrification is also complicated in solid waste systems, although it
may be easier to implement than nitrification. Denitrifiers are more robust
than nitrifiers; however, they require a sufficient organic carbon source for
high nitrate removal rates. Because of the carbon needs, denitrification may
occur most efficiently in young waste, rather than in older, partially oxidized
waste. Price et al. 93 evaluated the potential need for an external carbon source
in the laboratory and noted that a fresh layer of refuse contained sufficient
carbon to stimulate significant nitrate consumption. If a sufficient organic
carbon source is not readily available, partial denitrification may occur, which
may lead to the production of harmful intermediates (N 20 and NO), which
20 60
are potent greenhouse gases. '
Typically, in situ denitrification occurs in anoxic bioreactor landfills.
However, because of the potential for anoxic pockets to be present in aero-
bic systems, denitrification may also occur in portions of aerobic bioreactor
landfills that air does not reach.
1. HETEROTROPHIC DENITRIFICATION
Denitrification is an anoxic process that reduces nitrate to nitrite, nitric oxide,

nitrous oxide, and finally nitrogen gas, as shown in reactions (4)_(7)102:
NO3 + 2e- + 2H+ -+ NO2 + H2 0 (4)
NO2 + e- + 2H+ -+ NO + H 2 0 (5)
2NO + 2e- + 2H-+ N20 + H2 0 (6)
N 20 + 2e- + 2H+ -- N2(g) + H2 0 (7)
Typically, denitrifying bacteria are heterotrophic, facultative aerobes, which

use nitrate as an electron acceptor when oxygen is absent or limiting. A
potential advantage of denitrification is the simultaneous carbon and nitrate
destruction without requiring oxygen input. 38 Denitrification also recovers
half of the alkalinity consumed during nitrification. It is important to note
that processes in which nitrate is used as a terminal electron acceptor are
energetically favored over acetogenic, sulfate reduction, and methanogenic
processes. Thus in landfills in anaerobic/anoxic environments in which ni-
trate reduction occurs, inhibition of such processes may occur.
Researchers have evaluated in situ, or partially in situ, denitrification at
both laboratory and field scale. Burton and Watson-Craik' 8 operated a land-
fill test cell designed to denitrify externally nitrified leachate. Nitrate returned
to the landfill cell was efficiently consumed under the anoxic/anaerobic
landfill conditions, confirmed using labeled isotopic nitrate. Both Waste
Management" 9 and Aljarallah and Atwater 2 have completed similar studies
2
at field and laboratory scale, respectively. Aljarallah and Atwater noted that
denitrification was feasible in a bioreactor landfill; however, methane pro-
duction and waste degradation were hindered. A carbon balance was con-
ducted on the leachate and solid waste in their study and found that as the
nitrate concentration increased, less carbon was released in either the liquid
or gas form, suggesting that waste degradation was inhibited by high nitrate
concentrations (i.e., 800 mg/L as N). Additionally, it was noted that poor
5
leachate quality was produced (high organic strength). Jokela et al. 1 con-
ducted a similar laboratory study demonstrating that in situ denitrification is
possible and can result in the elimination of nitrogen. Ammonia was detected
in the effluent from the solid waste column, which was attributed to either
release from the waste or high leachate COD to nitrate ratio, which may pro-
mote the reduction of nitrate to ammonia-nitrogen (see Figure 1). It was also
concluded that at an oxidized nitrogen loading rate below 3.8 g N/total solids-
day, methanogenesis was not inhibited. High leachate COD concentrations
inhibited nitrification in the ex-situ process, presumably due to competition
for available oxygen.
Price et al.93 also conducted studies evaluating the ability of older waste
(with low organic carbon) to denitrify nitrified leachate. It was shown that
the landfill does have the capacity to denitrify, as significant nitrate consump-
tion was observed, and that fresh waste contained enough organic carbon to
support denitrification, while older waste required the addition of an exter-
nal carbon source. Additionally, it was observed that methanogenic activity
was inhibited during denitrification, but quickly resumed following nitrate
removal.
2. AUTOTROPHIC DENITRIFICATION
Nitrate removal in wastewaters containing high sulfur concentrations or re-

duced sulfur sources, such as hydrogen sulfide, may occur via autotrophic
denitrification. Thiobacillus denitrificans use an inorganic sulfur source (i.e.,
H 2 S, S, SO2-) rather than an organic carbon source when reducing nitrate to
nitrogen gas8 3 according to reaction (8).
2NO + 1.25HS- + 0.75H+ --* N 2 + 1.25SO2- + H 2 0 (8)
This nitrate removal mechanism produces sulfate. At low carbon to

nitrogen ratios this removal mechanism is favored over heterotrophic
denitrification. 62 Autotrophic denitrification may occur in landfills, especially
in older landfills or older portions of landfills where the carbon to nitrogen
ratio may be low. The increased sulfate concentrations may have an adverse
effect on methane production rates by limiting the amount of organic carbon
available to the methanogens due to competition with sulfidogens.
While operating their reactors, Onay and Pohlands3 observed the pres-
ence of autotrophic denitrification. To confirm their findings, a spike of nitrate
was added and gas samples from the headspace of the reactor were mea-
sured for nitrogen and hydrogen sulfide. It was found that 13 days after the
nitrate spike, the hydrogen sulfide present in the gas phase disappeared.
After the nitrate source was exhausted, the sulfate was converted back to
hydrogen sulfide. Onay and Pohland8 3 concluded that autotrophic denitri-
fication accounted for between 15% and 55% of the nitrate conversion to
nitrogen gas, with the variation being attributed to the mass of organics
present in the system. Additionally, it was stated that autotrophic denitrifi-
cation is advantageous, as it converts nitrate to nitrogen gas in the absence
of an organic carbon source and can utilize inorganic sulfur compounds.
High sulfate concentrations (increased to approximately 350 mg/L sulfate)
were produced; however, the impact of sulfate on methanogenesis was not

quantified.
3. DENITRIFICATION KINETICS
Traditionally, Monod kinetics are used to describe denitrification in wastewa-

ter systems. The nitrate removal rate is dependent on several factors that must
be accounted for in the rate expression. Because an organic carbon source
is desirable for rapid denitrification, the amount present in the system affects
the rate, as does the biodegradability of the carbon source. Additionally, pH
and dissolved oxygen (DO) levels affect the denitrification rate and can be
accounted for in a Monod expression in a multiplicative manner.
As in nitrification, the denitrification process in solid waste may be bet-
ter approximated by fixed-film theory rather than suspended, as the waste
8
may act as an attachment surface for the microorganisms.15 ',1 Mass transfer
effects may also be severe in denitrification processes and may be reflected
8 9
in higher half-saturation values when fitting the data to the Monod model.
It is unlikely the kinetics of in situ denitrification will fit well to either strict
Monod or biofilm kinetic models; rather, an expression combining both types
of consortia may be appropriate.
G. ANAMMOX
Biological oxidation of ammonia-nitrogen may also occur under anaerobic
conditions and is termed the ANAMMOX process (anaerobic ammonium oxi-
dation). Bacteria capable of ANAMMOX use ammonium as the electron donor
and nitrite as the electron acceptor, as shown in reaction (9)56 57:
NH+ + 1.26NO- + 0.085CO 2 + 0.02H+ --
N2 + 0.017H+ + 0.24NO3 + 1.95H 2 0 (9)
There has been little research concerning ANAMMOX in solid waste en-
vironments; however, studies conducted in wastewater have shown that
ANAMMOX readily occurs.4 5,56,57,1 06
Researchers have determined that the
microorganisms most often responsible for the ANAMMOX process are from
the Planctomycetales group. 56'129 This process is generally favorable in envi-
ronments in which retention time is long, operation is stable, nitrite is present,
and electron donors that would cause nitrite reduction via denitrification are
absent. Because of the potential for anaerobic regions located within an aer-
obic landfill, this biological ammonia-nitrogen removal mechanism may inci-
dentally occur simultaneously with nitrification. However, the growth rates of
the ANAMMOX bacteria are extremely slow; thus, ammonia-nitrogen removal
is slow as well. It is questionable whether or not the ANAMMOX microor-
ganisms will be able to compete with denitrifiers for nitrate and nitrite within
landfills.17 Removal rates have been shown to be less than half that of aerobic
29
nitrification.'
H. Dissimilatory Nitrate Reduction to Ammonium

Dissimilatory nitrate reduction to ammonium (DNRA) in anaerobic or anoxic
environments may also occur in landfills according to reaction (10).
NO- + 2H+ + 4H 2 --+ NH+- + 3H 2 0 (10)
As shown, ammonium is produced as a result of nitrate reduction. This path-

way is generally favored when the microbes are electron acceptor (nitrate)
limited in high organic carbon environments 92' 115 and has been shown to
occur readily in anaerobic digestion and anoxic sediments where the re-
dox potential is low.11 5 DNRA is favored over denitrification in anaerobic
and anoxic environments in environments with a high COD to nitrate ratio
because in an electron acceptor limiting environment it is more advanta-
geous for the microorganisms to metabolize nitrate to ammonium and gain
8 electrons per mole of nitrate than denitrify and only gain 5 electrons per
mole of nitrate., 5 In electron acceptor rich environments (higher COD to
nitrate ratios), denitrification is usually the favored nitrate reduction process
because the greatest need by the microorganisms is to gain energy. The mi-
crobes responsible for the DNRA process differ from denitrifiers in that they
are generally fermentive (obligate anaerobes, facultative anaerobes, and aer-
obes), using nitrate as electron sink, rather than being respiratory and using
22 1 5
nitrate as a terminal electron acceptor. 1
DNRA depends highly on redox conditions and the amount of labile
carbon available. 13' 34"130 Yin et al. 130 conducted experiments in Chinese and
Australian paddy soils and found that the partitioning of nitrate that was re-
duced to ammonium and to that being denitrified was greatly dependent on
the amount of labile carbon present, which was demonstrated by an increase
in ammonium production with increasing carbon. Buresh and Patrick 15 con-
ducted an experiment on estuarine sediment and found that approximately
15% of the nitrate was converted to ammonium at a redox potential of 0 mV.
When decreasing the redox potential to -200 mV, approximately 35 to 42% of
the nitrate was reduced to ammonium, while an increase in redox potential
(300 mV) resulted in a significant decline of ammonium production, sup-
porting the theory that DNRA is optimal in low redox environments. When
nitrate is added to systems, a general increase in the redox potential occurs.
If nitrate is added to environments with a sufficiently low redox potential,
DNRA may be favored. However, if the nitrate addition results in an increase
in redox above 0 mV, denitrification of the nitrate is more likely. Oxygen
also impacts DNRA; however, it is less sensitive to changes in oxygen than
34
denitrification.
In anaerobic or anoxic areas within the bioreactor landfill in which low

nitrate concentrations are present in areas containing young waste (high
degradable organic carbon) and low redox potentials, DNRA may be favored
over denitrification.1 1 5 The dissimilatory nitrate reduction pathway is not de-
sired because it results in an increase in ammonium concentration. However,
this removal mechanism may be limited because of competition from the
denitrifiers for nitrate. The nitrate-reducing bacteria require a tenfold greater
13
population than denitrifiers to reduce 50% of the nitrate. 93 Bonin reported
that a ratio of 1.8:1.0 denitrifiers to DRNA microbes is generally present in an
environment. In landfills, there is generally adequate denitrifying populations
naturally present to out-compete any DNRA capable microorganisms. Price
et al. 93 conducted laboratory studies in solid waste evaluating the denitrifica-
tion capacity of the waste and found that there was no noticeable increase
in ammonium due to DNRA. However, the redox potential of the laboratory
reactors was not measured. Because there had been several additions of ni-
trate to each reactor, it is possible the redox potential was high enough to
inhibit DNRA activity.
I. Simultaneous Nitrogen Removal Processes

Simultaneous nitrification and denitrification has been observed in waste-
water processes, particularly in trickling filter and other biofilm processes.
Because the potential for anoxic pockets in aerobic landfills is high, simulta-
neous nitrification and denitrification may occur in aerobic bioreactor land-
fills. Pochana and Keller' 7 conducted experiments evaluating the factors that
may affect simultaneous processes in activated sludge flocs. They determined
that the most influential parameters are DO, particle size, and carbon source.
Of particular interest is that as the floc size increases, the potential for anoxic
zones around the particles increases due to oxygen flux limitations. Solid
waste particles are large compared to activated sludge flocs; thus the proba-
bility of oxygen flux limitations is high, supporting the likelihood of simul-
taneous processes.
Because landfills are heterogeneous and may support several different
microenvironments simultaneously (i.e., aerobic, anaerobic, and anoxic), sev-
eral combinations of nitrogen transformation processes mentioned may be
present. In aerobic bioreactor landfills, it is possible that partial nitrification
(only resulting in the production of nitrite) followed by either ANAMMOX or
denitrification will occur naturally because of the heterogeneous nature of
the in situ environment. There will be portions of the landfill that are aerated
well, some only partially aerated, and others not aerated at all. As leachate
flows from one section of the landfill to another, it is possible that it will come
into contact with aerobic, anoxic and anaerobic regions, leading to multiple
nitrogen transformation processes. For example, leachate ammonium may be
converted only to nitrite before the leachate flows to an anaerobic pocket.
In that anaerobic pocket, the nitrite may then be converted to nitrogen gas.
The hydraulic conductivity of the landfill will be a factor, as the time dur-
ing which the leachate remains in each type of environment will ultimately
determine the extent of the reactions that may occur. The ability to predict
which nitrogen transformations will occur allows for more strategic design
and operation of bioreactor landfills.
J. Other Nitrate Processes

Nitrate may also have an abiotic fate in landfills. Leachate generally does
not have high nitrate concentrations; however, nitrate may be present if ni-
trification has occurred in situ, or if the leachate is nitrified externally and
then reinjected to the landfill. Nitrate sorption has been shown to occur in
soils, although not to the extent that ammonium sorption has been observed.
Kwok and Loh64 measured nitrate sorption in six different soils. Sorption
was detected, but in small amounts (average for all soils was 0.004 mol/kg).
Kowalenko and Yu 63 also evaluated the sorption of nitrate on soils and found
that up to 34% of additional nitrate was removed from soils when perform-
ing an extraction using potassium chloride. Sorption of nitrate by waste is
probable. Because of the large variability of waste types, there is bound to
be particles with negative charges that would allow for anion exchange.
Another fate of nitrate is the abiotic transformation via iron. Davidson
et al.2 4 proposed a method of abiotic nitrate removal called the "ferrous
wheel hypothesis" in which reduced iron [Fe(II)] abiotically converts nitrate
to nitrite in anaerobic environments; nitrite then reacts with the dissolved
organic matter to produce dissolved organic nitrogen. No evidence of this
occurring in compost or solid waste has been reported; however, because
leachate typically contains large amounts of iron(II) (3-5500 mg/L),1 the
possibility exists. Iron(II) has also been shown to reduce nitrate in basic
solutions to ammonia-nitrogen. Fanning 32 reported that a pH of 8 was optimal
for the reduction; however, the reduction proceeded at lower pH levels,
just at slower rates. Additionally, it was suggested that the reaction may be
influenced or catalyzed by the presence of silver and copper. Silver is not
generally found in leachates, but copper can be found at levels ranging from
6
0.005 to 10 mg/L. 1
Studies in acid forest soil have observed the disappearance of nitrate via
an abiotic mechanism. Dail et al. 23 conducted a radiolabeled study attempt-
ing to determine the fate of nitrate. They found that nitrate was incorporated
into an insoluble organic nitrogen form in both live and sterile soils, sug-
gesting abiotic fate attenuation. Additionally, in their study, there was more
attenuation of nitrate in soils with larger amounts of organic carbon, suggest-
ing the abiotic conversion is related to the soil carbon content. Because of
the large organic carbon content found in landfills, this nitrate transformation
mechanism could easily occur.
392 N. D. Berge et a!.
V. FUTURE RESEARCH DIRECTIONS
An understanding of the fate of nitrogen and possible mechanisms for

ammonia-nitrogen removal in bioreactor landfills may significantly increase
the capability of bioreactor landfills to more completely treat leachate in situ.
Bioreactor landfills are currently one of the most advantageous methods
available for solid waste management, but still have significant undeveloped
potential with respect to in situ leachate and waste treatment. An under-
standing of the fate of nitrogen, and thus the ways in which nitrogen can
be removed/treated allows for this undeveloped potential to be better devel-
oped. Additionally, understanding the fate of nitrogen may aid in developing
03
methods to remediate old landfills.1
Little research has been conducted evaluating the potential processes
of nitrogen transformation and removal in bioreactor landfills and is needed
before an in-depth understanding of the processes can be achieved and
used to optimize the operation of bioreactor landfills. Both laboratory- and
full-scale studies should be completed to evaluate the hypothesized, but
untested, nitrogen transformation processes. To date, no controlled full-scale
studies purposely evaluating in situ nitrification as a nitrogen transformation
process have been conducted. Additionally, laboratory-scale studies need to
be conducted to gain a better understanding of the rates and kinetics of the
nitrogen transformation processes, as well as to develop design requirements
for an in situ nitrogen removal system to facilitate full-scale testing.
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The Fate of Nitrogen in Bioreactor Landﬁlls

Article in Critical Reviews In Environmental Science and Technology · July 2005

Nicole Berge Debra R Reinhart

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ISSN: 1064-3389 print / 1547-6537 online

The Fate of Nitrogen in Bioreactor Landfills

N. D. BERGE and D. R. REINHART

Although bioreactor landfills have many advantages associ-

KEY WORDS: aerobic treatment, ammonia-nitrogen, denitrifica-

A new and promising trend in solid waste management is to operate the

Address correspondence to N. D. Berge, Department of Civil and Environmental Engi-

advantage is that increased waste degradation rates characteristic of bioreac-

II. BIOREACTOR LANDFILL OPERATION

Traditionally, landfills have been thought of as storage and containment sys-

conductivity may be due to waste heterogeneity or differences in compaction

A. Anaerobic Bioreactor Landfills

B. Aerobic Bioreactor Landfills

C. Hybrid Bioreactor Landfills

is hypothesized that this system acts to speed typical anaerobic degrada-

D. Facultative Bioreactor Landfills

III. AMMONIA-NITROGEN IN LEACHATE

TABLE 1. Ammonia-Nitrogen Concentrations in Both Conventional

Transition 120-125 76-125

FIGURE 1. Dominant form of ammoniacal nitrogen in solution at 25°C at various pH levels.

500 mg/L as N are inhibitory to the degradation process.66 Ammonium con-

IV. NITROGEN TRANSFORMATION AND REMOVAL PROCESSES

landfill may contain different amounts of nutrients, be at different tempera-

FIGURE 3. The deamination process.

ammonia-nitrogen is dissolved in the leachate and is ready to be transformed

operating the landfill as a bioreactor, leachate is recycled, and hence

where NH 3 -N is the free ammonia concentration, (mass/volume), NH+-N the

the mechanisms in which it is conducted and operated have been thoroughly

NH+ + 1.502 -+ NO- + 2H+ + H 2 0 (2)

The second step of the nitrification process is the oxidation of nitrite to

NO 2 + 0.5002 --+ NO3 (3)

degradation of solid waste. However, maintaining and controlling sufficient

environments, other types of bacteria may be responsible for conversion

Several researchers have evaluated the potential use of in situ, or partially

Traditional nitrification kinetics in wastewater systems are derived from the

first-order substrate-limiting growth at low ammonia-nitrogen concentrations

Denitrification is an anoxic process that reduces nitrate to nitrite, nitric oxide,

Typically, denitrifying bacteria are heterotrophic, facultative aerobes, which

Nitrate removal in wastewaters containing high sulfur concentrations or re-

2NO + 1.25HS- + 0.75H+ --* N 2 + 1.25SO2- + H 2 0 (8)

This nitrate removal mechanism produces sulfate. At low carbon to

were produced; however, the impact of sulfate on methanogenesis was not

Traditionally, Monod kinetics are used to describe denitrification in wastewa-

NH+ + 1.26NO- + 0.085CO 2 + 0.02H+ --

N2 + 0.017H+ + 0.24NO3 + 1.95H 2 0 (9)

H. Dissimilatory Nitrate Reduction to Ammonium

NO- + 2H+ + 4H 2 --+ NH+- + 3H 2 0 (10)

As shown, ammonium is produced as a result of nitrate reduction. This path-

In anaerobic or anoxic areas within the bioreactor landfill in which low

I. Simultaneous Nitrogen Removal Processes

J. Other Nitrate Processes

V. FUTURE RESEARCH DIRECTIONS

An understanding of the fate of nitrogen and possible mechanisms for