Balas PDF 99

i
MODELING OF METHANE GENERATION, OXIDATION AND EMISSION IN

LANDFILLS

by

Balasingam Palananthakumar

A thesis submitted in partial fulfillment of the requirement for the degree of Master of
Engineering

Examination Committee Dr. C. Visvanathan (Chairperson)
Dr. N.T. Kim Oanh
Ir. Karl Iver Dahl Madsen

Nationality Sri Lankan
Previous Degree B.Sc. Eng. (Civil Engineering)
University of Peradeniya
Peradeniya, Sri Lanka

Scholarship Donor The Government of J apan

Asian Institute of Technology
School of Environment, Resources and Development
Bangkok, Thailand
August 1999

ii
Acknowledgements

First, I wish to express my sincere gratitude to my adviser Dr. C. Visvanathan for his overall
supervision of this work, brainstorming guidance whenever I was confused, friendly
discussion, providing valuable reference materials and his unreserved willingness to improve
the quality of this research throughout. I was really challenged to give my best because of his
constant eagerness.

I would like to extend my profound gratitude and honest thanks to Ir.Karl Iver Dahl Madson
for his supports and encouragement in modeling work from beginning of the study. I would
also like to express my profound gratitude and heartfelt thanks to Dr.N.T.Kim who accepted
to work as committee member and provided critical comments and suggestions.

My sincere gratitude and appreciation is also due to Dr. Patrick Hettiarchi, Associate
Professor, University of Calgary for providing reference materials and information for this
study.

My sincere thanks are due to all Environmental Engineering staff, especially Khun Varin for
assisting in the ambient lab, Khun Peter for making the necessary materials available for use
and Khun Marasee and Khun Aree for cooperating in official matters.

My sincere appreciation is extended to the Government of J apan, which awarded me the
scholarship for my entire graduate study.

I am indebted to Mr.Dinesh Pokherel who helped me in numerous ways, particularly during
the experimental set up. I am also thankful to Ms. Wilai for her sporadic helps in lab works. I
can not forget members of thesis group who have helped in one way or another. My sincere
appreciation also goes to all my friends who made Asian Institute of Technology as my home.

I deeply respect my siblings for their sacrifications, inspirations and supports continuously to
uplift me. Finally, I gratefully dedicate this piece of work to my late parents who were the
initial source of inspirations and sharing all hardships and upheavals of my soul during the
early stage of my life.

iii
Abstract

Methane emission from landfills to the atmosphere, generation in landfills and oxidation in
landfill covers are topics of major interest because of methane's role in the greenhouse effect,
photochemistry of the troposphere, explosive threats, migration of hazard potential, health and
safety issues and energy applications. Applications of modeling techniques in landfills will be
useful to find ways to control these hazards associated with methane emissions.

A methane inventory model was structured to estimate methane emissions from landfills at
the country or regional level. Then, it was used as a policy assessment tool for analyzing
possible future emission patterns. It identified the restriction of degradable organic carbon
(DOC) in waste by effective solid waste management as the best among other options such as
promotion of methane recovery and methane oxidation. As this package contains many
educational features, it could also be used as a good guide or professional training tool for
people who are interested in landfill gas management.

The sensitivity of methane generation rate was analyzed by the methane generation model to
assess the effects of variables such as initial conditions, specific growth rate and reaction rate
constants. It concluded that hydrolysis rate constant (K
h
) and initial organic carbon
concentration in waste (C
(S)
) are the most important parameters affecting the methane
generation directly.

A methane oxidation model, which was constructed from semi-empirical equations derived
from Monod kinetics, inhibitor effects on enzymatic activity and experimental data, confirms
that the TCE behaves as a fully competitive inhibitor on the enzymatic activity of methane
oxidation.

The experimental study conducted to determine the effect of volatile organic compounds
(benzene) on methane oxidation shows no effects until the benzene increased to 800 g/m
3
.
When it was increased to 1400 g/m
3
there was significant effect observed with some
interference in measuring actual methane. It indicates the threshold limit of benzene on
methane oxidation could be between these two concentrations.

iv
Table of Contents

Chapter Title
Page

Title Page i
Acknowledgment ii
Abstract iii
Table of Contents iv
List of Figures vii
List of Tables ix
List of Abbreviations x

1 Introduction
1.1 Rationale 01
1.2 Objectives of the Study 03
1.3 Scope of the Study 03

2 Literature Review 04
2.1 Solid Waste Management and Landfills 04
2.2 Global Warming and Landfill Gases
2.2.1 Fundamentals of Greenhouse Gases 06
2.2.2 Impact of Greenhouse Gases 07
2.2.3 Methane contribution of landfills 08
2.3 Landfill Gas Generation
2.3.1 Gas Production 10
2.3.2 Different Phases of Biodegradation 11
2.3.3 Movement of Landfill Gases 12
2.4 Methane Oxidation in Landfills.
2.4.1 Mechanisms of Methane Oxidation 14
2.4.2 Influences of Different Parameters 15
2.5 Landfill Gas Mitigation
2.5.1 Mitigation Options 19
2.5.2 Solid Waste Management Practice 20
2.5.3 Landfill Gas Collections 21
2.5.4 Promoting Methane Oxidation 22
v

2.6 Landfill Methane Models
2.6.1 Existing Solutions 24
2.6.2 Models for Inventory of Methane Emissions from
Landfills
25
2.6.3 Numerical Modeling of Gas Generation 26
2.6.4 Modeling of Methane Oxidation 27

3 Methodology
3.1 Work Outline 30
3.2 General Modeling Techniques 30
3.3 Application of Modeling Techniques
3.3.1 Methane Inventory Model 31
3.3.2 Methane Generation Model 32
3.3.3 Methane Oxidation Model 35
3.4 Experimental Study
3.4.1 Experimental Outline 36
3.4.2 Benzene Analysis 37
3.4.3 Calculations 37

4 Results and Discussion
4.1 Outline of Results and Discussion 40
4.2 Methane Emissions from Landfills
4.2.1 Frame Work 40
4.2.2 Components of Package 41
4.2.3 Interface 45
4.2.4 Technical Significance 46
4.3 Model for Methane Generation in Landfills
4.3.1 Basic Considerations 48
4.3.2 Sensitivity Analysis 49
4.4 Methane Oxidation Model
4.4.1 Methodology Development 52
4.4.2 Empirical Formula 55
4.4.3 Simulations and Validations 58
vi
4.5 Effects of VOC on Methane Oxidation 61

5 Conclusions and Recommendations 65
References 68

Appendices
Appendix A Methane Inventory Model : Data and
Calculations
Appendix B Methane Generation Model: Data and
Calculations
Appendix C Methane Oxidation Model: Data and
Calculations
Appendix D Experimental Data and Calculations
Appendix E Useful Photographs

vii
List of Figures

Figure Title Page

2.1 Solid Waste Disposal Leading to Global Warming Problem 05
2.2 Global Warming Scenario
06
2.3 Effect of Greenhouse Gases on Environment 08
2.4 Share of Individual Sources (%) of Methane in Estimated Global
Emission
09
2.5 Percentage of Methane Produced Worldwide from Landfills 09
2.6 Schematic Diagram of Pattern of Carbon Flow at Anaerobic
Condition
10
2.7 Generalized Phases in the Generation of Landfill Gase 11
2.8 Amounts of Methane Consumed in 42 Days At 270c by Methane
Oxidizing Bacteria in Media of Different Initial pH Values
17
2.9 Variation of Oxidation Rates with Temperature 17
2.10 Variation of Methane Oxidation Rates with Moisture Content 18
2.11 Methane Balance Diagram 19
2.12 Trends of Waste Generation, Recovery and Disposal in US 20
2.13 Sulfate Reducing Reactor 23
2.14 Model Kinetics Comparison Using First Order Model as Basis for
Optimizing the Constant of Zero Order Model For Period of 35 Years
(1957 1992)
25
2.15 Examples of Model Predictions. 26
2.16 Effect of Hydrolysis Rate on Total Methane Generation 28
2.17 Effect of Acidogenic Decay Rate on Total Methane Generation.
28
3.1 Organic Pathways in Landfill Microbial Ecosystem
30
3.2 Experimental Setup for Column System
30
4.1 Typical Input Sheet for Estimation for a Place 31
4.2 Graphical Output Sheet of Case Study
31
4.3 The Typical Simulation Sheet
32
4.4 Effects of Initial Solid Carbon on Rate of Methane Generation 35
4.5 Effects of Hydrolysis on Rate of Methane Generation 36
4.6 Comparison of Empirical Curve with Experimental Data for Methane
Oxidation Rate
37
4.7 Comparison of Empirical Curve with Experimental Data for Methane
Oxidation Rate
37
viii
4.8 The Model Block Representing Methane Utilization 58
4.9 The Model Block Representing Methanotroph Population 58
410 Validation of Methane Oxidation for Uninhibited Fresh Soils 59
4.11 Validation of Methane Oxidation for Inhibited Lysimeter Soils 60
4.12 Observed Methane Oxidation with Different Rate of Methane Supply 62
4.13 Variations of Methane Oxidation with Different Rate of Methane
Supply
62
4.14 Observed Methane Oxidation with Different Amount of Benzene
injection Nominal Values for Initial Concentrations Nominal Values
for Initial Concentrations
63

ix
List of Tables

Table Title Page

2.1 Comparison of Properties of Greenhouse Gases 07
2.2 Consumption of Methane with Various Concentration Oxygen and
Nitrogen
15
2.3 Consumption of Methane with Various Concentration Methane and
Nitrogen
16
4.1 Nominal Values for Initial Concentrations 48
4.2 Nominal Values for Variables 49
4.3 Classification of Inhibitors Based on Properties Various Trials of
Empirical Function for Methane Oxidation Rate in Terms of
Temperature
54
4.4 Various Trials of Empirical Function for Methane Oxidation Rate in
Terms of Temperature
55
4.5 Various Trials of Empirical Function for Methane Oxidation Rate in
Terms of Moisture Content.
56
4.6 Optimum values of Parameters for Fresh Soil 59

x
List of Abbreviation

Total porosity
Retarding factor

Max. Specific Growth Rate of Acidogenic Biomass
M
Max. Specific Growth Rate of Methanogenic Biomass
AIT Asian Institute of Technology
C Carbon
C
A
Concentration of A ML
-3

C
(aq)
Concentration of Aqueous Carbon ML
-3

C
(AC)
Concentration of Acetate Carbon ML
-3

C
PMO
Constant for potential of methane oxidation
C
(S)
Concentration of Solid Carbon ML
-3

CFC Chlorofluorocarbon
CH
4
Methane
CO
2
Carbon dioxide
COD Chemical Oxygen Demand
DOC Degradable Organic Carbon
D
z
Diffusion Coefficient
E Enzyme
G Lumped parameter
GC Gas Chromatography
GHG Greenhouse gases
H
2
S Hydrogen Sulfide
ha hector
IDRC International Development Research Center
IPCC Inter -Governmental Panel on Climate Change
K Maximum rate of substrate utilization per unit mass of
microorganism
T
-1

k Coefficient of permeability LT
-1

K
dA
Death rate constant of Acidogens T
-1

K
dM
Death rate constant of Methanogens T
-1

k
h
First Order Hydrolysis Constant T
-1

K
i
Inhibitor constant M
-1
L
3

K
m
Oxidation affinity
xi
Ks Half saturation constant ML
-3

K
SA
Half saturation constant of Acidogens ML
-3

K
SM
Half saturation constant of Methanogens ML
-3

K
SS
Half saturation constant of Substrates ML
-3

I Inhibitor
L Litter
LFGTEP Landfill gas to energy project
MC Moisture contents %
mg Milligram
min Minutes
mL Milliliter
MO Methane Oxidation
MPB Methane Producing Bacteria
MSW Municipal Solid Waste
N Nitrogen
N
2
O Nitrous Oxide
NH
3
Ammonia
O
2
Oxygen
O
3
Ozone
ORP Oxidation Redox Potential
PMO Potential of Methane Oxidation MT
-1

ppb Parts per billion
ppm Parts per million
S Substrate
S
-
Sulfide
SO
4
2-
Sulfate
SRB Sulfate Reducing Bacteria
sqm Square meter L
2

TEI Thailand Environmental Institute
UNEP United Nation Environment Prevention
USEPA United State Environmental Agency
SS Stainless Steel
TCE Tri Chloro Ethane
Tg 10
12
gram
UV Ultra violet
xii
V
max
Maximum oxidation rate MT
-1

VOC Volatile Organic Compound
V
r
Velocity LT
-1

V
z
Convective velocity LT
-1

X Concentration of microorganism ML
-3

Y Yield of Methanotroph per Methane Utilized
Y
A
Yield of Acidogen per Carbon Utilized
Y
CH4
Yield of Methane per Methanogenic Carbon Utilized
yr Year
Y
M
Yield of Methanogenic Carbon per Acetate Carbon Utilized

1
Chapter 1

Introduction

1.1 Rationale

The greenhouse effect has recently been receiving a great deal of scientific and popular
attention. Worldwide, many researchers and scientists are engaged in looking for the reasons
of heat blanketing that causes the phenomenon called global warming. Methane from landfills
has been recognized as one of the importent element of greenhouse gas in addition to carbon
dioxide, nitrous oxide and chloroflocarbon. It has twenty-one times of global warming
potential of carbon dioxide (Augenstein, 1990).

Methane also plays important role in photochemistry of the troposphere. Increases in
atmospheric methane reduces the concentration of the hydroxyl radical (OH) and thus
increases the methane lifetime, and result in increases in troposheric ozone. It is the only long
lived gas that shows chemical feedback effects (Gardner, 1993). In addition, its increased
concentration in the atmosphere causes explosion threats in neighborhood environment.

Atmospheric concentration of methane has grown from 700 ppbv in pre-industrial times to
over to 1700 ppbv today. The global annual input of methane to the atmosphere is estimated
to be 535125 Tg (Smith, 1997), of which about half is considered to be both anthropogenic
and originating from biospheric processes, particularly anaerobic bacterial fermentation.
Decomposition of refuse in municipal landfills is believed to be one of the major components
of this biogenic methane, but past estimates of the emissions from this source have varied
greatly, between 20 and 70 Tg per year (Lay, 1998) which is between 6% and 18% of the total
methane source (Bingemer, 1998). More reliable estimations are clearly needed and past
results show that landfills are notable anthropogenic source of atmosphere methane in many
countries, especially in developed countries.

This methane source has been targeted in many developed countries as one that is capable of
control by recovery and it potentially provides a way of reducing current greenhouse gas
emissions and its adverse effects. Recovered methane either is flared or used as a source of
energy. However, it is not applicable everywhere, specially small-scale landfills and open
dumps in developing countries, because of the lack of methane production and not meeting
design regulations for gas collection.

In contrast, in developing countries, urban refuse disposal often is in open dumps, which do
not result in much methane emission even though they create a range of other environmental
problems (TEI, 1996 and Smith, 1997). However, as these dumps will be replaced in the
future by covered landfills it is likely that methane production will increase, and in most cases
this will not be recovered for use as fuel or flare, but released to the atmosphere.

2
Microbial processes mediate many chemical transformations in landfill, and carbon and
nitrogen cycle in cover soil. The transformation occurs through refuse decomposition by
anaerobic microorganisms (biodegradation) producing methane and other compounds, and
oxidation of methane by aerobic methanographs in cover soil. The biodegradation of solid
waste depends on the composition of waste and continues for a long time in landfill for final
stabilization. Problems associated with biodegradation of solid waste and methane oxidation
are the products and by products of these reactions, mainly leachate and landfill gases with
trace amount of metals and volatile organic compounds (VOC).

The generation of landfill gas exerts pressure to the surrounding area, and landfill gas escapes
through the easiest route. The mechanisms of migration are complex and depend on various
parameters such as surrounding and top cover soil properties, landfill type, age of landfill,
moisture content, pH, temperature, compaction, surrounding pressure. Gas escapes from top
cover directly or migrates horizontally to hundreds of meters away from landfill before being
released into atmosphere. However, some portions of methane is utilized in landfill cover
before released into atmosphere. This phenomenon attracts scientists and researchers to
investigate the fate of methane gas in landfill cover soils.

First, researchers identified the presence of bacteria responsible for methane utilization.
Further studies on these bacteria are followed later with contributions on clear identification
of characteristics of bacteria. Methanotrophs, a gram negative, hetrographic, aerobic bacteria
present at the top few centimeters of landfill cover oxidizes methane and produces carbon
dioxide and water.

Microbial methane oxidation by soil mechanism can play a significant role (~10%) in
reducing methane concentration in atmosphere (Faso, 1996 and EPA, 1998). These bacteria
are also found to use up common methane from the atmosphere at its atmospheric
concentration. Information on interaction between factors influencing methane oxidation in
soils is not completely understood. However, some of the factors influencing methane
oxidation are identified as oxygen concentration, methane concentration, carbon dioxide
requirements, oxidation redox potential, pH, temperature, moisture content along with some
physical property of soil (Pascal, 1996; Whalen, 1990). Besides them, there is a speculation
that toxic components, VOCs, moving with landfill gas affect this microbial activity (Pokhrel,
1998).

It is also possible to oxidize methane anaerobically with alternative electron acceptors
(Pareek, 1998). However, bacteria that perform this process have never been isolated.
Nevertheless, there is strong evidence for anaerobic methane oxidation by sulfate in marine
system (Hansen, 1988). Also anaerobic methane oxidation by ions may occur, while very
little is known about alternative electron acceptors. However, since anaerobic oxidation is
very low portion compare to total methane oxidation (<5%) it will not be considered in this
studies

Therefore, methane emission from landfill to atmosphere, generation in landfill and oxidation
in landfill cover are topics of major interest because of methane role in the greenhouse effect,
3
photochemistry on troposphere, explosive threats, migration of hazard potential, health and
safety issues and energy applications. Study on effects by soil environment at the rate of
methane oxidation is necessary to understand the relationship among them. Applications of
modeling techniques in landfills will be useful to find ways to control it.

1.2 Objectives of the Study

This study is directed to achieve a multi purposes, namely;

1. Application of modeling techniques and sensitivity analysis
For methane inventory (macro level)
For methane generation in landfill (micro level)
For methane oxidation in landfill cover (micro level).

2. Experimental study of VOC effects on methane oxidation rate in landfill cover.

1.3 Scope of the Study

In the view of stated objectives of this study, the scope of modeling is limited to the following
conditions,

Excel spread sheet collaborated with Visual Basic is used for modeling of methane
emission from landfills

The guidelines established by IPCC in 1995 with some amendments are used to formulate
the model for methane inventory from landfills

"Vissim" software is used as a mathematical tool for modeling of methane generation in
landfills

The methane generation model is formed using biokinetic model equations describing the
dynamics of the microbial landfill ecosystem

The methane oxidation phenomenon is modeled using experiment results from laboratory
scale lysimeter installation filled with mixture of different soil

Three different concentrations of benzene are used to analyse the effect of VOC on
methane oxidation in landfill soil

4
Chapter 2

Literature Review

2.1 Introduction

In 1960, nations began to institute environmental protection measures (Constantinos, 1983).
Environmental engineering explored in response of such perceived environmental needs.
Insufficient cooperation between environmental protection and waste management still causes
pollution phenomena with various human health repercussions. One such case is municipal
solid waste (MSW). The objectives of the literature review are to provide a concise
relationship between MSW and global warming problem, fundamental idea of global
warming potential, details of methane generation and oxidation, and some previous modeling
works on it.

2.2 Solid Waste Management (SWM) and Landfills

Solid wastes are waste materials discharged and discarded as unnecessary from everyday
life. These inevitable products of humans daily activities affect the environment thereby
leading to health hazards and non-congenial to the aesthetic point of view. With due
consideration to these, which is both detrimental to human and the environment, an effective
solid waste management program is necessary and justifiable.

Recycle and reuse, incineration, composting and landfilling are some options available for
implementation of effective SWM practice. Solid waste management planning requires basic
information on the composition and properties of solid waste being generated to determine the
appropriate processing technology and recovery options. For metropolitan cities which
generates substantial amount of solid waste daily, the need to study the characteristics of the
various components making up the city waste is vital to its overall solid waste management.
Those are namely;
- Key environmental issues related to solid waste,
- Appropriate design conditions,
- Financial availability
- Community awareness of waste generators

Historically, landfills have been the most economical and agreeable method for the disposal
of solid waste throughout the world. Landfills are the physical facilities used for the disposal
of residual solid waste in the surface soils of earth. They produce landfill gas (mixture of
methane, carbon dioxide and other trace volatile toxic compounds) that threats global
environment, mainly global warming.

Landfills characteristically have two contrasting microbial ecosystems; often with sharp
gradients between them; anaerobic methanogenic zones occur in the upper refuse layer, and
methanotrophic zones in aerated cover soils. Rates for both methane production and oxidation
can exceed observed rates for other terrestrial ecosystems by large factors. Field flux
5
measurements (net emissions) vary over 7 orders of magnitude, from less than 0.0004
g/m
2
.day methane (Smith, 1997). These net emissions, of course, are the results of methane
production, oxidation and gaseous transport processes in the cover soil.

Fig. 2.1 Solid Waste Disposal Leading to Global Warming Problem.

Worldwide, 450-500 million-ton waste is generated every year (See Fig.2.1). Consequent of
normal solid waste management practice, recycle, reuse, composting and incineration, 320-
350 million ton waste goes into landfill disposal and it emits 9-70 Tg/yr methane (Lay et al.,
1998) in addition to a huge amount of carbon dioxide. These gasses create the global warming
problem.

6
2.3 Global Warming and Landfill Gas

2.3.1 Fundamentals of Greenhouse Gases

Before the industrial revolution (1750-1800) the amount of CO
2
in the atmosphere was 270
ppm and has increased substantially to the present level of 356 ppm. This figure is projected
to double by 2100. As the amount of greenhouse gases increase, additional heat will be
trapped in the atmosphere causing the phenomenon called " global warming", also known as
"greenhouse effect".

Greenhouse gasses are found naturally in the atmosphere, in small quantities. They absorb
outgoing long wave infra red radiation or heat energy, which the earth and the atmosphere
normally radiate back to outer space as illustrated in Fig. 2.2. Greenhouse gas makes the earth
warm and inhabitable. The major greenhouse gases are carbon dioxide (CO
2
), methane (CH
4
),
nitrous oxidize (N
2
O) and ozone (O
3
). In addition, there are human produced gases utilized
for industrial and economic development that have the capacity to absorb heat, similar to
natural greenhouse gasses as well as to destroy the ozone layers, which binds the earth's out
atmosphere. These gases are chlorofluoro-carbons (CFCs), hydrochlorofluoro-carbons
(HCFCs), hydrofluoro-carbons (HFCs), and perflurinated- carbons (PFCs). The concentration
increment of greenhouse gases is shown in Table. 2.1.

Fig. 2.2 Global Warming Scenario.
Source: Pokhrel (1998)

7
Table. 2.1 Comparison of Properties of Greenhouse Gases

Greenhouse Gases
Greenhouse
potential per
molecule of
carbondioxide
@

Increase in
concentration per
year
#

%
Contribution
to greenhouse
effects
*

%
Atmospheric
residence
time^
years
Carbondioxide 1 0.50 49 120
Methane 25 1.00 19 10.5
Chloroflorocarbon 12000 5.00 17 55
Nitrous Oxide 320 5.00 5 132
Others 0.25 10
@
Source: TEI (1996)
#
Source: Oanh (1996)
*
Source: Foley (1991)
^
Source: Peter and Kirks (1993))

Greenhouse gases vary in atmospheric lifetime and in radiative effects, also known as global
warming potentials (GWPs) as shown in Table. 2.1. GWP defines warming effects caused by
a unity mass (1kg) of a given gas relative to that of carbon dioxide.

2.3.2 Impact of Greenhouse Gases

The effect of the greenhouse gases on the global energy system is shown in Fig.2.3. The
major effect of greenhouse gases is change in global temperature. Food production on the
other hand can be affected in arid and semi arid regions due to low precipitation. Some of the
places might become desert where as the cropping system is shifted to upland areas. Sea level
rise is predicted based on increase in temperature. Increase in sea level can result the most of
the worlds low laying low areas to be waterlogged. Changing temperatures and rainfall
patterns will impose the variety of pressures upon plants and animal life of different
ecological zones. The most affected ecological system is coral reefs, the earths most diverse
ecosystem with as many as 3000 species (Pokhrel, 1998). Wildlife habitat and vegetation are
also affected resulting in extinction of endangered species. So, once it is disturbed it will be a
long run procedure to restore the ecological balance.

8

Fig. 2.3 Effect of Greenhouse Gases on Environment
Source: UNEP (1993)

2.3.3 Methane Contribution of landfill

Methane (CH
4
) is one of the main sources of greenhouse effects because it has global
warming potential greater than other greenhouse gases and its contribution on greenhouse
effects is 17% (see Table. 2.1). In 1992, the IPCC/OECD reported that global methane
emission from anthropogenic sources was 360 million tones/yr. of which emission from
landfill accounted for between 20-70 million tones/yr. This is more than 6% of total methane
emission to atmosphere through out the world. Percentagea of various sources of methane
emission into atmosphere is shown in Fig.2.4.

The proportion of methane produced world wide from landfills is illustrated in Fig. 2.5.

The IPCC established guidelines to determine methane emission from MSM landfill in 1995.
This simple method, based on the mass balance approach, incorporates no time factor and can
be applied to the total waste emanating from the country. The calculation is based on the
amount of waste generation and landfill, the fraction of degradable organic carbon (DOC), the
fraction of DOC that actually degraded into biogas and the fraction of biogas that was
released as methane.
9

Fig. 2.4 Share of Individual Sources (%) of Methane in Estimated Global Emission
Source: Iserman (1994)

Fig. 2.5 Percentage of Methane Produced Worldwide from Landfill
Source: TEI (1996)

Rice paddies
22%
Landfills
7%
Biomass burning
7%
Domesticated ruminants
13%
Coal minings
5% Unknown
fossil fuels
10%
Gas Production and
Distribution
5%
CH
4
Hydrate
1%
Ocean
2%
Freshwater
1%
Wetlands
19%
Termites
7%
Undomistaked
ruminants
1%
Europe
25%
Asia
22%
South America
8%
Oceania
2%
North America
43%
10
2.4 Landfill Gas Generation

2.4.1 Gas Production

Solid waste placed in the landfills undergoes a number of simultaneous and interrelated
biological, chemical and physical changes. Various types of reactions occur inside the landfill
depending upon site conditions, waste characteristics, oxygen, temperature, moisture content,
nutrients and other factors. The most important reactions occurring in landfills are those
involving the organic MSW that lead to the evaluate of landfill gases and, eventually liquids.
Pathways leading to the production of methane and carbon dioxide from anaerobic digestion
of organic fraction of solid waste are shown in Fig 2.6 and 2.7.The chemical reaction for the
anaerobic decomposition of solid waste can be written as,
(bacteria)
Organic matter +H
2
O biodegraded +CH
4
+CO
2
+other gases
organic matter

In the anaerobic zone of the mature landfill, the gas phase is represented by methane (50 - 70)
% and carbon dioxide (30 - 40)%. Microimpurities, the main components of which are
nitrogen, hydrogen, carbon monoxide, hydrogen sulfide, ammonium, may constitute only few
percent. (Nozhevnikoa et al., 1993).
Fig. 2.6 Schematic diagram of pattern of carbon flow at anaerobic condition
Source: Metcaff and Eddy (1993)

Lipids Polysaccharide Protein Nucleic acids
Fatty acids Monosaccharides Amino acids Purines &
pyrimidines
Simple
aromatics
Other fermentation
products (e.g. propionate,
butyrate, succinate, lactate
ethanol etc)
Methanogenc substrates
H
2
, CO
2
, formate, methanol,
methylamines, acetates
Methane +carbondioxide
Theoretical
stages
Hydrolysis
Acidogenesis
Methano
genesis
11
2.4.2 Different Phases of Biodegradation

The Landfill gas is the end product in the series of waste decompositions. Normally, the
process of waste decomposition is analyzed into five phases. (see Fig.2.7)

1. Initial adjustment:
It is the initial phase, in which the organic biodegradable components in waste undergoes
microbial decomposition in aerobic condition soon after they are placed.

2. Transition phase:
In it, oxygen is depleted and anaerobic conditions begin to develop.

3. Acid phase:
In the acid phase, hydrolysis of high mass compound takes place and its products are
compounds suitable for microorganism to use as energy or carbon sources.

4. Methane fermentation phase:
Methanogenic bacteria converts acetic acid and hydrogen formed in the acid phase to CH
4
and
CO
2
.

5. Maturation Phase:
It is the final phase where the rate of gas generation is diminished because most of the
nutrients have been removed during the previous phases and substrates that remain in landfill
are slowly biodegradable.

Fig. 2.7 Generalized Phases in the Generation of Gases.
Source: Tchobanoglous (1993)

12

It is impossible to develop a kinetic equation for actual conditions inside a landfill since
various unknown parameters are responsible for gas production. The simplest equation used
to describe time rate of production of gas is expressed with a first order equation with reaction
rate depending on substrate concentration. The modified Monod equation relating rate of
substrate utilization both to the concentration of microorganisms in the system and to the
concentration of substrate surrounding the organism is expressed as (Tchobanoglous, 1993),

dS
dt
KXS
Ks S
=
+
..Equation 2.1
Where,
K =Maximum rate of substrate utilization per unit mass of microorganisms (T
-1
)
X =concentration of microorganisms (mass/ volume)
Ks = waste concentration at rate of one half of maximum rate of substrate
utilization (m/v)
S =concentration of substrate surrounding the microorganism (mass/ volume)

The equation can be approximated as,
dS
dt
KX = When S >>Ks ..Equation 2.2
(Zero-order reaction)
And
SX
Ks
K
dt
dS
= When S <<Ks ..Equation 2.3
(First-order reaction)

The production rate of gas in landfill is important to determine the landfill gas flux through
the landfill cover soil. High rate of production and mature landfill creates more flux and old
landfill produces with low flux. This parameter is important for the design of landfill gas
recovery and landfill gas management systems.

2.4.3 Movement of Landfill Gas

Normally, gases produced in soils are released to the atmosphere by means of molecular
diffusion and pressure driving force. Movement of landfill gas is multidirectional and
mathematical expression for the movement contains higher order differential expressions.
Based on certain assumption a simplified differential equation of landfill gas migrating
vertically upward is expressed in one dimensional control volume as follows (Tchobanoglous,
1993);

(1+)( C
A
/t) = - V
Z
(C
A
/
Z
) + D
Z
(
2
C
A
/
Z
2
) + G ..Equation 2.4

13
Where,
= total porosity
=retardation factor accounting for sorption and phase change
C
A
=concentration of compound A, g / cm
3

V
Z
=velocity in vertical direction
D
Z
=effective diffusion coefficient (=D (
gas
10/3
/
2
), cm
2
/s
G =lumped parameter used for account for all generation terms, gm/cm
3
.s
Z =depth, m.
t =time, s

To calculate convective velocity in vertical direction, Darcys law can be used to describe the
mechanism of gas flow in landfill with the condition of laminar flow (Reynoldss number less
than 1). This condition can be achieved with the mean grain size of the porous medium less
than 0.2 cm (Emcon, 1980). Darcys law is expressed as:
V
r
=- k
dh
dr
..Equation 2.5
Where,
Vr = gas velocity
k = coefficient of permeability

d h
d r
= Pressure gradient

The design of cover systems incorporated with gas control requires an understanding of the
physical, chemical and biological processes governing gas migration and comprehensive
mathematical model to describe gas migration across landfill cover systems described herein.
Flow through a landfill cover is essentially multiphase involving a water phase and a gas
phase. The gas phase may include such as CH
4
, CO
2
, O
2
, N
2
and water vapor. The effect of
moisture infiltration into a landfill cover has an impact on gas migration, but considering the
time scales, such effects can be neglected. However, the effect of moisture saturation on gas
permeability should be taken into account.

14
2.5 Methane Oxidation in Landfills

2.5.1 Mechanisms of Methane Oxidation

The recent studies says that methane oxidation plays significant role in the rate of methane
emission from landfills. Here, rate of oxidation depends on the both biochemical and physical
process in the soil ( Hettiarachi et al., 1998). The presence of natural sink of methane was
realized based on the discrepancy between theoretical methane production and atmospheric
methane concentration, and encouraged scientists and researchers to investigate and identify
its existence. The identification was important from two points of view; the reduction of
potentially hazardous seeps of methane around landfill sites, and other methanogenic
environments; and a reduction in theoretical yield of greenhouse gas from landfills.

Generally methane oxidation happens at two conditions, namely,

Aerobic condition:
Methane utilizing bacteria are found to be a more diverse group of organism (Whittenbry et
al., 1970), with methanotrophs designated for methylotrophic bacteria that can use methane
for carbon and energy source (Christopher et al., 1983). The methanotrophs form a
specialized group of bacteria which contain the enzyme system responsible for oxidizing
methane, in presence of molecular oxygen, to form metabolic products carbon dioxide and
water (Barratt, 1995);

CH
4
+2 O
2
CO
2
+2 H
2
O +(883 kJ )

Theoretically, each mole of CH
4
disappears with two moles of O
2
to produce one mole of
CO
2
. The actual value doesnt agree with theoretical value because of carbon assimilation.
The maximum carbon conversion efficiency observed is as high as 43 %. The more efficient
the bacterium is in assimilation, that is efficient in utilizing energy released by oxidation of
CH
4
for cell synthesis, the greater the disparity from the theoretical ratio of 1 CH
4
: 2 O
2
, with
their ratio comes equilibrium once population density reached to its equilibrium condition.
Water formed makes favorable environment for methanotrophic activity helping the oxidation
process (Pokhrel, 1998).

Anaerobic condition:
It is possible thermodynamically, to oxidize methane (organic matter) anaerobically with
alternativeelectron acceptors (Pareek, 1998). Furthermore, anaerobic methane oxidation by
sulfate in marine system shows strong evidence (Hansen, 1988). Anyway, bacteria that
perform this process have never been isolated. Also anaerobic methane oxidation by ion may
occur, while very little is known about alternative electron acceptor. As anaerobic oxidation is
very low portion compare to total methane oxidation (<5%) it will not be considered in this
study.

15
2.5.2 Influences of different Parameters

Methane oxidation rate is not constant in all types of soil and all environmental conditions.
There are various parameters influencing methane oxidation rate. Although the actual
oxidation in soil are not yet completely understood, some identified parameters responsible to
control methane oxidation are oxygen, methane and carbon dioxide concentration, oxidation
redox potential, pH, temperature, types of soil including compaction status of soil, moisture
content, N-amendment, N-turnover, and soil organic matter (Pokhrel, 1998). Some of the
influencing parameters and the effects are explained below.

1) Oxygen Concentration:
In aerobic methane oxidation process, concentration of oxygen in soil voids plays major role
with high rate of oxidation at high concentration of oxygen. High rate of methane oxidation is
observed at oxygen concentration between 10 % to 40 % and decrease on either increase or
decrease in oxygen concentration as shown in Table 2.2.

Table. 2.2 Consumption of Methane with Various Concentration Oxygen and Nitrogen

Partial pressure of Methane consumed per day
Oxygen % Nitrogen % Sample A mL Sample B mL
0 70 0.00 0.00
10 60 1.05 0.94
20 50 0.88 0.88
30 40 1.05 1.05
40 30 - 0.94
60 10 0.35 0.52
70 0 0.23 0.29
Note: Methane consumed per day by methane oxidizing bacteria during 6 days at 32
0
C
Source: William and Zobell (1989)

2) Methane Concentration:
The threshold methane concentration for methane oxidation was found to be 1 nmol CH
4
(Roslov, 1992). Atmospheric methane oxidizers have ability to sustain long-term oxidation of
sub atomic concentration with high affinity enzyme system and a rather low V
max
(K
m
=30-51
nm CH
4
; V
max
=0.7-3.6 nmol CH
4
/ hr / g soil) the kinetic properties being sufficient to permit
maintenance and cell growth with atmospheric methane as substrate. Increase in methane
concentration also decreases the carbon conversion efficiency. Laboratory experiment
methane consumption at different headspace concentration indicates the increase in oxidation
rate at upto 40% methane concentration. (see Table.2.3).

16
Table. 2.3 Consumption of Methane with Various Concentrations of Methane and
Nitrogen
Partial pressure of Methane consumed per day
Methane % Nitrogen % Sample A mL Sample B mL
0 70 0.00 0.00
10 60 0.33 0.40
20 50 1.00 1.00
30 40 - 0.94
40 30 1.80 1.80
60 10 1.74 -
70 0 1.86 2.04
Note: Methane consumed per day by methane oxidizing bacteria during 6 days at 32
0
C
Source: William & Zobell (1949)

3) Carbondioxide:
The increase in carbon dioxide in initial mixture was considered to enhance multiplication and
oxidation. Increase in CO
2
above 20 to 30 % resulted in reduction in methane oxidation. The
carbondioxide was required for initial metabolism and no more carbondioxide was required
for methanotrophic activities. High concentration of carbondioxide means less oxygen and
methane. This results in reduction in methane oxidation rates.

4) Oxidation redox potential:
Methane oxidation is high at higher oxidation redox potential with some exceptions. A survey
of change in redox potential in the soil profile showed where the layer of methanotrophic
bacteria could exist in sufficient numbers, affect methane emission from soil (Pokhrel).

5) pH :
There is an optimum pH range for maximum methane oxidation. Methane consumption rate at
various pH ranges observed by William and Zobell reported the favorable pH value as 6.6 as
shown in Fig. 2.5.1. From the figure it can be seen that, pH values on either side of neutral
ranges are not favorable for methane oxidation.

6) Temperature:
Effect of temperature on methane oxidation in a fresh soil sample, determined by Pokherl
(1998) is shown in Fig.2.8. The figure indicates the high rate of oxidation at temperature
between 30 to 36
0
C with complete inhibition at 46
0
C. Very low oxidation is seen at 5
0
C.
Whalen et al.(1990) also has made similar observations. However, the survivability of
observation methanotrophs between freezing and thawing cycle is not well understood. (
Pokherl, 1998)
17

Fig. 2.8 Amounts of methane consumed in 42 days at 27
0
C by methane oxidizing
bacteria in media of different initial pH values
Source: William & Zobell (1989)

Fig. 2.9 Variation of Oxidation Rates with Temperature
(for fresh soil sample, moisture content 16% and initial headspace CH
4
=3.5-4.5%.)

7) Moisture Content:
Moisture content also plays important role in methane oxidation. (Pokherl, 1998) found
optimum moisture that falls within range between 15 to 20% (see Fig.2.10). Decrease in
oxidation rate at high moisture content is explained by reduced gas diffusion between soil and
gas phase (Pascal & Cleempul, 1996), and presence of diffusion barrier between the bacteria
and their substrates, methane and oxygen.
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0 10 20 30 40 50
Temperature
O
C
M
e
t
h
a
n
e

o
x
i
d
a
t
i
o
n

r
a
t
e
(
1
0
-
6

g

C
H
4

/

g

s
o
i
l
.
h
)
18

Fig. 2.10 Variation of Methane Oxidation rates with Moisture content
(for fresh soil sample incubated at 30
0
C, initial headspace CH
4
=3-4%)

8) Nutrients :
Addition of ammonium ion is found to have inhibition effect with rate of methane oxidation
(Whittenbury et al., 1970). In landfill containing low C/N ratio, methane oxidation can be
suppressed because of increased turn over ( Smith, 1997).

9) Methane Flow:
Conditions and patterns of methane flow too effect soil methanotrophy. Once established, the
methanotrophs survive under intermittent flow conditions. The methanotrophic activity is
directly related to the detention time of the CH
4
in the oxidation layer. Source strength of
landfill gas, as well as gas permeability will affect this factor. Although it is possible to
decrease the permeability of this layer, CH
4
flow rate will be mainly governed by the gas
permeability of the hydraulic barrier layer. This is because the effective permeability is
determined by the lowest permeability in a layered structure ( Hettiarachi et al., 1998 ).

Methane oxidation rate decrease with the increase in depth depending upon soil type and
moisture content. The decrease of oxidation is due to absence of aerobic microorganism well
below ground level. While sufficient information on factors influencing methane oxidation in
soils is available in literature, the interaction among variables are not well known.

0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 5 10 15 20 25 30
Moisture contents (%)
M
e
t
h
a
n
e

o
x
i
d
a
t
i
o
n

r
a
t
e

(
*
1
0
-
6

g

C
H
4

/

g

s
o
i
l
.
h
)
19
2.6 Landfill Gas Mitigation

2.6.1 Mitigation Options

Today, many countries and environmental protection organizations are committed to
mitigating methane emission from landfills and large opened dumps by encouraging the
program called "control of methane emission from landfills" and developing environmentally
and economically developemnt development beneficial landfill gas to energy (LFGTE)
projects (Wetherill et al., 1997). The various pathways into which landfill methane is
partitioned are shown in Fig.2.11, which illustrates both methanotrophic oxidation and
engineered control systems (pumped gas recovery) may reduce emissions.

Fig. 2.11 Methane Balance Diagram.

It is hard to control whole migration of landfill gas. However, there are some methods by
which it can be controlled to reduce atmospheric emission, minimize surface and subsurface
migration, and minimize release of odorous materials, to reduce explosions, and collect for
energy production. Those are namely,
- Effective solid waste management (SWM) practice,
- Landfill gas collections and
- Promoting methane oxidation in landfills.

20
2.6.2 Effective Solid Waste management Practice

Solid waste management is a key role in solving environmental problem in many countries.
Source separation, recycling, incineration, composting and landfilling are some of the main
practice in solid waste management program. The choice of proper option varies from place to
place depending upon various factors that have been discussed in section in 2.1.

Typical solid waste management practice to provide the way of reducing current greenhouse
gas emissions and its adverse effects in USA is shown in Fig. 2.12.

Fig. 2.12 Trends of Waste Generation, Recovery and Disposal in US.

As we discussed in section 2.3 organic carbon is the key component in generation of landfill
gas. It potentially influences in effective solid waste management to provide the way of
reducing current greenhouse gas emissions and its adverse effects. They include,
- Source separation and applications of triple "R" (Reduction, Reuse and Recycle)
principle in large extent before go for landfill disposal.
- To encourage composting in case of waste that content high DOC (degradable organic
carbon).
- Only low DOC waste to sanitary landfill.

In the past, the term sanitary landfill was used to denote a landfill that the waste placed in the
landfill was covered at end of the each dailys operation. Today, Sanitary landfill refers to an
engineered facility for the disposal of MSW designed and operated to minimized public health
and environmental impacts.

21
2.6.3 Landfill Gas Collections

According to USEPA regulations, landfills should have vent pipes for releasing landfill gases.
It avoids accumulates landfill gas in bottom. Landfill gas collection system can be categorized
into two basic types such as vertical well system and horizontal trench system. The common
system for landfill gas collection is the vertical well system. Horizontal wells may be installed
to recover landfill gas from active landfill for controlling gas migration (Wetherill et al.,
1997). Two methods are in use to collect landfill gas, namely passive control and active
control system.

Passive systems:
- They are functional due to the natural pressure gradients (i.e. internal landfill pressure
created by landfill gas generation) or concentration gradient to convey the landfill gas to
the atmosphere or a control system. This type of control system is applicable when the
landfill gases are produced at a higher rate so that it can move in the desired direction.
(Tchobanoglous)

Active control system:
- It is applicable for landfill producing landfill gas not enough to exert pressure for its
movement by convection and diffusion. In this system some energy is required for
removal of landfill gas.

Generally, recovered methane either flares or uses as source of energy. Although flare convert
landfill gas into carbon dioxide and water it is not advisable due to production of smoke and
particulate which are considered as air pollutants. Use as source of energy is economical and
environmentally friendly method to reduce landfill gas emissions. There are three primary
approaches in using landfill gas. They include,
- Direct use of gas locally,
- Generation of electricity and distribution through power grid and
- Processing and injection into a gas pipeline.

However, use of landfill gas is not practical every where because of
- High impurities: H
2
S in landfill gas, which causes corrosion in IC combustion engine
that converts gas into electric energy.
- Low gas production rate from landfills.
- Landfill does not meet regulations to collect gas.
- High investment cost.
- Lack of skill labour.

22
2.6.4 Promoting Methane Oxidation

Landfill cover soils is also a critical component in mitigation of landfill gas in addition to
separate buried waste or contaminated materials from the surrounding environment, restrict
infiltration of water into waste, and limits release of gas from waste. Since methanotroph
bacteria in landfill cover utilize methane it can be controlled to reduce atmospheric emission
(Hettiarachi et al., 1998). Mechanism of methane oxidation and factors influencing in
methane oxidation are discussed in section in 2.4.

Incorporation of soil methonography in landfill cover design promotes methane oxidation in
landfill cover soil. Maximum oxidation occurs when the soil is aerobic and there is enough
moisture in the soil. The optimum soil moisture content is between 11% and 15% depending
on the soil parameter ( Pokhrel, 1998 and Whalen, 1990). To be aerobic, the soil should be
more porous to allow oxygen to diffuse deep into the soil. This design should be very precise
to minimize the infiltration of excess water, which make leachate production.

Leachate recirculation overcomes this problem, meanwhile it helps to maintain desired
moisture in the landfill cover soil which enhances methane oxidation and increases landfill
compaction. In contrast, it is also favorable to methane generation bacteria in landfills, which
increases methane production.

In methane control strategy, Pareek et al.(1998) added sulfate in recirculation line, called
sulfate reducing reactor (See Fig.2.13). Here, sulfate has been used as electron acceptor and
the degradation of organic matter was carried out under sulfate reducing condition by sulfate
reducing bacteria (SRB). Methane producing bacteria (MPB) and SRB compete for the
utilization (oxidation) of organic matter as follows,

Organic matter CH
4
+CO
2

Organic matter +SO
4
2-
S
2-
+CO
2

The second reaction becomes predominance as thermodynamically and kinetically, SRB are
more favored than MPB in this competition.

Henry (1995) has confirmed anaerobic methane oxidation in presence of sulfate. Therefore,
this arrangement will be also instrumental in anaerobic oxidation of produced methane.
Furthermore, the produced sulfide (S
2-
), which remained in leachate as dissolved sulfide, was
collected and treated to convert sulfide (S
2-
) to sulfate (SO
4
2-
) and recycled back at top of
landfill reactors as shown in Fig.2.13.

Generally, leachate from new landfills has 50- 1000 mg/L sulfate (SO
4
2-
) (Tchobanoglous,,
1993). When there is high concentration of sulfate (SO
4
2-
) it can be reused for this purpose.
SRB
MPB
23

Fig. 2.13 Sulfate Reducing Reactor
Source: Pareek (1998)

Hilger's (1998) study in long term laboratory stimulation (under direction of Mortan S.Balarz)
showed that addition of NH
4
-
and N0
3
-
had stimulated methane oxidation in soil; grassed soil
had reached high methane uptake than bare soil and lime amended soil had consumed more
methane. These results will be also useful to accelerate methane oxidation in landfill cover
soil.

Unsaturated
zone
Saturated
zone
1. Water injection port
2. Thermometer
3. Gas bag
4. Sand layer
5. Solid waste packed layer
6. Control cock of water level
7. Pump
8. Aeration tank
9. Settling
24
2.7 Landfill Methane Models

2.7.1 Existing Solutions

A landfill methane model is a tool that can be used to estimate methane generation rate,
methane oxidation rate and total methane emission from landfill. This section reviews their
features and examines their current predictive abilities. Exiting models are only partially
validated. However, their forecast is not very far from real situations and they are widely
used. Historically, models have been used in landfill process since 1970. Now, models are
used for applications that include the sizing of landfill gas collection system, evaluating the
benefits of gas recovery projects and controlling gaseous emission to environment.

Augentein (1990) has used a model to estimate total methane emission from US landfills and
evaluation of methane net contribution and significance of these emissions to the atmospheric
methane build up and green house phenomenon. This shows methane emission from landfills
in 'US' increases 1-2% of atmospheric methane build up and it contributes 2-10% impact of
green house effects.

Zison (1993) has made some efforts to develop landfill gas production curve using various
models. In this study, model order or order of kinetics; decay rate constant and mass
substrates are considered as major factors in formulating the production curve model. Then,
he used first order kinetic model as basis and optimized other model parameters (shown in
Fig. 2.14). His results suggest that that order of kinetics are not very important in landfill gas
production.

Augenstein (1992) and Pacey (1992) have reviewed and examined predictive ability of
landfill methane models. This shows that gas generation model uncertainties arise from no of
sources such as difficult to trace waste placement, history, location and composition for older
landfills and difficult to measure biological parameters, nutrients, temperature and pH and
difficult to deduce collection efficiency and difficult to estimate or measure moisture contents.
Gas generation profile in landfill where waste placement occurs at slowly changing or
constant rate of many years is effected to the greatest extent by the yield rate parameters. The
profile assumed for unit batch output tends to become less important as the interval of
placement increase.

These research findings demonstrate the importance of the modeling of landfill methane is a
topic of major interest, because of its role in the greenhouse effect, migration hazard potential,
health and safety issues, and energy applications. The modeling process still needs
improvements and refinements, I feel that a concerted effort to compile generation data on a
range of landfills, including some from different countries to test data against plausible model
variations should permit the development of approaches in forecasting methane generation,
migration and hence, recovery.
Some models that involve with the objectives of this study are detailed in following
sections.
25

Fig. 2.14 Model Kinetics Comparison Using First order Model as Basis for Optimizing
the Constant of Zero order Model for 35 years Period (1957 1992)
Source: Zison (1993)

2.7.2 Models for Inventory of Methane Emissions from Landfills

Methane gas plays an important role in the earth's thermal budget and photochemistry of the
troposphere. Atmospheric methane concentration has been increasing in the past three
decades at the rate of 1-2% per year. Because of the impact of methane on the environment, it
is important to quantify the total methane emissions.

Basically inventory methodology contents two main steps such as calculation of municipal
solid waste (MSW) landfilled and methane generation rate. MSW landfilled find from total
amount of MSW, which is calculated from population and waste disposal per capita, and
portion of incineration. Then methane emission to atmosphere is determined from total
methane generation and recovery.

To determine methane generation rate, Sheldon-Arleta model and Scholl Canyon kinetic
models can be used. Even though both of them are first order, Sheldon-Arleta model is two-
stage model and Scholl Canyon kinetic model is single stage model (see Fig. 2.15 ). Two-
stage model doesn't make any sense since estimation of total methane emission from landfill
is time independent. So Scholl Canyon models developed by EPA is preferable to quantity
total methane emission from landfill

26
Fig. 2.15 Examples of Model Predictions.
Source: Zison (1993)

Scholl Canyon kinetic models is based on characteristics of substrate-limited bacterial growth
and It does not take into consideration various parameters which is specific for each landfill.
It assumes that the gas production rate is at its peak after a time period of negligible duration
during which anaerobic conditions are established and the biomass build up. Thereafter, the
gas production rate is assumed to decrease according to that, methane production rate is
proportional to remaining methane potential to be produced.

The IPCC established guidelines to determine methane emission from MSW landfill in 1995.
This simple method, based on the mass balance approach, incorporates no time factor and can
be applied to the total waste emanating from the country. The method assumes that an
instantaneous release of methane takes place from the refuse during the year it is landfilled.
The calculation is based on
- the amount of waste generation and landfill,
- the fraction of degradable organic carbon (DOC),
- the fraction of DOC that actually degraded into biogas and
- the fraction of biogas that was released as methane.

In contrast to landfill, estimations of greenhouse gas from MSW open dumping were less. The
IPCC recommended the simplified methodology relating to landfill calculations under the
assumption that MSW open dumping conversion of actual DOC to methane was 50% of the
MSW landfill conversion.

27
The calculation of greenhouse gas emission from landfill is based on IPCC guide lines as
follows,
Methane emission (Gg/yr.) =Total MSW (Gg/yr.)
x Fraction MSW landfill.
x Fraction DOC in MSW
x Fraction actual DOC dissimulated
x 0.55 g C as CH
4
/ g C biogas
x Conversion ratio (16/12)
- recovered CH
4
(Gg/yr).

The calculation of greenhouse gas emission from open dumping is based on the following
equation,

Methane emission (Gg/yr) =Total MSW (Gg/yr.)
x Fraction MSW open dumped
x Fraction DOC in MSW
x 0.275 g C as CH
4
/ g C biogas
- recovered CH
4
(Gg/yr

Where Total MSD =population x waste generation rate

However, the assumptions made here are questionable. Namely,
- No time factor: It is quite acceptable during steady state.
- Instantaneous release of methane: It takes atleast 1 years.
- No consideration of natural oxidation of methane: According to researchers,
considerable amount of (~10%) methane oxidize within landfills.

2.7.3 Numerical Modeling of Gas Generation

El Fade et al.(1995) has developed a numerical model for gas generation in sanitary landfills.
This model highlights the significance of the biochemical and biological parameters that
control gas in sanitary landfills. Several simulations have been performed to assess the model
sensitivity to its biochemical and biological parameters. These parameters include the pH, the
hydrolysis rates of the different waste constituents and biokinetic constants of the two
microbial populations of the simplified ecosystem such as acidogens and methanogens. To
asses the effects of assumed initial conditions, simulation with varied initial carbon
concentrations including aqueous, acetic acid, acidogens and methanogens initial ware
conducted. The temperature was held constant during all sensitivity analysis of simulation.

28

Fig. 2.16 Effect of Hydrolysis Rate on Total Methane Generation
Source: El Fade et al.(1995)
Fig. 2.17 Effect of Acidogenic decay Rate on Total Methane Generation
Source: El Fade et al.(1995)
29
This system appears reasonably well buffered. The simulation without chemical feed back on
the equilibrium shows higher pH values than with chemical feed back, however both well
within the optimal pH range for methanogens. That is, the chemical component effects are
minimal during applying through its pH feed back. Consequently no further sensitivity
analysis was per formed with respect to chemical parameters.

The simulation with different hydrolysis rate shows major effect (see Fig. 2.16) on methane
generation because hydrolysis of solid organic carbon to aqueous carbon is first step in the
process. So a change in the hydrolysis rate generally results in early start of methane
generation and higher peaks for all forms of organic carbon. Therefore, the hydrolysis rate is
most important parameters that directly affects gas generation in sanitary landfills.

Biokinetic parameters come next in order of performance. These parameters include specific
growth rate, the half saturation concentration and decay rate of acidogens and methanogens.
Model is not very sensitive to acidogen parameters (see Fig. 2.17) because in general,
acidogen grow is very faster than methanogens and consequently, concentration of aqueous
carbon, acidogens and acetic acid are two or three orders of magnitude higher than
methanogens.

The simulations indicated that a change in the initial concentration of aqueous carbon does
not effect the final steady state values of aqueous and acidogens carbon and the acetic acid
and methanogens have a more pronounced effect on gas generation than aqueous and
acidogens.

30
Chapter 3

Methodology

3.1 Work Outline

Conventional way of standard engineering practice for newly proposed studies consists of
three basic steps; first laboratory scale study, then the pilot scale study, finally the full-scale
operation. Nowadays, mathematical simulation is in common use before full-scale operation.
It minimizes workload of laboratory and pilot scale studies, which are the most time
consuming steps. Based on it, the objectives of this studies are to model methane generation,
methane oxidation and methane emission in landfills, and to check the affect of VOC on
methane oxidation in landfills. Here, the analysis of methane from landfills is aimed on global
environmental protection, mainly mitigation of green house gases. It also assessed the
potential of energy recovery option from landfill gas. The following sections present the
detailed methodological approach adopted in this research.

3.2 General Modeling Techniques

Models are necessary to both describe and predict landfill processes in micro and macro level.
Current modeling practice provides limited predictive capacity that cannot be achieved easily
by monitoring or measuring variables. Generally, the modeling process includes following
steps.

1. Selection of model objectives: Initially, model objectives should be well defined to
proceed modeling work. The selection of models for investigating landfills is governed by
goals of the study.

2. Problem formation: Based on objectives, a clear statement of the limitation of modeling
formation is necessary because modeling technique are derived from a diverse collection
of interdisciplinary methods.

3. Model construction: Construction of model involves with five basic steps, namely;
- Identifying the physical, biological and chemical process, and corresponding physical
laws and biological chemical kinetics governing the rates of mass flow between
compartment and boxes
- Listing the assumption made, including simplicaton of physical laws
- Constructing system of mathematical equations that describe the behavior of the
system. The system of equation is constructed by writing a statement of conservation
of mass or energy
- Evaluating boundary conditions
- Solving the mathematical equations.

31
4. Model calibration: The calibration data procedure is designed to use field measurement
to guide choosing the empirical coefficients in models and to determine if the boundary
and initial condition are consistent with interior measurement for the model chosen.

5. Model validation: Validation testing is designed to confirm that the calibrated model is
useful over the range of conditions defined by the calibrations and validation data sets. It
is important and time-consuming step in modeling work. Usually it involves with
independent data collected from real field or laboratory scale study.

6. Prediction: After making sure the validity, it can be used for prediction. It is the final
stage of modeling work.

3.3 Application of Modeling Techniques

3.3.1 Methane Inventory Model

Methane inventory model is a tool used to estimate methane emission from the landfill to
atmosphere. The guidelines established by IPCC to estimate methane emission are already
discussed in section 2.6.2. It has several uncertainties, namely:
No time factor
Instantaneous release of methane takes place from the refuse during the year it is
landfilled
No consideration of natural oxidation of methane.

To overcome these uncertainties, following assumptions are made with IPCC guidelines,
Steady state methane production through out the year
Any changes in waste characteristics will take 1 years to effect methane production
More than 10% of methane oxidize within landfills.

Modified Governing Equation:
The calculation of greenhouse gas emission from landfill is based on the following modified
equation,

Methane emission (Gg/yr) =Total MSW (Gg/yr)
x Fraction landfilled in MSW.
x Fraction of DOC in landfilled
x g C as CH
4
/ gC biogas
- oxidized CH
4
(10%)
- recovered CH
4
(Gg/yr).
..Equation 3.1

32

Where, =0.5 for closed landfill and 0.275 for open dump.
Total MSW =population x waste generation rate.

Since this method is based on the mass balance approach of organic carbon, it is applicable
everywhere. Place to place, only following coefficients will be varied.
Total MSW (ie, population X waste generation rate)
Landfilled fraction.
Fraction of DOC (degradable organic compound)
Methane recovered

Specimen calculation to use this for a particular region (all cities in Thailand) is presented in
Appendix-1.2.

Data:
For case studies, the data (Appendix A) taken from literatures (Rayes and Edwards, 1991 and
TEI, 1996) were used.

Output:
Using this model, following objectives have been achieved,
Prediction of trend of methane emission from landfills to atmosphere according to
prevailing solid waste management practice.
Simulation in rate of methane emission from landfills with different options such as
fraction of DOC, fraction of methane oxidation and fraction methane recovery.
Recommendations to mitigate methane emission from landfills to atmosphere.

3.3.2 Methane Generation Model

Here, landfills are considered as solid substrate batch reactor. Methane generation is obtained
from the solution of system ordinary differential equations developed from fundamental
principle governing the microbial process and biochemical reaction associated with gas
generation in anaerobic system. The development of these equations describe the dynamics of
the landfill ecosystem including
the hydrolysis of biogasifiable waste components,
microbial utilization of aqueous carbon by acidogenic micro organism,
growth and decay of acidogenic and methanogenic biomass,
the utilization of acetate produced by acidogens and
ending with consequent generation of methane and carbon dioxide by methanogenic
organism.

A simplified pathway leading to methane generation is shown in Fig. 3.1.

33
=
i
s h
dt
dC
i i
s
C k
) (
) (

Fig. 3.1 Organic Pathways in Landfill Microbial Ecosystem
Source: El-Fadel (1994a)

Governing Equations:
The application of the mass balance couple with Monod model to landfill ecosystem results in
a set of ordinary differential equations as follows;

Solid organic carbon utilization rate

..Equation 3.2
C
(s)i
C
(aq)
C
(CH4)
C
(CO2)
C
(XM)
C
(Ac)
C
(X
A
)
Solid organic carbon
Aqueous organic carbon
Acidogenic biomass carbon
Aceate carbon
Methanogenic biomass carbon
Methane carbon
Carbon dioxide carbon
34
) ( ) (
) )( (
) (
) ( ) (
A aq A
aq
A
A
i i
aq
X C Ks
C
Y
i
s h dt
dC
C C k
+
=

) (
) (
) (
) ( ) (
A A
aq A
aq A
A
X
X d
C Ks
C
dt
dC
C K =
+
) (
) (
) (
) ( ) (
M M
Ac M
Ac M
M
X
X d
C Ks
C
dt
dC
C K =
+
) ( ) (
)] )( [( )] )( )( 1 [(
) (
) (
) (
) ( ) (
M Ac
Ac
M
M
A A aq A
aq
A
A
Ac
X C KsM
C
Y X d C Ks
C
Y A Ac dt
dC
C C K Y Y
+ +
+ =

) (
)] )( )( 1 [(
) (
) (
4
)
4
(
M M
Ac M
Ac
M
M
CH
X d
C Ks
C
Y
M CH
dt
dC
C K Y Y + =
+
) (
) (
)] )( )( 1 )[( 1 (
)] )( )( 1 )[( 1 (
) (
) (
4
) (
) ( )
2
(
M M Ac M
Ac
M
M
A A aq A
aq
A
A
CO
X d C Ks
C
Y M CH
X d C Ks
C
Y A Ac dt
dC
C K Y Y
C K Y Y
+ +
+ =
+
+

Aqueous organic production rate,

..Equation 3.3

Acidogenic biomass production rate,

..Equation 3.4

Methonogenic biomass production rate,

..Equation 3.5

Acetate production rate,

..Equation 3.6

Methane generation rate,

..Equation 3.7

Carbon dioxide production rate,

..Equation 3.8

Data:
Validations data (Appendix B) has been taken from literature (El-Fadel et al., 1994b).

Output:

Sensitivity of methane generation rate was analyzed to assess the effects of variables such
as initial conditions, specific growth rate and reaction rate constants.
Options to control methane generation based on the needs.

35
2
,
2
2
4
, 4
4
] [
] [
] [
] [
* *
O m CH m K O
O
K CH
CH
PMO MO
+ +
=
3.3.3 Methane Oxidation Model

Anaerobic methane oxidation is not considered in this study because of its low contribution
(less than 5%) in total methane oxidation. As aerobic methane oxidation (MO) required both
oxygen and methane, both substrates could be limiting the oxidation process. Monod equation
could be applicable. The major influencing parameters in potential of methane oxidation are
discussed in section 2.5.2. As data in affect of methane oxidation with temperature and
moisture content are available in depth, only both of them were considered in this study.
There are two strategies to present predictive relation of MO; firstly, finding empirical
relationship between PMO and soil environment variables; then, correlation of MO and PMO
using Monod kinetics model. It has leaded a semi-empirical formula for methane oxidation.

Governing equation:
The following double Monod expression is used as basic governing equation in this study.

..Equation 3.9
Where,
MO =Methane oxidation rate
PMO =potential of MO
Km, CH
4
=half velocity constant of CH
4

Km, O
2
=half velocity constant of O
2

[CH
4
] =concentration of O
2

[O
2
] =concentration of CH
4

Potential of methane oxidation is given by,
PMO =C
PMO
*F(t)*F(m)
..Equation 3.10
Where,
C
PMO
=Constant for PMO
F(t) =Functions of temperature.
F(m) =Functions of moisture content.

Data:
To make empirical equations and to validate the model, the experimental data (Appendix C)
reported by Pokherl (1998) were used.

Output:
By using model as a tool, following goals have been achieved;
Empirical expressions for potential of methane oxidation (PMO) related with temperature
and moisture content of the landfill cover soil.
Inhibitor effects on the methane oxidation rate.
Recommendations to improve methane oxidation in landfill cover.

36
3.4 Experimental Study

3.4.1 Experimental Outline

In modeling work, validation is important step to make sure the validity of it. Usually it
involves with independent data sets that could be generated experimentally. In this study, the
models have been validated using data obtained from literatures and the experimental data
have been created only to check the affect of VOC (Benzene) on methane oxidation scenario.

Experimental set up to simulate methane oxidation with different concentration of Benzes is
shown in Fig. 3.2. Only Lysimeters, LYS2 and LYS3 were used for this research work.
Benzene feeding unit with feed pump and timer was used to change benzene-feeding
concentration periodically. Gas collected from sampling probe and from the top outlet was
analyzed directly for methane, carbon dioxide, oxygen and nitrogen concentration using GC
(gas chromatography) connected with integrator system, in which helium was used as carrier
gas. Since benzene concentration is very low, first it was accumulated in charcoal tube and
then measured using GC. Details of measurement of benzene are discussed in following
sections.

Fig. 3.2 Experimental Setup for Column System

37
3.4.2 Benzene Analysis

As discussed in previous section, benzene could not be measured directly due to its low
concentration. Therefore, the sampling method recommended by the Manual of Analytical
Method of U.S National Institute for Occupational Safety and Health (NIOSH) was used.
Here, the charcoal tube that contents activated carbon was used to collect the gas sample. The
sampling air rate of air check sampler (SKC Model 224-PCXR8) was adjusted at
approximately 0.33 L/min. The absorbed benzene in the charcoal tube were desorbed by using
1 mL acetonitrle (CH
3
CN) and shaken for 30 minutes in ultrasonic bath. A 0.5 L sample of
solvent (benzene dissolved in acetonitrle) was injected into the Shimadzu 14A gas
chromatography that uses a flame ionization detector (FID). The column was operated
isothermally at 110
o
C with nitrogen flow rate of 35 mL/min. Standard solution for benzene 4,
16, 32 ppm were used to calibrate the standard curve of gas chromatography. Peak for
benzene was was used to identify benzene concentration in solvent and corresponding area
was interpreted in ppm using standard curve.

Standard curve is attached in Appendix D-1.1.

3.4.3 Calculations

1. Percentage Methane Oxidation

Air flow rate at the top =V
1
mL/min
Gas flow at the bottom =V
2
mL/min

Total flow =(V
1
+V
2
) mL/min
=V mL/mim (say)

Percentage of methane inflow =0.6* V
2
/V*100%
=Y % (say)
Percentage of methane outflow =X % (from Gas Chromatography)

Total methane consumed in the system
=(1-X/Y)*100%
=P % (say)
(assuming no methane accumulation inside the system)

Methane oxidation rate =0.6*V
2
*P mL/min.

The sample calculation is presented in Appendix D-2.

V
1
V
2
V
38
Benzene in
outflow
2. Concentration of Benzene in Outflow

Benzene =C
a
gm
-3
Benzene =C ppm
Volume =V
a
m
3
Volume =1 mL

Using benzene mass balance,
C
a
=C/ V
a
..Equation 3.11

Where,
C
a
=Actual concentration of benzene (g/m
3
)
C =Concentration of benzene in solvent (ppm)
V
a
=Actual volume of sampled gas (m
3
)

Furthermore,
V
a
=Q
a
*t/1000 ..Equation 3.12

Where,
V
a
=Actual volume of sampled gas (m
3
)
Q
a
=Actual flow rate (L/ min)
t =Duration of sampling (min)

Sample calculation is done in Appendix D-1.2.
Absorbed
Benzene in
charcoal tube
Desorbed
Benzene in
solvent
(CH
3
CN)
39

CHAPTER 4 40
4.1 Outline of Results and Discussions.................................................. 40
4.2 Methane Inventory Model................................................................ 40
4.2.1 Frame Work..................................................................................... 40
4.2.2 Details of Package Components...................................................... 41
4.2.3 Interface........................................................................................... 46
4.2.4 Technical Significance..................................................................... 46
4.3 Methane Generation Model ............................................................. 48
4.3.1 Basic Considerations........................................................................ 48
4.3.2 Sensitive Analysis............................................................................ 49
4.4 Methane Oxidation Model ............................................................... 52
4.4.1 Methodology Development - Effect of Inhibitors on Methane Oxidation
Enzymatic Activity......................................................................................... 52
4.4.2 Empirical Relationship..................................................................... 55
4.4.3 Simulation and Validation............................................................... 58
4.4.5 Experimental Study: Effect of VOC on Methane Oxidation Rate... 61

Fig. 4.1 Typical Input Sheet for Estimation for a Place........................................................................42
Fig. 4.2 Graphical Output Sheet of Case Study....................................................................................43
Fig. 4.3 The Typical Simulation Sheet.................................................................................................45
Fig. 4.4 Effects of Initial Solid Carbon on Rate of Methane Generation..............................................50
Fig. 4.5 Effects of Hydrolysis on Rate of Methane Generation............................................................50
Fig. 4.6 Comparison of Empirical Curve with Experimental Data for Methane Oxidation Rate.........57
Fig. 4.7 Comparison of Empirical Curve with Experimental Data for Methane Oxidation Rate.........57
Fig. 4.8 The Model Block Representing Methane Utilization..............................................................58
Fig. 4.9 The Model Block Representing Methanotroph Population.....................................................58
Fig. 4.10 Validation of Methane Oxidation for Uninhibited Fresh Soils................................................59
Fig. 4.11 Validation of Methane Oxidation for Inhibited Lysimeter Soils.............................................60
Fig. 4.12 Observed Methane Oxidation with Different Rate of Methane Supply...................................62
Fig. 4.13 Variations of Methane Oxidation with Different Rate of Methane Supply............................62
Fig. 4.14 Observed Methane Oxidation with Different Amount of Benzene injection..........................63

Table. 4.1 Nominal Values for Initial Concentrations..............................................................................48
Table. 4.2 Nominal Values for Variables.................................................................................................49
Table. 4.3 Classification of Inhibitors Based on Properties.....................................................................54
Table. 4.4 Various Trials of Empirical Function for Methane Oxidation Rate in Terms of Temperature55
Table. 4.5 Various Trials of Empirical Function for Methane Oxidation Rate in Terms of Moisture
Content. 56
Table. 4.6 Optimum values of Parameters for Fresh Soil.........................................................................59

40
Chapter 4

Results and Discussion

4.1 Outline of Results and Discussions

Based on the defined objectives and scope limitations, the results presented herein cover
mainly mathematical modeling and experimental studies. Mathematical models investigated
the scenario of landfill methane in two different stages namely macro and micro level. The
landfill methane inventory model analyzed the estimation of total methane for a particular
region or country at a macro level. Meanwhile, methane generation and methane oxidation
models minutely examined the sensitivity of involving microbial species. In the case of the
methane oxidation model, the methodology was further developed to visualize the effects of
inhibitor on the rate of methane oxidation.

Meanwhile, experimental study dealt in finding the effect of VOC on methane oxidation. For
the present study, benzene was picked as the volatile organic compound. The experimental
study was conducted in laboratory scale.

4.2 Methane Inventory Model

4.2.1 Framework

As discussed in previous section 2.2, the trend of methane emission from landfills presents a
fraction of the Greenhouse Gas Scenario System (G2S2). Therefore, an accounting structure
for estimating methane emission is needed in environmental point of view. The methane
inventory model was structured to estimate methane emissions from landfills at the country or
regional level. Then, it was used as a policy assessment tool for analyzing possible future
emission patterns.

Emissions projections are based on demographics, policies, and economic and technical
assumptions. It provides emissions estimates for base years and 15 years of future. The
package also includes general information, slide-show, case study and reference bank (Useful
References and Websites). This model incorporates two different parts: static part (example)
and the dynamic part (simulation). Additionally, they are equipped with a help file. General
information contains rationale and concept of work. Similarly, the slide-show illustrates issues
and practical remediations, and they have been arranged in topic-wise. Lastly, an equally
useful element of this software package is the reference bank. This part consists of a
bibliographic list of a variety of reference materials on solid waste disposal and landfill
management, and a list of useful Internet web-sites related to landfill gas control.

Methane release from landfills is calculated by estimating the amount of municipal solid
waste (MSW) landfilled, the degradable organic carbon content (DOC) of the landfilled
41
waste, and the degradation rate of the DOC to gaseous form. Methane releases from the
dissimulated carbon in landfills is estimated based on the fraction of landfill gas that is
released as CH
4
. Finally, methane releases from landfills may be adjusted by estimating the
proportion of methane that is recovered and oxidized within the landfill.

The prime components of the package are prepared in Microsoft-Office 97 program. General
information and reference bank (Useful reference and websites) are prepared in MS-Word 97
program. Slide-show is prepared in PowerPoint and the remaining elements; namely, main
menu (Table of contents), examples and explanations and simulation in MS- Excel 97
program utilizing visual basic features. The auxiliary software named ViSsim and Netcapes
(or Internet Explorer) will be helpful to glance the additional features such as micro models
and websites linked useful documents and information. Details of package components are
discussed in the following sections.

4.2.2 Details of Package Components

4.2.2.1 General Information

This is a stimulus section, which discusses about rationale, motive and hypothesis of this
work. This has been prepared for the following topics:
Rationale
Solid Waste Management and Landfills
Methane Inventory Model
Governing Equations

This section is also linked with a slide-show case study titled "Solid Waste Disposal Leading
to Global Warming Problem". Furthermore, some words in this session are linked with related
features to make user understand easily

4.2.2.2 Slide -Show

This has been prepared to convey the facts related adverse effect of methane emission and its
control measures. It could be viewed in MS-Power point environment. It contents total around
40 slides in following topics;
Greenhouse Gases and Landfill Gas
Methane Generation in Landfills
Methane Oxidation in Landfill covers
Methane Emission from Landfills

Slides subtitled 'methane generation in landfills' and 'methane oxidation landfill covers' are
linked with corresponding models that were developed to investigate landfill methane
scenario at micro level. To browse those models, technical software named 'ViSsim' is
needed.
42

4.2.2.3 Explanation and Examples

This section explains the basic hypothesis of estimation and guides step by step to estimate
methane emission for a particular place or region. Users, especially beginners in this area, are
expected to spend few minutes before going onto the simulation session. It furnishes two
examples of estimation for Thailand (cities) and Canada (Ontario). Unlike simulation and case
study sheets, example sheets contain both input and output in same sheet and these sheets are
static for particular year as they were assigned with fixed input parameters. Moreover, the
sheet for new estimation is dynamic and incorporated with help file and comment box (see
Fig 4.1 )

Fig. 4.1 Typical Input Sheet for Estimation for a Place

4.2.2.4 Case Study

This study predicted the trend of methane emission from landfills at Ontario in Canada based
on prevailing solid waste management practice. Then, the methane emission rate was
Replace '?' with
appropriate value or
word and enter
43
simulated with adjustments in the fraction of DOC, methane oxidation and methane recovery.
Finally, it leads to make some recommendations to reduce methane emission in Ontario.

The graphical output of methane estimation is shown in Fig. 4.2 for following conditions,
- Prevailing condition - Same trend of current practice (1.11% population growth,
DOC=13%, MO=10%, MR=15%).
- Reduction of DOC into 10%
- Increment in fraction of Methane Oxidation into 15%
- Increment of fraction of Methane Recovery into 20%

Fig. 4.2 Graphical Output Sheet of Case Study

The details of calculation could be seen by clicking corresponding calculation buttons (see
Fig. 4.2). Estimations of total methane emission for Canada (Ontario) has same order of
magnitude of previous estimation using the computer model developed by U.S.EPA. Further,
it shows that the reduction of DOC fraction in MSW is the most effective way to reduce the
total methane emission to atmosphere from landfills. The detailed method of effective SWM
practice to reduce methane emission is explained in Section 2.6.2. Methane recovery is
another important option when it is used as a source of energy. Advantages and restrictions of
methane recovery are discussed in Section 2.6.3. Natural methane oxidation is also easy,
44
economical and environmental friendly way to reduce the methane emission from landfills.
Incorporation of soil methonography in landfill cover designs to promote methane oxidation
is discussed in Section 2.6.4.

4.2.2.5 Simulations

The previous section gives a confidence from the applicability of this model in Canada
(Ontario). As this method is based on the mass balance approach of organic carbon, it is
applicable everywhere. Place to place, only following coefficients will be varied,
- Total MSW (ie, population X waste generation rate)
- Landfilled fraction.
- Fraction of DOC (degradable organic compound)
- Methane recovered.

This session provides a route mathematically to simulate methane emission rate with fraction
of DOC, fraction of methane oxidation and fraction methane recovery. It will be helpful to
find the ways to control methane emission based on needs.

Moreover, this simulation session is developed in MS-Excel program incorporating VBA
macros as additional tool in feature creation. It includes the following components:

Control sheets
Help files
Input sheets
Output sheet
Database

In this session, users can access mainly three sections; namely, data input, graphical out put
and database. Control sheets are hide and protected to avoid anonymous changes.
Additionally, first two-section are equipped with a help file.

Input: The user is expected to provide data, which are required in the process of simulation,
into the confined blue-shaded cell for that purpose. After finishing all necessary inputs into
corresponding cells, the cell-pointer has to be taken out of the cell where input was given last.
Now this program automatically makes necessary calculations to estimate net methane
emission rate and draws the graph in the sheet named graphical output.

Furthermore, the database gives guideline-values for data input. Solid waste data that is used
to estimate methane emission are largely unreliable. Due to inconstancies in data recording,
definition, collection method and seasonal variation, the data can be considered approximate
albeit more accurate than most. For planning purpose, however the data presented in this
database sheet is sufficient.
45

Fig. 4.3 The Typical Simulation Sheet

Output: After entering the data in the "Data Input" sheet, the output can be viewed in
"Graphical Output" Sheet. Simulation by assigning different individual values for fraction of
DOC, methane oxidation and methane recovery is expected to provide the user with varieties
of scenario related to control of landfill methane emission.

4.2.2.6 Useful References and Websites

This database compiles totally more than two hundred reference-materials and websites
related to the solid waste disposal and landfills. It is expected that the users would benefit
from the information thus compiled in a single sourcebook. The information is categorized
into two different groups such as websites and bibliographic-list. Again, websites are arranged
into three sub-titles namely landfills, solid waste disposal and organizations. To browse
websites, additionally Netscape or Internet Explorer is needed.

46
4.2.3 Interface

This package is prepared by using Microsoft-Office 97 application software, with the
following programs: MS-Word 97, MS-PowerPoint 97, and MS-Excel 97.

Excel 97 with Visual Basic Application (VBA) is used in preparation of simulation games.
The hardware requirement for the use of this software is IBM-compatible computer capable of
running Windows 95 or latest windows 95.

The computer must meet the following minimum hardware requirements to use this software
package.
1) IBM-compatible computer capable of running Windows 95, a Pentium 100 or better
processor is highly recommended for performance reasons.
2) Hard disk with 100 MB of free space.
3) A 3.5-inch floppy disk driver.
4) 8 MB or more of RAM-memory
5) Microsoft mouse or other compatible pointing device
6) For additional features, Microsoft Internet Explorer Browser or Netscape.

4.2.4 Technical Significance

The intention of this package is originated from a need of structure to estimate methane
emission quickly for a region or country. It considers various practical and real-life uses in
policy assessment to control landfill methane emission. This package enables the end-users
with limited knowledge and technical background in environmental issues to clearly
understand various aspects of landfill methane emission scenario.

Some important features of this software package are as follows:

User-friendly interface, help files and comment boxes are provided to increase users
affinity for the operation of the software.

Estimations of total methane emission for Canada (Ontario) shows same order of
magnitude of previous estimation using computer model developed by U.S.EPA.

Through simulation of wide range of input and information, environmental managers,
policy makers and planners will be able to easily visualize varieties of scenario related to
control of methane emission from landfills.

Simulation section could be used to predict the trend of methane emission rate with
different combinations,
- With same trend of current practice in solid waste management.
- With various adjustment in solid waste management practice.

47
Simulation results show that the reduction in fraction of DOC is the most effective way to
reduce the total methane emission to atmosphere from landfills. This phenomenon could
be used to minimize quantity of methane production in landfills.
- To do it, segregate waste before landfilling as high-organic substance and low-organic
portion.
- Use high-organic substance for composting and send remaining portion for landfilling.
- This practice will also give useful product. (ie composted materials could be used as
fertilizer)

Based on simulation results, another easy and economical way to reduce the methane
emission from landfills is enhancing natural methane oxidation. By providing optimum
conditions for methonotrophy bacteria, we can simply achieve 15% oxidation in landfill
cover soils. Careful design will promote upto 30% (Hilger, 1998).

Although methane recovery reduces the methane emission, it is not applicable
everywhere, specially in small-scale landfills because of low gas production rate and not
meeting design regulations. However, this method will recover the investment when
collected gas is used as source of energy.

This package contains many educational features, for example, detailed information of
solid waste disposal leading to global warming effect, subject-wise slide-show,
explanation with examples for beginners in this area, case study, simulation, and
bibliographic-listing and related web-site lists.

This package can also be used as a good guidance or professional training tool for people
who interest in landfill gas management.

48
4.3 Methane Generation Model

4.3.1 Basic Considerations

The numerical model (the set of Equations 3.2-3.10) used by El-Fadel et al. (1994) represents
performance of a unit bioreactor under anaerobic conditions. An actual landfill or landfill cell
consists of a number of unit bioreactors. If unit bioreactor performance is known, then landfill
performance can be determined by summing biogas generation of all unit bioreactors
involving in the landfill. A complete model for a landfill is developed by such summation
procedures. It follows then that simulation of landfill biogas generation can be achieved by
defining unit bioreactors in landfill, determining their performance and integrating them over
whole landfill. However, the performance of a unit bioreactor is good enough for this study
because the prime aim of this study is knowing sensitivity of methane generation in view of
its control.

Based on the general modeling techniques discussed in section 3.2, the first the unit bioreactor
or segment in landfill must be defined. Randomly, a unit volume of waste in landfill under
anaerobic condition is considered for this study. The set of Equations 3.2 3.10 were applied
to construct a model using mathematical tools in technical software named ViSsim. To solve
these equations, Rungekutta 2
nd
order method with step size 0.01 was used. By assigning
random values for model parameters, the numerical behaviors of the solution of these
equations and overall mass balance (See Appendix B) were checked. Then, the values
published in literature (El-Fadel et al., 1994) were used as nominal values for model
parameters and initial concentrations for sensitive analysis. Those nominal values used for
this study are tabulated in Table 4.1 and 4.2.

Table. 4.1 Nominal Values for Initial Concentrations

Variables
Initial value
(kg.m
-3
)
Rationale
C
(AC)
0.01 Range observed in leachate from actual landfills
C
(aq)
0.01 Range observed in leachate from actual landfills
C
(S)
30 Typical range reported from MSW
C
(XA)
0.00015 Order of magnitude based on laboratory microbial studies
C
(Xm)
0.00000015 Order of magnitude based on laboratory microbial studies

Source: El-Fadel et al., 1994

49
Table. 4.2 Nominal Values for Variables

Variables
Nominal
value
Rationale

day
-1
10
Nominal value reported in anaerobic digestion
M
day
-1
0.25
Range reported in anaerobic digestion
K
dA
day
-1
0.05
K
dM
day
-1
0.03
K
h
day
-1
0.00002
Range reported in methane fermentation studies
where first order kinetics were applied to simulate
hydrolysis of cellulosic materials.
K
SA
kg.m
-3
0.05
K
SM
kg.m
-3
0.5
Y
A
kgVSS.kg
-1
COD 0.15
Y
CH4
kgVSS.kg
-1
COD 0.15

Y
M
kgVSS.kg
-1
COD 0.06

Source: El-Fadel et al., 1994

Halvadakis (1983) also used the same set of equations for modeling of methanogenenis in
solid-waste landfill bioreactors. He validated the model with field data taken from Mountain
View Landfill (California, USA) and reported same range values for those model parameters
(See Appendix B-1). Therefore, the need of validation with field data is not important in this
study. However, the result of present model was compared with same field data (See Fig. B-
10). It does not fit well with this field data because variables are not incorporated with
temperature.

4.3.2 Sensitivity Analysis

As discussed in section 3.1, laboratory simulation cannot be easily achieved by monitoring or
measuring variables to understand landfill process in micro level. Therefore, there is a need of
mathematical simulation before going into full-scale operation. The constructed model was
used for this purpose. The variables and initial concentrations changed from the nominal
value stated in Table 4.1 and 4.2 to check sensitivity of methane generation rate. It showed
that hydrolysis rate constant (K
h
) and initial organic carbon concentration in waste (C
(S)
) are
important parameters affecting the methane generation directly. Effects of initial solid carbon
and hydrolysis rate constant on the are show in Fig.4.4 and 4.5.

50
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)Kh/2
Kh
2Kh
Kh/2
Kh
2Kh

Fig. 4.4 Effects of Initial Solid Carbon on Rate of Methane Generation

Fig. 4.5 Effects of Hydrolysis on Rate of Methane Generation

0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
C(s)/2
C(s)
2C(s)
51

Except initial solid carbon C(s) and hydrolysis rate (K
h
), specific methanogeneius growth rate
(m), methanogeneous half velocity constant (K
s,m
) also showed significant difference only in
lag period. Other variables did not show much effect on methane generation scenario (See
Fig. B-1 and Fig. B-9).


Sensitivity of methane generation rate analyzed to assess the effects of variables such as
initial conditions, specific growth rate and reaction rate constants shows that hydrolysis
rate constant (K
h
) and initial organic carbon concentration in waste (C
(S)
) are important
parameters affecting the methane generation directly. This result is useful for landfill
managers or designers to practice effective solid waste management in view of landfill gas
control.

Municipal solid waste in many countries contents organic and paper waste more than 60%
of total (Hoornweg et al, 1999). So, the exile of both organic and paper waste results
reduction of 60% organic carbon (from 27kg.m
-3
to 11kg .m
-3
) in waste, and according to
present model, it leads more than 50% reduction in methane generation rate (from 0.005
to 0.002 kg/m
3
waste.day). These phenomena could be used to minimize quantity of
methane production in landfill as follows;
Extraction of organic and paper waste from MSW by source separation or waste
processing and composting (Composted materials could be used as fertilizer)
Landfilling remaining portion.

Based on sensitivity analysis, the reduction of hydrolysis rate constant (K
h
) is another
important event in landfill gas mitigation program. Generally, landfill waste reports the
hydrolysis rate constant (K
h
) between 0.0002 day
-1
and 0.001 day
-1
(Halvadakis, 1983)
(see in Appendix B-2) It ranges the rate of methane generation between 0.005 and 0.02
kg/m
3
waste.day . Therefore, this is the most effective way to reduce methane generation
in landfill. As hydrolysis rate constant (K
h
) depends on waste characteristic and soil
environment, this could be implement as follows;
By avoiding organic substances which have high-hydrolysis rate constant
Proper cover design to avoid water infiltration into the landfills. It will be also
useful to reduce the amount of leachate from landfills.
Draw back of landfilling low-hydrolysis substances is a long after-care period.

On the other hand, when there is recovery facilities the practice should be vice versa to
collect methane effectively.

52
] [ * *
] [
4
,
4
4
] [
] [
4
X PMO
dt
CH d
CH m K CH
CH
+
=
1
2
,
2
2
] [
] [
+ O m K O
O
4.4 Methane Oxidation Model

4.4.1 Methodology Development - Effect of Inhibitors on Methane Oxidation
Enzymatic Activity

The aerobic oxidation of methane into CO
2
and H
2
O is described in Section 2.4.1. The rate of
utilization of methane is described in Equation 3.9 by using the Monod model (MONOD,
1949). This may generally be appropriate for low substrate concentrations. When substrate
concentration is high, some of the components in this equation become nearly constant.

In batch experiments, oxygen is not limiting factor. Therefore,

Then, Equation 3.9 becomes as follows,

. .Equation 4.1

Where,
PMO =potential of methane oxidation rate
Km, CH
4
=half velocity constant of CH
4

Km, O
2
=half velocity constant of O
2

[CH
4
] =concentration of CH
4

[O
2
] =concentration of O
2

Potential of methane oxidation is given by,
PMO =C
PMO
*F(t)*F(m)
..Equation 4.2
Where,
C
PMO
=Constant for PMO .
F(t) =Functions of temperature.
F(m) =Functions of moisture content.

The above equation takes into consideration only the main variable of temperature and
moisture content. It has not incorporated with toxic components. Influence of toxic
component depends on type of its reaction with enzyme. Various mathematical models have
been proposed to describe the effects of inhibition on enzymatic activity.

In this study, inhibition occurs due to the presence of another inhibitory substance. This type
of inhibition may be divided into two limiting cases:
53
] [ * *
] [
) 1 ( ] [
] [
X K
dt
S d
i
K
i
SS
K S
S
+ +
=
] [ * *
] [
) 1 )( ] ([
] [
X K
dt
S d
i
SS
K
i
K S
S
+ +
=
(1) Totally Competitive Inhibition: Here, the binding of the substrate and inhibitor to the
enzyme are mutually exclusive. The reaction steps at equilibrium may be represented as:

E +S ES
E +I EI
ES P +S

The substrate utilization rate may be written in terms of the concentration microbial species
(X) and free substrate (S) and inhibitor concentrations (i) may be written as:

..Equation 4.3

where,
K - maximum rate of substrate utilization (T
-1
);
K
SS -
half velocity constant of substrate(ML
-3
);
Ki - inhibition constant (ML
-3
) and
[X] - concentration of the microbial species that carries out the rate limiting
transformation (ML
-3
).

(2) Totally Non-Competitive Inhibition: Here, the inhibitor and substrate can
simultaneously bind to the enzyme, forming a ternary complex. The simplest model would be
one in which binding of either substrate or inhibitor does not influence the affinity of either
species to complex with the enzyme. Thus, in addition to above equations, the following
reactions are to be considered at equilibrium:

EI +S EIS

ES +I EIS

..Equation 4.4

Between the two limiting cases presented above, several intermediate cases can be
considered. A summary of these cases is represented in Table 4.1.

54
] [
] [
*
] [
4
X K
dt
CH d
Y
dt
X d
dM
=
] [ * *
] [
) 1
4
4
( ] [
] [
4
X PMO
dt
CH d
i
K
i
SM
K CH
CH
+ +
=
Table. 4.3 Classification of Inhibitors Based on Properties

Type Description
1.a. Fully competitive

b. Partially competitive
Inhibitor adsorbs at substrate binding site

Inhibitor and substrate combine with different groups;
inhibitor binding affects substrate binding
2.a. Noncompetitive

b. Noncompetitive
Inhibitor binding does not affect ES affinity, but ternary EIS
(enzyme-inhibitor-substrate) complex does not decompose into
products

Same as 2.a except that EIS decomposes into product at a
finite rate different from that of ES

1. Mixed Inhibitor

Combination of above
Source: Gheewala (1995)

Classification of inhibitor needs microbial analysis of enzymatic activity. There are
significant data on inhibitor effects on methane oxidation by TCE (Pokhrel, 1998) and
benzene (presented in next section), but no data on microbial analysis of involved enzymatic
activity. This study assumes it as fully competitive inhibitors and develops governing
equation of model to validate the data. Then, the proposed equation to assess effect of
inhibitors on methane oxidation is as follows

..Equation 4.5

Furthermore, concentration of methanotroph bacteria is represented by following equation,

..Equation 4.6

Where, Y - Yield of methanotroph per methane
K
dM
- Decay coefficient of methanotroph.

55
4.4.2 Empirical Relationship

1. Function of Methane Oxidation Rate in Temperature

Effects of temperature on methane oxidation were examined by Pokherel (1998) using
incubated fresh soil sample. The perceived rate of methane oxidation at a wide range of
temperature (10-50
o
C) is attached in Appendix C (Table C-1). Various types of curve were
tried to fit with those data. Equation and properties of trial curves, and corresponding R
2

values are tabulated in Table 4.2.

Table. 4.4 Various Trials of Empirical Function for Methane Oxidation Rate in Terms
of Temperature

Order of
Polynomial
Form of Equation R
2
No. of
peaks
2 y =-0.0024x
2
+0.1268x - 0.6358 0.75 1

3 y =-0.0002x
3
+0.0098x
2
- 0.1248x +0.4468 1.00 2

4 y =1E-06x
4
- 0.0003x
3
+0.0134x
2
- 0.1716x +0.6042 1.00 2

5 y =1E-06x
4
- 0.0003x
3
+0.0134x
2
- 0.1716x +0.6042 1.00 2

Logarithmic y =0.2947Ln(x) - 0.3002 0.22 -

Power y =0.0185x
0.92
0.29 -

Exponential y =0.1368e
0.0306x
0.10 -

Note: y = rate of methane oxidation (*10
-6
CH
4
/g soil), x = temperature (
o
C)

Based on the R
2
values in Table 4.2, logarithmic, power and exponential curve are unfit with
experimental data. Even though 4
th
and 5
th
order polynomial are fit with data, their unusual
shapes and number of peaks did not permit to take into consider because generally, the high
activity of microorganism is observed only at a particular range of temperature. 2
nd
order
polynomial obey this rule but R
2
value is less than 3
rd
order polynomial. Therefore, most
agreeable one is 3
rd
order polynomial (see Equation 4.7) at the range of temperature between
20
o
C - 40
o
C. Comparison of experimental data with this empirical curve is shown in Fig. 4.4.

y =-0.0002x
3
+0.0098x
2
- 0.1248x +0.4468 (at 16%) ..Equation 4.7

56
2. Function of Methane Oxidation Rate in Moisture Content

According to Pokherel's (1998) another investigation, incubated fresh soil sample at 30
o
C
with a range of moisture content (5-25%) yielded distinct rate of methane oxidation (See
Table C-1 in Appendix C). Many trials made to fit a curve with these experimental data are
tabulated in Table 4.3.

Table. 4.5 Various Trials of Empirical Function for Methane Oxidation Rate in Terms
of Moisture Content.

Order of
Polynomial
Form of Equation R
2
No. of
peaks
2 y =-78.814x
2
+28.066x - 1.3557 0.95 1

3 y =214.45x
3
- 178.04x
2
+41.709x - 1.889 0.96 1

4 y =14049x
4
- 8528.2x
3
+1721.9x
2
- 126.15x +3.0695 1.00 2

5 y =14049x
4
- 8528.2x
3
+1721.9x
2
- 126.15x +3.0695 1.00 2

Logarithmic y =0.5908Ln(x) +1.92 0.56 -

power y =31.505x
2.1061
0.68 -

Exponential y =0.0634e
13.202x
0.48 -

Note: y = rate of methane oxidation (*10
-6
CH
4
/g soil), x = moisture content (%)

Like previous approach in methane oxidation in terms of temperature, the experimental data
shows more deviation from logarithmic, power and exponential curves. Furthermore, 4
th
and
5
th
order polynomial were eliminated from consideration due to unusual shape and number of
peaks. 2
nd
and 3
rd
order polynomial are almost same shape and same number of peaks.
However, 3
rd
order polynomial has R
2
value more than 2
nd
order. Finally, again 3
rd
order
polynomial in Equation 4.8 was become as most agreeable.

y =214.45x
3
- 178.04x
2
+41.709x - 1.889 (at 30
o
C) ..Equation 4.8

The comparison of experimental data with this empirical curve is shown in Fig. 4.5.

57
y =214.45x
3
- 178.04x
2
+41.709x - 1.889
R
2
=0.9561
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0% 5% 10% 15% 20% 25% 30%
Moisture content (%)
R
a
t
e

o
f

m
e
t
h
a
n
e

o
x
i
d
a
t
i
o
n

(
*
1
0
-
6

C
H
4
/
g

s
o
i
l
)
Exp. Data
Polynomial
y =-0.0002x
3
+0.0098x
2
- 0.1248x +0.4468
R
2
=0.9997
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0 10 20 30 40 50
Temperature (
o
C)
R
a
t
e

o
f

m
e
t
h
a
n
e

o
x
i
d
a
t
i
o
n

(
*
1
0
-
6

g

C
H
4
/
g

s
o
i
l
)
Exp. Data
Ploynomial

Fig. 4.6 Comparison of Empirical Curve with Experimental Data for Methane
Oxidation Rate
(for fresh soil sample with moisture content 16% and initial headspace CH
4
=3 - 4 % )

Fig. 4.7 Comparison of Empirical Curve with Experimental Data for Methane
Oxidation Rate
(for fresh soil sample incubated at 30
o
C with initial headspace CH
4
=3.5 - 4.5 % )

58
4.4.3 Simulation and Optimization

The oxidation model was structured from kinetic Equation 4.4 and empirical Equations 4.5
and 4.6 using mathematical tools in 'ViSsim' software. To solve these differential equations,
Rungekutta 2
nd
order method at step size 0.1 was selected. The two main blocks representing
methane utilization and methnotroph population are shown in Fig.4.6 and 4.7.

Fig. 4.8 The Model Block Representing Methane Utilization

Fig. 4.9 The Model Block Representing Methanotroph Population

After checking the numerical behavior of these equations, it was simulated at temperature
37
o
C and moisture content 15%. It was matched with experimental data (Table C-2) at the
conditions tabulated in Table 4.4. Optimization tool in Vissim environment was used to get
optimum value of these parameters.

1/S [CH4] *
Cpmo
d[CH4]/dt
-1
[X]
F(mc)
F(T)
[CH4]
------------------------------------------
{[CH4]+Ks,CH4(1+VOC/Ki)}
+
-
[X] d[X]/dt 1/S
Decay of Methanotroph
Growth of Methanotroph
59
0
0.5
1
1.5
2
2.5
3
3.5
0 50 100 150 200 250 300 350
Time(hrs)
M
e
t
h
a
n
e

(
m
g
)
Model
Exp
Table. 4.6 Optimum values of Parameters for Fresh Soil

Parameters
Units

Optimum
Values

K
S M

C
PMO

Y
K
dM

K
i

Initial concentration of
methnotroph, X

mg CH
4
/g soil
(mg CH
4
)
-2
(g soil)
2
h
-1

h
-1

g soil/ mg TCE

mg CH
4
/g soil

20
5.0*10
-3

0.7
2.0*10
-3

3.4

30

Fig. 4.10 Validation of Methane Oxidation for Uninhibited Fresh Soils
(for 10g fresh soil with 15% moisture content incubated at 37
o
C)

Then, the simulation was proceeded for lysimeter soil. Different values were checked for
initial methonotroph concentration until the result of model fits with experimental data in
Table C-5 (TCE 0 g). It fitted with the data when the initial concentration was 101 g/ g soil
(see Fig. 4.9). Finally, the model was simulated for inhibited soil (TCE 1.4 g). Again, the
optimization tool was used to find the inhibitor constant (K
i
). The result of the model was fit
with data in Table C-5 (TCE 1.4 g) when K
i
was 3.390 g soil/ g TCE. The validation of the
out come of methane oxidation from model with experimental data for lysimeter soil is shown
in Fig. 4.9.
60

Fig. 4.11 Validation of Methane Oxidation for Inhibited Lysimeter Soils.
(for 10g fresh soil with 15% moisture content incubated at 37
o
C)


The assumption made for TCE as fully competitive inhibitor is satisfied with experimental
data. Even though it should be confirmed by microbial analysis, it gives a clue for
microbial analysis to find the effect of TCE on enzymatic activity of methane oxidation.

Validations with the experimental data pronounced basic values of kinetic coefficients for
methanotroph bacteria and inhibitor coefficient for TCE for the particular soil
environment. Hereafter, assigning different values for TCE could leads further
simulations. Therefore, it is cut down the number of experimental simulations.

More over, the threshold point of TCE on methane oxidation also could be found by
assigning different values for TCE concentration. It will be useful for planners to find the
allowable limit of TCE in methane oxidation enhancing program.

The present model fits with batch experiments. Gas transportation model in soil (Equation
2.4) coupled with this model will represent methane migration and oxidation scenario in
lysimeter. Even it could be furnished to visualize this scenario in a real landfill.

0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 20 40 60 80 100
Time (hrs)
H
e
a
d
p
a
c
e

M
e
t
h
a
n
e
(
m
g
)
Model-0.0
Model-1.4
Exp.- 0.0
Exp.- 1.4
g TCE
g TCE
g TCE
g TCE
61

4.4.5 Experimental Study: Effect of VOC on Methane Oxidation Rate

The experimental study was conducted to determine the methane oxidation rate in landfill
cover soil at laboratory scale. This experimental study was mainly focused on the effect of
volatile organic compounds on methane oxidation. For the present study, benzene was picked
as volatile organic compound. The details of experimental set up and the methodology of
measuring parameters such as CH
4
, N
2
, O
2
, VOC (benzene), moisture content, temperature are
discussed in section 3.4. Schematic diagram of the experimental set-up is shown in Fig. 3.2.
Whole experimental run was carried out at ambient temperature (28 to 34
0
C) in column
system. Moisture content of the soil in lysimeter was maintained at 8-9%. Oxidation rate in
percentage was determined with injection of benzene concentration. An interrelationship
between the behavior of methanotroph bacteria and toxic chemicals was tried to identify from
this experiment.

First, the experiment was started with low rate of gas supply 2.5 mL/min (60% CH
4
and 40%
N
2
). It took 8 days to show the first methane at the column headspace. The time taken to reach
top of the column by gas is reasonable. Because according to the volume of lysimeter (34 L)
and the gas flow rate mentioned above, gas will take around 10days to reach the headspace of
the column.

Initially, the headspace methane concentration was high. Later, it stepped down because
oxidation of by methanotroph. After it showed 100% oxidation, the gas supply was increased
into 3.6 mL/min. There was immediate drastic drop observed in oxidation rate and however
then, it developed into 97% oxidation (See Fig.12). It indicates methanotrophs could be more
specific with available amount of methane substrate.

When the gas supply was increased into 5mL/min the oxidation rate was become stable at
76% oxidation (2.265 mL/min). Totally, it took nearly 60 days for steady state. The approach
of steady state was quite slow compare to the previous researchers work ( Kightly, 1995 and
Pokherel, 1998). The reason could be due to soil type, moisture content and methane supply.
Kightly (1995) reported 14 days to take steady state for nutrient amended soil with 40%
moisture content. Pokhrel(1998) reported around 40 days with 11% moisture content and 5
mL/min gas supply rate. Therefore, less gas supply rate (2.5 mL/min) and less moisture
content (9%) could be caused long time to reach steady state.

Notable effects on methane oxidation rates were observed in the column system at different
supply rates. (See Fig. 12). Oxidation rate increased when gas supply rate increased, although
decrease in percentage oxidation was noticed. At small flow rates between 2.5 and 3.6
mL/min, the oxidation rate was increasing with increase in methane supply rate. The increase
in oxidation rate was not proportional to supply rate, rather low increase in oxidation rate was
observed. It behaves according to Monod kinetics (Monod, 1949). This is clearly shown in
Fig. 13. High rate of methane supply caused only small increase in oxidation rates indicates
the condition of constant methane oxidation capacity approaching zero order kinetics (see
Equation 2.2). Average oxidation rates at various methane supply rates are shown in Fig. 4.13.
62

Fig. 4.12 Observed Methane Oxidation with Different Rate of Methane Supply

Fig. 4.13 Variations of Methane Oxidation with Different Rate of Methane Supply

0
1
2
3
0 1 2 3 4
Methane suply (mL/min)
O
x
i
d
a
t
i
o
n

r
a
t
e

(
m
L
/
m
i
n
)
0
1
2
3
4
0 10 20 30 40 50 60
Time (days)
(
m
L
/
m
i
n
)
Methane supply
Oxidation
63
As shown in Fig. 4.14, when the system was steady state oxidation benzene was started to
inject through gas supply line. The detailed arrangement of benzene injection is shown in Fig.
3.2. Water saturated with benzene was used for this purpose. Initially, benzene was fed at low
concentration, then it was increased step by step. Effects of different benzene concentration in
methane oxidation are shown in Fig. 4.14. First 30 days after started benzene feeding,
emission of benzene from lysimeter was maintained around 400-450 g/m
3
. From Fig. 4.14, it
can be seen that the oxidation was constant through out the period.

Fig. 4.14 Observed Methane Oxidation with Different Amount of Benzene injection

Then, the benzene feeding was increased into 750-800 g/m
3
. The initial stage of 2
nd
step
showed slight increment on the methane oxidation and later it suddenly increased into
extreme level. More over, GC used for the measurement of methane showed 5 additional
peaks close to methane peak, which is indication of presence of other gases. (See Appendix
D-4). As the GC was calibrated to recognize only CH
4
, N
2
, O
2
and CO
2
, the additional peaks
were unable to be identified.

With this conflict oxidation performance, the experiment was moved to 3
rd
stage with benzene
emission 1400-1450 g/m
3
. In this stage, those additional peaks joined together with methane
peak and troubled to show the actual area of methane peak. This unusual shape of peak is
shown in Appendix D-5. This stage was continued only 20days. Consequence this problem,
the benzene feeding was stopped.

After the benzene feeding stopped, the additional peaks observed during previous stage were
disappeared and methane can be measured. From Fig. 4.14, it can be seen that the oxidation
was less to previous stages. It could be because of inhibitor effect by accumulated benzene
0
1
2
3
4
60 70 80 90 100 110 120 130 140
Time(days)
(
m
L
/
m
i
n
Methanesupply
Oxidation
Benzene
400-450 g/m
3

Stopped
Benzene
Feeding
Benzene
1400-1450g/m
3

Benzene
750-800 g/m
3

64
inside the lysimeter. However, the ongoing work will strengthen the reason. Experiment is
still on progress.

According oxidation results, the benzene did not affect methane oxidation upto 800 g/m
3
.
When it was increased to 1400 g/m
3
there was significant effects observed with some
interference to measure actual methane. It means threshold limit benzene on methane
oxidation between these two concentrations. There was a slight increase of oxidation observed
in 2
nd
stage because of high water content with benzene feeding.

As discussed in section 3.4, there were two similar columns used in this study; one with
methane supply for real purpose and other one with N
2
supply for control experiment. The
control experiment column was checked periodically. It did not show any significant
interference through out the experiment. Therefore, it confirms that all results observed in this
system are due to benzene feeding.

Effects of TCE on methane oxidation were examined by Pokherel (1998) using incubated
lysimeter soil sample. He reported inhibitor effects by TCE at high concentration. This
supports to the result of the present work.
65
Chapter 5

Conclusions and Recommendations

Based on the work presented in this study, a number of conclusions have been drawn. In turn,
certain suggestions are made for further pursuing the present research effort. The following
paragraphs present the conclusions and recommendations.

The methane inventory model is a structure to estimate methane emission quickly for a region
or country. It considers various practical and real-life uses in policy assessment to control
landfill methane emission. This package could be handled by the end-users with limited
knowledge and technical background in environmental issues to clearly understand various
aspects of landfill methane emission scenario. User-friendly interface, help files and comment
boxes could provide to increase users alliance for the operation of the software. Through
simulation of a wide range of input and information, environmental managers, policy makers
and planners could easily visualize varieties of scenario related to control of methane
emission from landfills. The simulation section could be used to predict the trend of methane
emission rate for different combinations; namely, with the same trend of current practice in
solid waste management and with various adjustments in solid waste management practice.

Simulation results of the methane inventory concluded that the reduction in fraction of DOC
is the most effective way to reduce the total methane emission to atmosphere from landfills.
This phenomenon could be used to minimize the quantity of methane production in landfills
by effective solid waste management. Based on simulation results, another easy and
economical way to reduce the methane emission from landfills is enhancing natural methane
oxidation. Although methane recovery reduces the methane emission, it is not applicable
everywhere, specially in small-scale landfills because of low gas production rate and not
meeting design regulations. However, this method will recover the investment when collected
gas is used as a source of energy.

Moreover, inventory model contains many educational features, for example, the detailed
information of solid waste disposal leading to the global warming effect, the subject-wise
slide-show, the explanation with examples for beginners in this area, the case study,
simulation, and bibliographic-listing and related web-site lists. So, this package could also be
used as a good guide or professional training tool for people who are interested in landfill gas
management.

Sensitivity of methane generation rate was analyzed by the methane generation model to
assess the effects of variables such as initial conditions, specific growth rate and reaction rate
constants. It concluded that hydrolysis rate constant (K
h
) and initial organic carbon
concentration in waste (C
(S)
) are the most important parameters affecting the methane
generation directly. This result is useful for landfill managers and designers to implement
effective solid waste management in view of landfill gas control.

66
The methane oxidation model has been constructed from semi-empirical equations derived
from Monod kinetics, inhibitor effect on enzymatic activity and experimental data, and
validated with different sets of experimental data. Therefore, it could be used to find
optimums condition in terms of temperature and moisture content for maximum methane
oxidation in landfills. Moreover, the model validations with experimental data accept that the
inhibitor TCE is fully competitive inhibitor. Although the type of inhibitor should be
confirmed by microbial analysis, model result could be a clue for microbial analysis to find
the effect of TCE on enzymatic activity of methane oxidation.

Also, validations with the experimental data in methane oxidation model pronounced basic
values of kinetic coefficients for methanotroph bacteria and inhibitor coefficient for TCE for
the particular soil environment. Hereafter, the model could be used to find the threshold point
of TCE on methane oxidation. Therefore, it cut down the number of experimental simulations.

The experimental study conducted to determine the effect of volatile organic compounds
(benzene) on methane oxidation did not show any effects until the benzene increased to 800
g/m
3
. When it was increased to 1400 g/m
3
there was significant effect observed with some
interference in measuring actual methane. It concluded that the threshold limit of benzene on
methane oxidation could be between these two concentrations. To enhance methane oxidation
in real landfill, VOC should be maintained less than this limit.

Based on the result of the present study, the following suggestions are proposed for further
study;

The study on the methane inventory is Western-biased. It should be modified into
developing countries. Moreover, additional work should be done to bring all the
components of methane inventory model into the same flat form.

The review part of the methane generation model concluded that published actual landfill
methanogenesis data are scarce and uncertain. The experimental work on lab-scale
bioreactor will fill this important information gap.

The model formulation on methane generation does not respond to temperature variations
over time. The known sensitivity of methanogenic microbial populations to temperature
dictates the inclusion of this factor in the model structure. It is recommended that
additional modeling work should be done in this respect

Empirical formulas for methane oxidation in terms of temperature and moisture were
derived from a only few data points. It is good to confirm these equations with more
experimental data.

The modeling study on methane oxidation fits with batch experiments. This study could
be furnished to visualize this oxidation scenario in a lysimeter or real landfill with
incorporation of the gas transportation module in soil.

67
Some literature reports anaerobic oxidation in presence of SRB (Sulfate Reduction
Bacteria). Furthermore, SRB reduces methane generation by competing with MPB
(Methane Producing Bacteria) for utilization of organic matters in landfills. . It is
recommended that a research work should be done in this respect.

68
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Appendix - A
Methane Inventory Model: Data and Calculations

A-2
A-1 Estimation of Methane Emission for Thailand and Ontario (Canada)

A-1.1 Published Data

Table. A-1 Input Data for Methane Inventory Model

Data
Thailand
#
(Cities)
Canada^
(Ontario)
1. Population

2. Waste generation/Capita

3. Landfill fraction in MSW
Closed landfill
Open dump

4. Fraction DOC in MSW

5. Fraction DOC dissimulated

6. Fraction of C as Methane ()
Closed landfill
Open dump

7. Convention ratio

8. Methane Oxidization
Closed landfill
Open dump

9. Methane Recovered
Closed landfill
Open dump
X 1000

Mg/capita.yr

%
%

%
%
5882.400

0.321

0.300
0.700

0.120

0.770

0.550
0.275

1.333

10.000
-

-
-
12535.900
0.628
0.800
0.200
0.130
0.770
0.550
0.275
1.333
10.000
-
15.000
-
#
Source: TEI (1996)
^Source: Rayes (1991)

A-1.2 Specimen Calculation

Considering Thailand data set from Table A1,

Waste generated =Population X Waste generaton/Capita
=1888.250 Gg/yr

A-3

Using equation 3.1 for closed landfills,

Methane emission =1888.250 Gg/yr
x 0.3 x 0.12 x 0.77 x 0.55 x 1.33 x 0.9 x 0.9
=34.546 Gg/yr

Similarly for opened dump,

Methane emission =44.782 Gg/yr.

Total methane emission =79.328 Gg/yr

Table. A-2 MSW Genartion Rate Used in Ontario Case Study

Year Waste Generation Rate
(Kg/day)
1940

1945

1950

1955

1960

1965

1970

1975

1980

1985

1990
0.88

0.88

0.88

0.88

0.88

0.97

1.07

1.37

1.75

1.75

1.75
Source: Rayes (1991)

A-4
Table. A-3 Prevailing Trends of Methane Emission from MSW in Ontario from Model

Year Population
(in 1000s)
Waste
generation
kg/capita.day.
Landfill
fraction
DOC
fraction
Recovered
Methane
Gg/yr.
Methane emission
Gg/yr.

1940 7000 0.88 1.00 0.13 0 148.542
1945 7420 0.88 1.00 0.13 0 157.455
1950 7865 0.88 1.00 0.13 0 166.902
1955 8337 0.88 0.98 0.13 0 173.378
1960 8837 0.88 0.91 0.13 0 170.654
1965 9368 0.97 0.93 0.13 0 203.776
1970 9930 1.07 0.92 0.13 0 235.708
1975 10525 1.37 0.9 0.13 0 312.948
1980 11157 1.75 0.93 0.13 21.893 415.968
1985 11826 1.75 0.94 0.13 46.912 422.211
1990 12536 1.75 0.96 0.13 76.177 431.673
1995 13288 1.75 0.97 0.13 81.589 462.340
2000 14085 1.75 0.99 0.13 88.268 500.185
2005 14930 1.75 0.99 0.13 93.564 530.197
2010 15826 1.75 0.99 0.13 99.178 562.008
2015 16776 1.75 0.99 0.13 105.128 595.729
2020 17782 1.75 0.99 0.13 111.436 631.473
Note: Population growth rate assumed 1.2%

A-5
A-2 Slide-Show: Solid Waste Disposal and Landfill Gas

Appendix - B
Methane Generation Model: Data and Calculations

B-2
B-1 Simulation of Methane Generation- Substrate Physical Characteristics

1. Hydrolysis Constants

k
h
max k
h

Readily hydrolysis substance 0.00142 . 0.001278
Moderately hydrolysis substance 0.00147 0.000420
Slowly hydrolysis substance 0.00042 0.000250

2. Biokinetic Constants

Acidogenic bacteria:

A
=10.000 day
-1
Y
A
=0.150 mg C
(XA)
/ mg C
(aq)

K
SA
=0.050g C
(aq)
/L K
DA
=0.0500 day
-1

Methanogenic bacteria:

M
=0.250 day
-1
Y
M
=0.0600 mg C
(XM)
/ mg C
(Ac)

K
SM
=0.500 g C
(Ac)
/L K
DM
=0.0300 day
-1

3. Yield Coefficients for Organic Carbon Pathways

Acidogens / Aqueous carbon:
Y
A
=0.150
Y
AC
=0.900
Y
ACO2
=0.100
Methanogens /Acetic acid:
Y
M
=0.060
Y
CH4
=0.600
Y
MCO2
=0.400

4. Initial Concentrations

Aqueous carbon =0.001 g C/L
Acidogens =0.001 g C/L
Acetic acid =0.0001 g C/L
Methanogens =0.0001 g C/L

Note:
Effect of pH on Methanogenic Microbial Growth Rate Constant is maximum when pH
between 6 and 8.The constants become zero when pH<4.50 or pH>9.00
Density of refuse =600 kg/m
3

Source: Havadakis (1983)
B-3
0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
a/2
a
2a
0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
Ksa/2
Ksa
2Ksa
B-2 Sensitivity Analysis on Methane Generation

Fig. B-1 Effect of Acidogenic Specific Growth Rate on Rate of Methane Generation

Fig. B-2 Effect of Acidogenic Half Saturation Constant on Rate of Methane
Generation
B-4
0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
Kda/2
Kda
2Kda

Fig. B-3 Effect of Acidogenic Decay Rate on Rate of Methane Generation

Fig. B-4 Effect of Methanogenic Specific Growth Rate on Rate of Methane Generation

0.000
0.005
0.010
0.015
0.020
0.025
0.030
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
m/2
m
2m
B-5
0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
C(aq)/10
C(aq)
10C(aq)
0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
Ksm/2
Ksm
2Ksm

Fig. B-5 Effect of Methanogenic Half Saturation Constant on Rate of Methane
Generation

Fig. B-6 Effect of Aqueous Initial Carbon on Rate of Methane Generation
B-6
0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
C(Xa)/10
C(Xa)
10C(Xa)
0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
C(Xm)/10
C(Xm)
10C(Xm

Fig. B-7 Effect of Acidogen Initial Carbon on Rate of Methane Generation

Fig. B-8 Effect of Methonogen Initial Carbon on Rate of Methane Generation

B-7

Fig. B-9 Effect of Acetic Acid Initial Carbon on Rate of Methane Generation

Fig. B-10 Comparison of Model Result with Field Data

0.000
0.005
0.010
0.015
0.020
0.025
0 100 200 300 400 500 600
Time (Days)
G
e
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

M
e
t
h
a
n
e

c
a
r
b
o
n
/
m
3

w
a
s
t
e
)
Kh/2
Kh
2Kh
C(ac)/10
C(ac)
10C(ac)
0.00
0.01
0.02
0.03
0.04
0 100 200 300 400 500 600
Time (Days)
M
e
t
h
a
n
e

G
n
e
r
a
t
i
o
n

R
a
t
e

(
K
g

C
H
4
/

m
3

w
a
s
t
e
)
Model
Fied Data
B-8
B-3 Overall Carbon Mass Balance of Methane Generation Profile

Note:
Simulation of the model for 600 day showed 3.01*10
-14
Kg Carbon/m
3
waste loss when all
yield coefficients were 1. It is negligible compare to initial carbon 27 kg/ m
3
waste.

+
+
+
+
+
+
+
0
Soild Carbon
Aqueous Carbon
Acidogenic Biomass
Acetate Carbon
Methonogenic Biomass
Methane Carbon
Carbon dioxide Carbon
Carbon Balance
B-9

Table. A-1 Corrected, Reduced and Normalized Cumulative Methane gas Data from
Mountain View Landfill in California (USA)
Source: Havadakis (1983)

Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
1.31 0.03
1.52 0.04
1.62 0.04
2.32 0.05
2.43 0.05
2.50 0.05
3.30 0.07
3.52 0.07
3.61 0.08
4.30 0.09
4.44 0.09
4.58 0.05
4.70 0.10
7.29 0.14
7.63 0.15
8.30 0.16
8.48 0.16
8.63 0.17
9.29 0.18
9.61 0.18
10.29 0.20
11.29 0.21
11.70 0.21
14.37 0.26
14.72 0.26
15.40 0.28
15.73 0.28
16.29 0.30
16.56 0.30
17.29 0.32
17.39 0.32
17.61 0.32
18.30 0.34
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
18.61 0.35
21.40 0.41
21.69 0.42
22.30 0.43
22.64 0.44
23.29 0.45
23.63 0.46
24.32 0.48
24.64 0.48
25.29 0.50
25.63 0.51
28.29 0.57
29.31 0.58
30.42 0.60
30.49 0.60
31.41 0.62
31.58 0.63
35.67 0.70
37.71 0.74
38.72 0.76
40.75 0.80
42.73 0.83
44.38 0.86
46.40 0.91
47.48 0.92
48.52 0.93
49.70 0.94
50.68 0.95
51.65 0.95
52.88 0.96
53.67 0.97
54.52 0.97
55.57 0.98
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
56.66 0.98
57.63 0.99
58.57 0.99
59.70 1.00
60.64 1.01
61.56 1.01
62.55 1.02
63.65 1.03
64.64 1.03
65.58 1.04
66.58 1.05
67.63 1.06
68.63 1.07
70.58 1.08
71.35 1.09
71.70 1.10
72.66 1.11
74.59 1.13
77.68 1.16
79.56 1.18
81.54 1.20
84.65 1.23
85.65 1.24
86.67 1.25
87.89 1.26
88.64 1.27
91.64 1.31
92.58 1.32
93.62 1.33
94.56 1.34
10
95.56 1.35
96.60 1.36
98.67 1.38
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
99.67 1.39
100.68 1.40
101.74 1.41
102.61 1.42
105.57 1.45
106.53 1.46
107.71 1.47
108.59 1.48
109.59 1.49
111.52 1.51
112.71 1.52
113.60 1.53
114.52 1.54
115.61 1.55
116.64 1.56
118.66 1.58
119.70 1.59
120.68 1.60
121.64 1.61
122.70 1.62
123.35 1.63
123.69 1.63
126.68 1.67
127.67 1.68
128.62 1.69
129.62 1.70
130.65 1.71
133.62 1.74
140.63 1.82
142.49 1.84
147.48 1.89
149.63 1.93
151.50 1.95
154.42 1.98
156.58 2.01
156.61 2.01
158.62 2.03
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
161.58 2.06
163.42 2.09
163.64 2.09
164.51 2.11
165.57 2.12
169.43 2.18
171.46 2.21
175.51 2.27
176.45 2.28
177.55 2.30
182.57 2.37
183.45 2.38
183.61 2.39
184.56 2.40
185.44 2.41
186.52 2.43
189.53 2.49
190.44 2.50
190.60 2.51
191.42 2.52
191.56 2.52
192.46 2.54
192.62 2.54
193.40 2.56
193.53 2.56
196.42 2.61
196.55 2.62
197.46 2.62
198.46 2.64
198.48 2.64
199.38 2.66
200.33 2.67
200.60 2.68
203.61 2.73
204.55 2.74
205.55 2.76
210.60 2.86
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
212.57 2.90
218.57 3.02
219.55 3.04
221.60 3.07
225.60 3.14
226.57 3.15
228.62 3.18
230.45 3.22
231.45 3.22
232.55 3.24
235.40 3.29
235.63 3.29
239.64 3.36
240.47 3.37
245.60 3.44
247.59 3.47
249.60 3.51
254.60 3.60
256.46 3.61
260.59 3.66
261.58 3.67
263.60 3.70
266.46 3.75
270.62 3.83
273.53 3.89
275.53 3.92
277.57 3.96
280.54 4.02
282.58 4.06
284.53 4.10
287.55 4.16
11
290.46 4.23
291.51 4.25
294.53 4.31
297.39 4.37
298.48 4.40
301.41 4.48
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
304.44 4.54
305.39 4.56
308.47 4.64
310.48 4.69
312.44 4.74
315.43 4.83
317.41 4.88
319.40 4.93
322.59 5.01
324.38 5.06
326.57 5.11
329.44 5.15
331.56 5.18
333.41 5.20
336.42 5.24
338.43 5.26
340.57 5.29
343.57 5.38
345.40 5.46
350.42 5.59
352.40 5.66
354.51 5.72
357.55 5.82
359.51 5.89
361.54 5.96
366.55 6.13
368.53 6.19
371.46 6.29
371.53 6.37
375.40 6.44
378.49 6.56
379.44 6.60
382.53 6.71
385.65 6.86
389.67 7.03
391.63 7.15
394.64 7.24
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
396.66 7.32
401.60 7.51
403.65 7.59
406.63 7.72
408.67 7.81
410.50 7.90
413.65 8.03
415.65 8.13
417.69 8.22
420.67 8.35
422.67 8.44
424.60 8.53
427.59 8.67
429.60 8.76
431.65 8.85
434.57 8.91
436.60 9.10
438.63 9.16
441.63 9.31
443.59 9.10
445.64 9.52
448.65 9.73
449.53 9.78
449.58 9.78
449.63 9.79
449.67 9.79
449.71 9.79
449.75 9.79
449.79 9.80
449.83 9.80
449.88 9.80
449.92 9.80
449.96 9.81
450.00 9.81
450.04 9.81
450.08 9.81
450.13 9.82
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
450.17 9.82
450.21 9.82
450.25 9.82
450.29 9.82
450.33 9.93
450.38 9.83
450.42 9.83
450.46 9.84
450.50 9.84
450.54 9.84
450.58 9.84
450.63 9.85
450.67 9.86
450.71 9.86
450.75 9.87
450.79 9.87
450.83 9.87
450.88 9.87
450.92 9.88
450.96 9.88
451.00 9.88
451.08 9.88
451.13 9.89
451.17 9.89
451.21 9.99
451.26 9.89
451.29 9.89
451.33 9.90
12
451.38 9.90
451.42 9.90
451.46 9.90
451.50 9.90
451.54 9.91
457.65 10.31
459.64 10.40
463.63 10.64
464.65 10.73
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
466.59 10.87
469.60 11.06
471.63 11.25
473.63 11.38
476.59 11.56
478.60 11.71
480.60 11.88
483.63 12.06
485.64 12.15
487.63 12.24
490.64 12.38
492.63 12.47
494.59 12.55
497.59 12.67
499.63 12.75
501.66 12.83
504.63 12.95
506.68 13.03
508.65 13.11
510.64 13.22
512.61 13.27
515.67 13.37
518.64 13.48
520.60 13.54
522.68 13.60
525.65 13.68
527.61 13.73
529.60 13.78
512.64 13.85
534.65 13.88
536.66 13.94
541.63 14.05
546.60 14.22
550.61 14.32
553.65 14.10
Time
(days)
Methane
gas
(X 10
3
m
3
/kg)
557.55 14.51
560.83 14.59
562.65 14.65
564.60 14.71
567.67 14.80
570.50 14.93
574.69 15.05
577.68 15.17
583.67 15.41
585.65 15.50
588.64 15.64
592.65 15.82
595.65 15.97
597.65 16.07
602.63 16.31
606.49 16.49
606.57 16.50
609.59 16.63
609.70 16.66
610.65 16.70
613.60 16.87
616.68 17.05
618.71 17.17
619.58 17.24
620.53 17.28

13

14

Appendix - C
Methane Oxidation Model: Data and Calculations

C-2
Table. C -1 Average methane oxidation measured in fresh soil with different
temperature and moisture contents.

Moisture contents
(%)

6

11

15

20

5
Oxidation rates (at 30
0
C)
*10
-6
g CH
4
/g soil/h
0.04 0.73 1.22 0.97 0.78

Temperature
(
0
C)

5

20

30

37

45
Oxidation rates (at 16%)
*10
-6
g CH
4
/g soil/h
0.05 0.58 1.21 1.12 0.08

C-3

Table. C -2 Headspace methane concentration observed in batch experiment with 10
g soil with 15 % moisture and incubated at different temperatures.

Time Headspace methane concentration (%) at
h 5
O
C 20
O
C 30
O
C 37
O
C 45
% mg % mg % mg % mg
0 100.0 3.366 100.0 3.193 100.0 3.088 100.0 3.018
14 - - 99.5 3.073 96.7 2.920
35 - - 94.1 2.906 95.3 2.875
59 97.2 3.270 99.8 3.187 - 94.6 2.856
81 - - 88.0 2.717 93.1 2.811
107 - 96.6 3.084 76.7 2.369 87.4 2.638
133 - - - 85.3 2.574
156 - 94.1 3.006 54.6 1.686 80.8 2.439
180 - - 41.4 1.278 68.3 2.060
204 - - 24.0 0.741 42.7 1.290
228 - 70.9 2.263 12.5 0.385 27.9 0.841
252 93.3 3.139 - 0.0 0.000 17.0 0.513
275 - 59.8 1.909 - 6.0 0.180
300 - - - 0.0 0.000
344 - 49.2 1.572 - -
422 91.3 3.074 26.6 0.851 - -
443 - 10.1 0.322 - -
464 - 0.0 0.000 - -


C-4

Table. C -3 Headspace methane concentration observed in batch experiment with 10
g soil with different moisture contents and incubated at 30OC

Time from Moisture Contents
Incubation 6% 11% 15% 20%
h Headspace methane concentration (%)
% mg % mg % mg % mg
0 100.0 2.945 100.0 2.945 100.0 2.945 100.0 2.945
14 99.8 2.938 99.4 2.927 99.5 2.931 98.4 2.897
35 - 95.3 2.806 94.1 2.772 94.8 2.791
59 97.5 2.871 93.1 2.743 90.6 2.668 90.2 2.655
81 - - 88.0 2.592 87.9 2.588
107 - 88.3 2.600 76.7 2.259 82.3 2.424
133 - 85.8 2.528 67.1 1.975 75.7 2.230
156 97.5 2.871 84.2 2.479 54.6 1.608 72.8 2.144
180 - 71.7 2.111 41.4 1.219 61.5 1.810
204 - - 24.0 0.707 35.4 1.043
228 97.5 2.871 65.6 1.933 12.5 0.367 24.7 0.726
252 - 60.4 1.779 0.0 0.000 16.5 0.485
276 - - - 0.0 0.000
300 - - - -
320 - 41.0 1.209 - -
344 - 27.1 0.798 - -
398 - 12.2 0.359 - -
418 - 7.9 0.233 - -
422 93.8 2.761 - - -
443 - 3.2 0.093 - -
464 - 0.0 0.000 - -
560 92.3 2.717 - - -

C-5
Table. C -4 Headspace methane concentration with injecting different TCE volume.

TCE (g)
Time
0.0 1.4 1.9 2.9 3.75

0 4.11 4.14 4.02 4.24 6.63
25 3.72 4.09 6.25
48 3.25 3.85 5.84
74 1.36 2.85 3.52 5.51
96 0.00 2.38 2.69 3.32 5.31
118 2.01 1.66 3.03 5.17
141 1.75 1.21 2.83 5.16
167 1.60 1.01 2.65 5.13
191 1.59 0.90 2.53 5.10

Table. C -5 Batch experiment with lysimeter soil (10 cm depth, 16 % MC) by
incubating at three different temperatures.

Oxidation rates (g CH
4
/g soil/h*10
-6
) at Temperatures Initial Headspace
Conc. (%)
20 28 35
0.90 - 4.3 -
0.97 - - 5.3
0.99 2.8 - -
1.55 - - 6.7
1.60 3.4 - -
2.01 - 7.3 -
2.74 - - 8.1
3.10 5.5 - -
3.24 - 8.2 -
3.50 6 - -
3.77 - 9.2 -
3.93 - - 11.3
5.35 - - 11.5
5.50 7.5 - -
5.64 - 10.8 -

Appendix - D
Experimental Data and Calculations

D-2
D-1 Calculation of Methane Oxidation

Considering data set dated 05.04.1999 from Table D1,

Air flow rate at the top =V
1
=300 mL/min
Gas flow at the bottom =V
2
=5 mL/min

Total flow =(V
1
+V
2
) mL/min
=V =305 mL/mim

Percentage of methane inflow =0.6* V
2
/V*100
=Y =0.984
Percentage of methane outflow =X =0.291 (from Gas Chromatography)

Total methane consumed in the system
=(1-X/Y)*100
=P =70.49
(assuming no methane accumulation inside the system)

Methane oxidation rate =0.6*V
2
*P mL/min.
=2.16 mL/min.

Similarly, other data sets in Table D1 were calculated. Table D3 shows the methane oxidation
for each sample.

D-2 Calculation of Benzene Concentration

D-2.1 Standard Curve for Standard Solution:

Fig. D-1 Standard Curve for Benzene
A =1218.5C - 121.71
R
2
=0.9988
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
0 10 20 30 40
C (ppm)
A

(
a
r
e
a
)
V
1
V
2
V

D-3
The 4, 16 and 32 ppm benzene standard-solution were injected in gas chromatography in
order to set up the standard curve. The standard curve was plotted by concentration versus
area as shown in Figure D1

The equations from the standard curve were performed to calculate the concentration of
benzene as follows

C = (A +22,996) /9,918

Where,
C =Concentration of benzene in solvent (ppm)
A =Area of benzene peak from chromatogram

D-2.2 Specimen Calculation:

Considering data set dated 31.05.1999 from Table D2,

A =Benzene Peak area =110,143
Q
a
=Actual flow rate =0.33 L/ min
t =Duration of Sampling =60 min

From standard curve,
Benzene concentration in solvent C =13.424

Using equation 3.11,
Actual volume of sampled gas V
a
=Q
a
*t/1000
=0.0198 m
3

Using equation 3.12,
Actual concentration of Benzene C
a
=C/ V
a

=13.424/0.0198
=677.98
g/m
3

Table D3 shows the results of benzene concentrations with methane oxidation.

D-4
D-3 Experimental Results

Table. D-1 Headspace Methane Concentration

Gas supply Air
supply
Methane
Gas(%)
Date Time
mL/min mL/min mL/min CO
2
O
2
N
2
CH
4

26/02/99 11.30 2.5 300 1.50 0.540 20.448 78.556 0.456
27/02/99 9.00 2.5 300 1.50 0.491 20.520 78.551 0.438
01/03/99 11.00 2.5 300 1.50 0.414 20.682 78.827 0.077
03/03/99 13.00 2.5 300 1.50 0.351 20.795 78.809 0.045
05/03/99 13.00 2.5 300 1.50 0.351 20.682 78.827 0.077
07/03/99 13.00 2.5 300 1.50 0.414 20.682 78.827 0.000
09/03/99 13.00 2.5 300 1.50 0.542 20.542 78.916 0.000
13/03/99 13.00 3.6 300 2.16 0.540 20.448 78.556 0.456
17/03/99 14.00 3.6 300 2.16 0.491 20.556 78.795 0.158
19/03/99 13.30 3.6 300 2.16 0.500 20.500 78.800 0.200
22/03/99 16.30 3.6 300 2.16 1.043 19.734 78.959 0.263
24/03/99 13.00 3.6 300 2.16 0.826 20.075 78.905 0.194
26/03/99 17.30 3.6 300 2.16 0.648 20.354 78.980 0.022
30/03/99 11.00 5.0 300 3.00 0.934 19.933 78.824 0.309
02/04/99 13.00 5.0 300 3.00 0.983 19.880 78.878 0.259
05/04/99 13.00 5.0 300 3.00 0.682 20.177 78.815 0.291
06/04/99 13.00 5.0 300 3.00 0.892 19.881 78.946 0.281
08/04/99 13.00 5.0 300 3.00 0.892 19.881 78.946 0.281
16/04/99 20.30 5.0 0 3.00 13.800 5.088 74.233 8.826
17/04/99 11.00 5.0 0 3.00 14.319 4.500 74.000 8.200
19/04/99 14.00 5.0 0 3.00 0.543 20.396 78.642 0.418
20/04/99 13.00 5.0 300 3.00 1.657 18.903 78.946 0.252
21/04/99 13.00 5.0 300 3.00 1.707 20.373 77.678 0.242
22/04/99 19.00 5.0 300 3.00 1.925 20.420 77.405 0.250
23/04/99 12.00 5.0 300 3.00 0.405 20.461 78.878 0.257
24/04/99 18.00 5.0 300 3.00 0.459 19.933 79.359 0.248
25/04/99 13.00 5.0 300 3.00 1.326 19.078 79.355 0.241
26/04/99 13.00 5.0 300 3.00 1.365 19.069 79.318 0.247
27/04/99 14.00 5.0 300 3.00 1.559 19.140 79.062 0.238

D-5
Continuation of Table D-3

Gas supply
Air
supply
Methane Gas(%)
Date Time
2
O
2
N
2
CH
4

28/04/99 12.30 5.0 300 3.00 1.093 19.504 79.169 0.230
29/04/99 14.00 5.0 300 3.00 1.234 19.410 79.200 0.215
30/04/99 13.30 5.0 300 3.00 1.561 18.930 79.302 0.207
01/05/99 12.00 5.0 300 3.00 1.368 18.968 79.462 0.203
02/05/99 13.00 5.0 300 3.00 1.561 18.931 79.306 0.202
03/05/99 13.00 5.0 300 3.00 2.900 17.230 79.592 0.188
04/05/99 13.00 5.0 300 3.00 1.080 19.818 78.910 0.200
05/05/99 12.30 5.0 300 3.00 0.972 20.065 78.650 0.198
06/05/99 14.00 5.0 300 3.00 1.561 18.930 79.302 0.207
07/05/99 13.00 5.0 300 3.00 1.464 18.948 79.380 0.207
08/05/99 15.00 5.0 300 3.00 1.367 18.966 79.454 0.213
09/05/99 13.00 5.0 300 3.00 1.464 18.945 79.367 0.224
10/05/99 13.00 5.0 300 3.00 1.146 19.488 79.134 0.232
11/05/99 13.00 5.0 300 3.00 1.561 18.929 79.298 0.213
12/05/99 16.00 5.0 300 3.00 1.326 19.430 79.016 0.228
13/05/99 13.00 5.0 300 3.00 1.169 19.273 79.322 0.236
14/05/99 13.00 5.0 300 3.00 1.283 19.068 79.417 0.232
15/05/99 13.00 5.0 300 3.00 1.288 19.248 79.219 0.245
16/05/99 13.00 5.0 300 3.00 1.253 19.536 78.968 0.243
17/05/99 19.00 5.0 300 3.00 1.253 19.534 78.962 0.251
18/05/99 20.00 5.0 300 3.00 1.253 19.534 78.962 0.251
19/05/99 13.00 5.0 300 3.00 0.980 19.609 79.165 0.245
20/05/99 13.00 5.0 300 3.00 1.253 19.534 78.962 0.251
21/05/99 13.00 5.0 300 3.00 1.253 19.534 78.962 0.251
22/05/99 18.00 5.0 300 3.00 1.245 19.680 78.816 0.259
23/05/99 13.00 5.0 300 3.00 1.253 19.534 78.962 0.251
24/05/99 13.00 5.0 300 3.00 1.253 19.534 78.962 0.251
25/05/99 13.00 5.0 300 3.00 1.171 20.177 78.312 0.339
26/05/99 13.00 5.0 300 3.00 1.253 19.534 78.962 0.251
27/05/99 13.00 5.0 300 3.00 1.072 19.972 78.842 0.115
28/05/99 19.00 5.0 300 3.00 1.113 19.562 79.074 0.252
29/05/99 13.00 5.0 300 3.00 0.972 19.590 79.186 0.251

D-6

Air
supply
Methane Gas(%)
Date Time
Gas supply
mL/min
mL/min mL/min CO
2
O
2
N
2
CH
4

30/05/99 13.00 5.0 300 3.00 0.987 19.587 79.174 0.252
01/06/99 16.30 5.0 300 3.00 0.979 19.589 79.183 0.250
02/06/99 13.00 5.0 300 3.00 0.775 20.116 78.965 0.145
03/06/99 13.00 5.0 300 3.00 0.948 19.307 79.427 0.318
04/06/99 17.30 5.0 300 3.00 0.600 20.361 78.681 0.358
05/06/99 13.00 5.0 300 3.00 0.609 20.407 78.825 0.159
06/06/99 19.00 5.0 300 3.00 0.981 19.590 79.186 0.244
07/06/99 20.00 5.0 300 3.00 0.924 19.602 79.237 0.237
08/06/99 13.00 5.0 300 3.00 0.885 19.906 79.080 0.128
09/06/99 13.00 5.0 300 3.00 0.925 19.618 79.302 0.155
10/06/99 13.00 5.0 300 3.00 0.899 19.993 79.034 0.075
11/06/99 13.00 5.0 300 3.00 0.880 20.010 79.057 0.053
12/06/99 15.30 5.0 300 3.00 0.814 20.066 79.045 0.075
13/06/99 13.00 5.0 300 3.00 0.869 19.970 79.107 0.054
14/06/99 13.00 5.0 300 3.00 0.915 19.642 79.398 0.045
15/06/99 21.00 5.0 300 3.00 0.938 19.751 79.251 0.061
16/06/99 13.00 5.0 300 3.00 0.945 19.577 79.379 0.099
17/06/99 13.00 5.0 300 3.00 0.963 19.849 79.113 0.076
18/06/99 13.00 5.0 300 3.00 0.979 19.073 79.902 0.045
19/06/99 20.00 5.0 300 3.00 0.810 20.172 78.966 0.052
20/06/99 13.00 5.0 300 3.00 0.785 20.163 78.973 0.078
21/06/99 18.00 5.0 300 3.00 1.564 18.961 79.431 0.045
22/06/99 13.00 5.0 300 3.00 1.564 18.961 79.435 0.040
23/06/99 17.00 5.0 300 3.00 1.561 18.929 79.298 0.213
24/06/99 13.00 5.0 300 3.00 1.146 19.832 78.743 0.280
25/06/99 13.00 5.0 300 3.00 1.561 18.929 79.298 0.213
26/06/99 13.00 5.0 300 3.00 1.561 18.929 79.298 0.213
27/06/99 18.00 5.0 300 3.00 1.561 18.929 79.298 0.213
28/06/99 - 5.0 300 3.00 - - - -
29/06/99 - 5.0 300 3.00 - - - -
30/06/99 - 5.0 300 3.00 - - - -
01/07/99 - 5.0 300 3.00 - - - -
02/07/99 - 5.0 300 3.00 - - - -

D-7

Gas supply
Air
supply
Methane Gas(%)
Date Time
2
O
2
N
2
CH
4

05/07/99 - 5.0 300 3.00 - - - -
06/07/99 - 5.0 300 3.00 - - - -
07/07/99 15.00 5.0 300 3.00 0.576 20.154 78.791 0.479
08/07/99 16.00 5.0 300 3.00 0.673 20.142 78.745 0.440
09/07/99 18.00 5.0 300 3.00 0.785 19.846 78.921 0.448
10/07/99 18.00 5.0 300 3.00 0.786 19.857 78.966 0.392

Table. D-2 Benzene Analysis

Date
Area from
Chromtrograph
A
Concentration of
Benzene in
Solvent
C (ppm)
Duration of
sampling
t (min)
Actual of
volume of
sampled gas
V (m3)
Actual
concentration
Ca (g/m3 )
20.05.99 151134 17.557 300 0.099 177.34
21.05.99 151342 17.578 120 0.040 443.89
22.05.99 60516 8.420 60 0.020 425.26
31.05.99 110143 13.424 60 0.020 677.98
01.06.99 130344 15.461 60 0.020 780.85
14.06.99 141520 16.588 60 0.020 837.76
15.06.99 100453 12.447 47 0.016 802.51
24.06.99 255076 28.037 60 0.020 1416.02
25.06.99 190365 21.513 45 0.015 1448.65

D-8
Table. D-3 Result: Effect of Benzene on Methane Oxidation

Gas supply Air
supply
Methane Methane oxidation Benzene
Date Days
mL/min mL/min mL/min mL/min g/m
3
16/02/99 0 2.5 300 1.5 - -
26/02/99 8 2.50 300 1.50 8 0.120
27/02/99 9 2.50 300 1.50 12 0.176
01/03/99 11 2.50 300 1.50 84 1.266
03/03/99 13 2.50 300 1.50 91 1.363
05/03/99 15 2.50 300 1.50 99 1.485
07/03/99 17 2.50 300 1.50 100 1.500
09/03/99 19 2.50 300 1.50 100 1.500
10/03/99 20 3.60 300 2.16 51 1.090
13/03/99 23 3.60 300 2.16 36 0.775
17/03/99 27 3.60 300 2.16 78 1.682
19/03/99 29 3.60 300 2.16 72 1.553
22/03/99 32 3.60 300 2.16 63 1.360
24/03/99 34 3.60 300 2.16 73 1.571
25/03/99 35 3.60 300 2.16 97 2.093
26/03/99 36 3.60 300 2.16 97 2.092
27/03/99 37 3.60 300 3.00 69 2.090
30/03/99 40 5.00 300 3.00 69 2.057
02/04/99 42 5.00 300 3.00 74 2.209
05/04/99 45 5.00 300 3.00 70 2.112
06/04/99 46 5.00 300 3.00 71 2.144
08/04/99 48 5.00 300 3.00 73 2.177
16/04/99 57 5.00 0 3.00 85 2.559
17/04/99 58 5.00 0 3.00 86 2.590
19/04/99 59 5.00 0 3.00 99 2.979
20/04/99 60 5.00 300 3.00 74 2.232
21/04/99 61 5.00 300 3.00 75 2.262
No
feeding
22/04/99 62 5.00 300 3.00 75 2.239
23/04/99 63 5.00 300 3.00 74 2.218
24/04/99 64 5.00 300 3.00 75 2.243
25/04/99 65 5.00 300 3.00 76 2.265
400-450

D-9

Air
supply
Date Days
Gas supply
mL/min
mL/min mL/min % mL/min g/m
3
26/04/99 66 5.00 300 3.00 75 2.245 400-450
27/04/99 67 5.00 300 3.00 76 2.275
28/04/99 68 5.00 300 3.00 77 2.298
29/04/99 69 5.00 300 3.00 78 2.344
30/04/99 70 5.00 300 3.00 79 2.368
01/05/99 71 5.00 300 3.00 79 2.381
02/05/99 72 5.00 300 3.00 80 2.385
03/05/99 73 5.00 300 3.00 81 2.427
04/05/99 74 5.00 300 3.00 80 2.390
05/05/99 75 5.00 300 3.00 80 2.396
06/05/99 76 5.00 300 3.00 79 2.368
07/05/99 77 5.00 300 3.00 79 2.368
08/05/99 78 5.00 300 3.00 78 2.350
09/05/99 79 5.00 300 3.00 77 2.316
10/05/99 80 5.00 300 3.00 76 2.292
13/05/99 83 5.00 300 3.00 76 2.282
14/05/99 84 5.00 300 3.00 76 2.293
15/05/99 85 5.00 300 3.00 75 2.253
16/05/99 86 5.00 300 3.00 75 2.258
17/05/99 87 5.00 300 3.00 74 2.233
18/05/99 88 5.00 300 3.00 74 2.233
19/05/99 89 5.00 300 3.00 75 2.252
20/05/99 90
21/05/99 91 5.00 300 3.00 74 2.233
22/05/99 92
23/05/99 93 5.00 300 3.00 74 2.233
24/05/99 94 5.00 300 3.00 74 2.233
25/05/99 95 5.00 300 3.00 66 1.965
26/05/99 96 5.00 300 3.00 74 2.233
27/05/99 96 5.00 300 3.00 88 2.650
28/05/99 97 5.00 300 3.00 74 2.232
29/05/99 98 5.00 300 3.00 74 2.233
30/05/99 99 5.00 300 3.00 74 2.231
750-800

D-10

Gas supply Air
supply
Date Days
mL/min mL/min mL/min % mL/min g/m
3
01/06/99 100 5.00 300 3.00 75 2.239
02/06/99 101 5.00 300 3.00 85 2.558
03/06/99 102 5.00 300 3.00 68 2.031
04/06/99 103 5.00 300 3.00 64 1.907
05/06/99 104 5.00 300 3.00 84 2.515
06/06/99 105 5.00 300 3.00 75 2.257
07/06/99 106 5.00 300 3.00 76 2.278
08/06/99 107 5.00 300 3.00 87 2.608
09/06/99 108 5.00 300 3.00 84 2.527
10/06/99 109 5.00 300 3.00 92 2.772
11/06/99 110 5.00 300 3.00 95 2.839
12/06/99 111 5.00 300 3.00 92 2.771
13/06/99 112 5.00 300 3.00 95 2.836
14/06/99 113 5.00 300 3.00 95 2.863
15/06/99 114 5.00 300 3.00 94 2.814
750-800
16/06/99 115 5.00 300 3.00 90 2.699
17/06/99 116 5.00 300 3.00 92 2.770
18/06/99 117 5.00 300 3.00 95 2.862
19/06/99 118 5.00 300 3.00 95 2.842
20/06/99 119 5.00 300 3.00 92 2.761
21/06/99 120 5.00 300 3.00 95 2.864
22/06/99 121 5.00 300 3.00 96 2.878
23/06/99 122 5.00 300 3.00 78 2.351
24/06/99 123 5.00 300 3.00 72 2.148
25/06/99 124 5.00 300 3.00 78 2.351
26/06/99 125 5.00 300 3.00 78 2.351
27/06/99 126 5.00 300 3.00 78 2.351
28/06/99 127 5.00 300 3.00 - -
29/06/99 128 5.00 300 3.00 - -
01/07/99 130 5.00 300 3.00 - -
02/07/99 131 5.00 300 3.00 - -
03/07/99 132 5.00 300 3.00 - -
04/07/99 133 5.00 300 3.00 - -
1400-
1450

D-11

Gas supply Air
supply
Date Days
mL/min mL/min mL/min % mL/min g/m
3
05/07/99 134 5.00 300 3.00 - -
06/07/99 135 5.00 300 3.00 - -
07/07/99 136 5.00 300 3.00 51 1.539
08/07/99 137 5.00 300 3.00 55 1.659
09/07/99 138 5.00 300 3.00 54 1.633
10/07/99 139 5.00 300 3.00 60 1.806
11/07/99 140 5.00 300 3.00 78 2.351
Feeding
stopped

Table. D-4 Details of the Lysimeter

Parameters Dimension and Values
Soil Core ( Column ) Acrylic material tube
- Length 1.20 m
- Diameter 19.00 cm
Sampling Port Interval 20.00 cm
Soil Depth 90.00 cm
Soil Type Sandy soil
- Sand 85
- Silt / Clay 15
Soil Density 1410 kg / m
3
Soil Moisture Content 8-9
Ambient Temperature 28-34
o
C
Purge Gas 60 Methane +40 carbondioxide
Gas flow 2.5-5.0 mL/min
Air flow at top 300 mL / min
Amendment with nutrient No

D-12

D-4 Additional Peaks Shown by GC During Benzene Feeding 750-800 g/m
3

D-13

D-5 Strange Methane Peak Shown by GC During Benzene Feeding 1400-1450 g/m
3

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Control of landfill Gas
Control of landfill Gas
by by
Balasingam Palananthakumar Balasingam Palananthakumar
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Contents
Contents
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Solid Waste Definition
Solid wastes are the wastes arising from human and
animal activities that are normally solid and are
discarded as useless or unwanted. The term solid
wastes is all-inclusive, encompassing the
heterogeneous mass of throwaways from the urban
community as well as more homogenous accumulation
of agricultural, industrial, and mineral wastes.
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Refuse materials by kind, composition, and sources
Kind Composition Sources
Garbage
Rubbish
Ashes
Street
refuse
Dead
animals
Abandoned
vehicles
Industrial
wastes
Demolition
wastes
Construction
wastes
Special
wastes
Sewage
treatment
residue
Waste from preparation, cooking and
serving of food; market wastes; wastes
from handling, storage, and sale of
produce
Combustible: paper, cartons, boxes,
barrels, wood, excelsior, tree branches,
yard trimmings, wood furniture, bedding,
dunnage
Noncombustible: metals, tin cans, metal
furniture, dirt, glass, crockery, minerals
Residue from fires used for cooking and
heating and from on-site incineration
Sweeping dirt, leaves, catch basin dirt,
contents of litter receptacles
Cats, dogs, horses, cows
Unwanted cars and trucks left on public
property
Food-processing wastes, boiler house
cinders, lumber scraps, metal scraps,
shavings
Lumber, pipes, brick, masonry, and other
construction materials from razed
buildings and other structures
Scrap lumber, pipe, other construction
materials
Hazardous solids and liquids; explosives,
pathological wastes, radioactive
materials
Solids from coarse screening and from
grit chambers; septic tank sludge
Households,
restuarants,
institutions, stores,
markets
Streets, sidewalks,
alleys, vacant lots
Factories, power
plants
Demolition sites to be
used for new buildings,
renewal projects,
expressways
New construction,
remodeling
Households, hotels,
hospitals, institutions,
stores, industry
Sewage treatment
plants; septic tanks
Menu
Projection of average composition of
U.S. solid waste by year
a
Composition 1970 1975 1980 1990 2000
Paper
Yard wastes
Food wastes
Glass
Metal
Wood
Textiles
Leather and
rubber
Plastics
Miscellaneous
37.4
13.9
20.0
9.0
8.4
3.1
2.2
1.2
1.4
3.4
39.2
13.3
17.8
9.9
8.6
2.7
2.3
1.2
2.1
3.0
40.1
12.9
16.1
10.2
8.9
2.4
2.3
1.2
3.0
2.7
43.4
12.3
14.0
9.5
8.6
2.0
2.7
1.2
3.9
2.4
48.0
11.9
12.1
8.1
7.1
1.6
3.1
1.3
4.7
2.1
a
Percentage of waste stream as discarded on a dry mass basis.
Menu
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GHG and Climate Change
Human activities increase GHG concentrations and trap
more heat.
The Earths climate changes due to the buildup of GHG.
-The present associated rate of temperature change is significantly faster than past
(observed in 10,000 yrs)
Climatic changes have adverse effects on ecological
system, human health and socio-economic sectors.
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Human activities
increases GHG
Climate changes
(Biosphere, Atmosphere, Ice, Oceans)
Physical Responses
Biological Process I mpacts
Human Health
Water Resources
Crop Yields
Forest Composition
Coastal Areas
GHG and Impacts
Menu
Climate Change Impacts
Human health, natural ecological systems and socioeconomic
systems are all sensitive to both the magnitude and the rate of
climate change
Many physical and ecological system will be simultaneously affected
The ability of natural ecological system to migrate appears to be
much slower than the predicted rate of climate change
With the growth in atmospheric concentrations of GHGs,
interference with the climate system will grow in magnitude, and the
likelihood of adverse impacts from climate that could be judged
dangerous will become greater (IPCC, 1995)
Climate change can add to existing environment stresses.
Menu
GHG Changes Global Climate
Temperature
Precipitation
Sea Level Rise
Heath Impacts
Weather-related Mortality
Infectious Diseases
Air Quality- Respiratory Illness
Agriculture Impacts
Crop yields
Irrigation demands
Forest Impacts
Change in forest composition
Forest Health and Productivity
Water Resource Impacts
Change in water supply
Water quality
Increased Composition for water
Impatcs on Coastal Areas
Erosion of beaches
Inuadate coastal lands
Cost to defend coastal communities
Species and Natural Areas
Shift in ecological zones
Loss of habitat and species
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Changing Climate...
Climate has changed over the past century
Global mean temp increased by 0.5-1.0
0
F
Global sea level risen by 4-10 inches
Global precipitation over land increased by 1%
The balance of evidence suggests a discernible human
influence on global climate (IPCC, 1995)
Expected climate changed in future (by 2100)
Projected temperature increase of 4
0
F
Projected sea level rise of 20 inches
Likely increase in precipitation
Menu
Trends of Temperature and Precipitation
(1900 to Present)
Temperature Precipitation
Warming
Cooling
Increasing
Decreasing
Note : Cooling in southeast U.S may be due to aerosol influence
Source: Karl et al (1996)
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Increment of GHGs..
Atm concentration of GHGs have increased since
industrial revolution.
CO2 -30%; CH4 -100%, N2O -15%
Concentration of GHGs projected to reach double
pre-industrial levels by about 2060
Many GHGs remain in atmosphere for long time
(decade to centuries)
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The Effect of GH
There is natural greenhouse effects which keeps the earth
warm enough to be habitable.
-GHGs like CO2, CH4, and N20 and water vapor trap heat and warm the earths surface.
Many researchers proved the basic principles of GH
For a given concentration of GHG, the resulting amount of
radioactive forcing (heat trapping energy) can be predicted
with precision.
Exactly how the Earths climate will respond to enhanced
greenhouse gases will also depend on complex interactions
between the atmosphere, oceans, land, ice and biosphere.
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Change in GHGs...
Source: IPCC, 1995
CO
2
CH
4
N
2
0
Pre-Industrial 280pp
m v
700p
pbv
275
ppb v
In 1994 358pp
m v
1720
ppb v
312
ppbv
Rate of change 1.5
ppm
v/yr
10 pp
v/yr
0.8
ppbv/
yr
Atmospheric
lifetime (yr)
50-
200
12 120
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1422
177
40 37
1826
0
500
1000
1500
2000
C
O
2
C
H
4
N
2
0
H
F
C
/
P
F
C
T
o
t
a
l
Source: EPA(1997)
sinks not included
GHGs Emission from U.S (1995)
MMTCE
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The control of landfill gas is recent challenge in landfill
technology - environmental protection and energy
recovery.
Understanding landfill gas generation at a process level
aids its control efficiency.
The present session is aimed at advancing the art of
landfill gas control by prediction the gas generation
performance of a landfill bioreactor.
Predictions require a theoretical framework-
C(s) C(aq) C(X
A
) C(Ac) C(X
M
) C(CH
4
), C(CO
2
)
Hydrolysis Acidogenious Methanogenious
Governing Equations: 1st order reaction + Mass
balance + Monod kinetics
Methane Generation
Methane Generation
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Simulates successfully.
Cumulative methane generation matches
with field data at the MVCLP.
Sensitivity of methane generation with
different initial conditions, specific growth rate
and reaction rate constants.
Hydrolysis rate constant (K
h
) and Initial
organic carbon concentration in waste
{C
(S)
} are important parameters in affecting
the methane generation directly.
Results
Results
Menu
18% reduction in methane generation rate (from
0.000017 to 0.000014 kg/m
3
waste.day).
To do it,
- segregate waste before landfilling as high-organic
substance and low-organic portion.
- send high-organic substance for composting and send
remaining portion for landfilling.
- also gives useful product (ie composted materials
could be used as fertilizer).
Technical Significance
-
-
1
1
20% reduction (from 30 kg.m
-3
to 24kg .m
-3
) in organic carbon
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89% reduction in rate of methane generation.
It could be
- the most effective way to reduce methane
generation in landfill
- Also useful to reduce amount of organic
carbon in leachate
- Draw back: Long after-care period.
-
-
2
2
In case of recovery, practice vice versa for effective
methane collection.
-
-
3
3
Reduction of hydrolysis rate constant (K
h
) from 0.0002
day
-1
to 0.00002 day
-1
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MODELING OF METHANE GENERATION, OXIDATION AND EMISSION IN

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