Methane Generation Potential

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753532

review-article2018
WMR0010.1177/0734242X17753532Waste Management & ResearchPark et al.

Review Article

Waste Management & Research

Methods for determining the methane


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© The Author(s) 2018
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DOI: 10.1177/0734242X17753532
https://doi.org/10.1177/0734242X17753532

generation rate constant for the FOD journals.sagepub.com/home/wmr

model: a review

Jin-Kyu Park1 , Yong-Gil Chong2, Kazuo Tameda3 and Nam-Hoon Lee4

Abstract
In the first order decay (FOD) model of landfill methane generation, the methane generation potential (L0) and methane generation
rate constant (k) for both bulk municipal solid waste (MSW) and individual waste components have been determined by a variety
of approaches throughout various literature. Differences in the determination methods for L0 and k are related to differences in our
understanding of the waste decomposition dynamics. A thorough understanding of the various available methods for determining L0
and k values is critical for comparative study and the drawing of valid conclusions. The aim of this paper is to review the literature
on the available determining methods and the ranges for L0 and k values of both bulk MSW and individual waste components, while
focusing on understanding the decomposition of waste, including the role of lignin. L0 estimates in the literature are highly variable
and have been derived from theoretical stoichiometric calculations, laboratory experiments, or actual field measurements. The lignin
concentration in waste is correlated with the fraction of total degradable organic carbon (DOCf) that will actually anaerobically
degrade in the landfill. The k value has been determined by precipitation rates, laboratory simulations, aged-defined waste sample,
and model fitting or regression analysis using actual gas data. However, the lignin concentration does not correlate well with the k
value, presumably due to the impact of lignin arrangement and structure on cellulose bioavailability and degradation rate. In sum, this
review summarizes the literature on the measurement of L0 and k values, including the dynamics and decomposition of bulk MSW
and individual waste components within landfills.

Keywords
Landfill, municipal solid waste, first-order decay model, methane generation potential, methane generation rate constant

Received 19th April 2017, accepted 16th December 2017 by Associate Editor Rodrigo Navia.

Introduction
Landfills that are managed to minimize environmental impact model, and Afvalzorg model (Kamalan et al., 2011; Mou et al.,
and promote waste degradation can be integrated with technolo- 2014). The E-PRTR (Fr) and LandGEM models are single-phase
gies that include energy recovery systems. Many of the technolo- models, whereas the IPCC and Afvalzorg models are multi-phase
gies that have been used to promote more sustainable landfills models, which operate with a number of more detailed waste cat-
focus on the methods to foster waste treatment. Sustainable land- egories (Mou et al., 2014). The effect of the age of waste on CH4
fill practices address how best to manage the landfill, including production is incorporated into the first-order model. For each
leachate and landfill gas (LFG). Landfills are usually considered unit amount of waste, the FOD models consider that the CH4
to be anthropogenic sources of methane (CH4), which has histori-
cally been the largest source of greenhouse gas (GHG) emissions
1Ecowillplus Co., Ltd., Anyang, Republic of Korea
from the waste sector (Bogner et al., 2008). Time dependent 2Dreampark Establishment Department, Sudokwon Landfill Site
quantitative estimation of LFG production is the primary crite- Management Corporation, Incheon, Republic of Korea
rion that should determine the choice of method of gas utiliza- 3Graduate School of Engineering, Fukuoka University, Japan
4Department of Environmental and Energy Engineering, Anyang
tion. Due to the difficulties in precisely monitoring CH4 emissions
University, Republic of Korea
of whole landfill sites, modeling approaches are applied. These
approaches include first-order decay (FOD) LFG generation Corresponding author:
models, including the US EPA’s LFG emissions model Nam-Hoon Lee, Department of Environmental and Energy
Engineering, Anyang University, Samdeok-ro 37 beon-gil, Manan-gu,
(LandGEM), e-pollutants release and transfer registers (E-PRTR) Anyang-si, Gyeonggi-do, Republic of Korea.
(Fr) model, Intergovernmental Panel on Climate Change (IPCC) Email: nhlee@anyang.ac.kr
2 Waste Management & Research 00(0)

generation rate decays exponentially with time (Rajaram et al., generation potential in the landfill, because the value of L0
2012): includes a number of physical and environmental factors (e.g.,
moisture, temperature, and particle size) that influence CH4 gen-
G = WL0 ke-kt (1) eration (Wang et al., 2013a). The CH4 generation potentials in
field settings are lower, because landfills do not function as effi-
where G is the CH4 generation rate in volume per time, W is the ciently as anaerobic digesters or laboratory experiments (Bogner
mass of waste in place, L0 is the CH4 generation potential in vol- and Matthews, 2003; Fei et al., 2016).
ume per mass, k is the first-order rate constant in reciprocal time, In the literature, various methods are used to measure the L0 of
and t is the time elapsed after disposal of the waste. solid waste. Table 1 presents a range of L0 values from solid
The basic condition to obtain modeling results that are as waste landfill, and methods for determining L0. As observed in
suited as possible to the actual production of gas is the right these studies, L0 values vary greatly among the different landfills,
choice of assumption, with regard to the constants of the CH4 which are mainly due to differences between their waste compo-
generation potential (L0) and CH4 generation rate (k). L0 repre- sitions (Fei et al., 2016). In general, L0 values have been deter-
sents the total volume of CH4 generated from a specified quantity mined by a number of methods: the stoichiometric method
of disposed waste. The k value controls the predicted time over (Machado et al., 2009; Mor et al., 2006; Sanderson et al., 2008);
which CH4 is generated from the specified waste stream (Amini experimental methods (Cho et al., 2012; Jeon et al., 2007;
et al., 2012). These parameters are strongly dependent on the Tolaymat et al., 2010); model fitting or regression analysis using
chemical composition, properties of waste, and the condition of gas data (Amini et al., 2012; Wang et al., 2013a); and the IPCC
the process (e.g., waste density, pH, and moisture content). For model (Govindan and Agamuthu, 2014; Kumar et al., 2004;
this reason, the examination and critical estimation of the bio- Thompson et al., 2009).
chemical properties of wastes that take into consideration the Table 2 presents a range of L0 values for individual waste
controlling LFG emissions are of substantial importance for components. Food waste with high moisture content has a low L0,
determining the L0 and k values. As essential parameters, L0 and whereas paper wastes have a high L0. Over the lifetime of the
k values for both bulk municipal solid waste (MSW) and indi- landfill, the slowly degrading components, especially paper and
vidual waste components are widely studied and reported in the card waste, make the most significant overall contribution to CH4
literature. Furthermore, various review studies have been per- emissions (Donovan et al., 2011). Therefore to achieve signifi-
formed on anaerobic decomposition, the methane generation cant reduction in LFG generation, the reduction and sorting of
potential of MSW, biogas generation processes, LFG generation paper, card, and green waste should be prioritized (Pan and
models, and CH4 oxidation processes (Abushammala et al., 2014; Voulvoulis, 2007).
Barlaz, 2006; Fei et al., 2016; Gunaseelan, 1997; Kamalan et al., Another possible solution for the reduction of LFG generation
2011; Krause et al., 2016a; Mao et al., 2015; Micales and Skog, is mechanical biological treatment (MBT; Di Maria et al., 2013).
1997; Oonk, 2010; Scheutz et al., 2009). MBT leads to a significant reduction of LFG generation from
The aim of this paper is to review the literature on the availa- landfills as compared to the raw waste. De Gioannis et al. (2009)
ble determining methods and the ranges for L0 and k values of reported that 91% reduction of the LFG generation potential was
both bulk MSW and individual waste components, with the achieved after 8 weeks of aerobic treatment. In addition, there is
review focusing on understanding the decomposition of waste, a concept of anaerobic bioreactor landfill. In comparison with the
including the role of lignin. The following section reviews a wide traditional dry sanitary landfill, this method allows for better use
range of L0 values and their determining methods, and provides a of the energy potential of biogas and reduces the risk of uncon-
brief description of L0 in a landfill definition and discussion of trolled LFG emissions.
the relationship between lignin and the extent of decomposition
for individual waste components. The last section of the paper
provides a summary and analysis of the literature on the degrada- Stoichiometric method
tion rate of both bulk MSW and individual waste components in The CH4 yield (B0) can be calculated by assuming the total stoi-
both landfills, and laboratory- and field-scale simulations thereof. chiometric conversion of the organic matter to CH4 and carbon
dioxide (CO2) using Buswell’s equation (Raposo et al., 2011):
Methods for determining L0
[(a / 2) + (b / 8) − (c / 4)] × 22400
Overview of L0 values from the literature B0 = (2)
(12a + b + 16c)
The L0 of wastes is defined as the volume of CH4 that can be
produced per unit mass of waste under idealized conditions for Empirical formulae (CaHbOc) can be designed from experimental
CH4 formation (Krause et al., 2016a). The L0 is often used to refer elemental analysis determination. However, a limitation of this
to the ultimate CH4 yield, i.e., the maximum amount of CH4 pro- equation is associated with the stoichiometric estimates of waste
duced per unit mass of waste under anaerobic conditions. It fractions, which are not biodegradable, the moisture limitations,
should be noted that it is misleading to refer to L0 as the CH4 and also toxins, some fraction of the waste that is not accessible.
Table 1. L0 values at landfill level taken from the literature, and corresponding determination methods (DOC: degradable organic carbon, DOCf: fraction of DOC that can
decompose, MCF: CH4 correction factor for aerobic decomposition).

Landfill site DOC DOCf MCF L0a Method References


Park et al.

(m3 CH4 Mg−1)


Metropolitan center landfill, Salvador, 0.273 0.263 1 67.0 Stoichiometric equations with Machado et al.
Brazil biodegradable fraction (2009)
Loma Los Colorados landfill, Montenegro, – - - 105.0 Sanderson et al.
Chile (2008)
Gazipur landfill, Delhi, India 0.0835 0.580 1 45.2 Carbon content Mor et al. (2006)
India 0.11–0.16 0.77 0.4 31.6–46.0 Waste composition with the IPCC Kumar et al. (2004)
Jeram landfill, Bulk waste approach 0.12 0.5 0.8 44.8 model Govindan and
Selangor, Waste composition 0.08 0.5 0.8 29.9 Agamuthu (2014)
Malaysia approach
Canada Ontario 0.176–0.205 0.77 1 126–147 Thompson et al.
Nova Scotia 0.175–0.227 126–147 (2009)
Quebec 0.249–0.283 179–203
Alberta 0.195–0.228 140–164
British Columbia 0.212–0.261 153–188
Korea Sudokwon landfill site 1 0.18–0.30 0.57–0.63 1 56–88 Waste composition with waste- Jeon et al. (2007)
Sudokwon landfill site 2 0.13–0.21 0.55–0.60 1 37–58 component specific CH4 generation
Outer Loop landfill, USA – – – 54.8 potential Tolaymat et al.
(2010)
Landfills in Florida, USA – – – 67 Amini et al. (2012)
(traditional landfills)
70
(wet cell)
23 metro cities, India – – – 30.2–52.1 Kumar and Sharma
(2014)
USA National average waste – – – 59.1 Staley and Barlaz
composition (2009)
State average waste – – – 63.9
composition
Outer Loop landfill – – – 48.4±14
USA – – – 46 Kaplan et al. (2009)
4 landfills, Afvalzorg – – – 22–31 Krause et al.
Denmark IPCC 63–89 (2016b)
Landfills, USA A – – – 140 Waste composition with waste- Amini et al. (2013)
B – – – 74 component specific CH4 generation
C – – – 93 potential and calibration
USA 10 landfills – – – 100 Waste composition with waste- Wang et al. (2013)
T landfill – – – 85 component specific CH4 generation
potential and minimizing the SSE
3

(Continued)
4 Waste Management & Research 00(0)

Organic matter can be fractionated into easily biodegradable

Park et al. (2012b)


Faour et al. (2007)
compounds (carbohydrates, lipids, and proteins), and poorly bio-

Maciel and Jucá


Cho et al. (2012)

Sormunen et al.
degradable compounds (fibers, humic, and fulvic acids) (Batstone
References

et al., 2002; Lesteur et al., 2010). If the organic fraction composi-


tion (lipids, proteins, and carbohydrates) is known, the CH4 yield

(2013)

(2011)
can be estimated using the following general equation (Raposo
et al., 2011):
component specific CH4 generation

B0 = 415 × %Carbohydrates +

Nonlinear regression using field


potential and a correction factor

(3)
Waste composition and waste-

496 × %Proteins + 1014 × %Lipid


Model fitting using field data

The coefficients in this equation are derived from stoichiometric


conversion of model compounds representing average formulae
for carbohydrates (C6H10O5), proteins (C5H7O2N), and lipids
(C57H104O6) (Angelidaki and Sanders, 2004; Raposo et al., 2011).
However, in practice, not all of the organic matter in waste is
Method

subject to microbial degradation. This makes the production of


data

LFG much lower than the theoretical value. The elemental com-
position value therefore overestimates the biochemical methane
potential (BMP) value (Lesteur et al., 2010). It is important to
note that the theoretical CH4 potential must be adjusted by a bio-
degradability factor.
(m3 CH4 Mg−1)

L0 values for waste can be calculated using the theoretical


CH4 potential and the biodegradable portion (BF) of the waste, as
56–69

18–20
123.9

shown in (Machado et al., 2009):


100

115

100
76

95
87
L0a

B0 × BF
L0 = (4)
1+ w

The water content, w, is used to consider only the dry mass of


MCF

potentially degradable organic matter. The BF value can be cal-



culated using the ratio between the BMP value and the values
predicted by stoichiometric equation (equation (2)). For example,
the BF value at the Metropolitan Landfill, Salvador, Brazil is
F value of 0.5 is used, and the density of CH4 is assumed to be 0.714 kg/m3.

found to be 0.263, excluding plastic and rubber content (Machado


DOCf

et al., 2009).


The linear relationship between BF and lignin has been mod-


elled by Chandler et al. (1980). Several kinds of substrate, such
as manure, newspaper, straw, leaves, and other agricultural mate-
rials, were used to develop the model, predicting the effect of
lignin content on BF (Lesteur et al., 2010). Chandler’s model is
DOC

as follows:


BF = 0.83 − (0.028 × lignin ) (5)

where lignin (0 < lignin < 20%) is the VS lignin content.


Sudokwon landfill site 2, Korea

Sudokwon landfill site 1, Korea

LFG is formed as a result of the biodegradation of organic


Ämmässuo landfill, Finland

carbon in the waste: stoichiometry shows that per kilogram of


Muribeca landfill, Brazil

organic carbon (= 83.3 mol) that anaerobically degrades, about


Table 1. (Continued)

1.87 m3 of LFG normalized to 1 atm and 0°C (= 83.3 mol × 22.4


L/mol) is produced (Scharff and Jacobs, 2006). Anaerobic
Three landfills

decomposition can be hindered in specific microenvironments,


Landfill site

21 landfills
Landfill A

due to unsuitable environmental conditions, and the heteroge-


CSWMC
SSWMC

neity of the waste composition. This is accounted for by assum-


aAn

ing that only a fraction (ζ) of the waste is converted into LFG.
Park et al. 5

Table 2. L0 values for individual waste components taken from the literature.

Country Component DOC DOCf MCF L0 (m3 CH4 Mg-1) References


USA Leaves Source: Eleazer et al. (1997) 30.6 Kaplan et al.
Grass 136.0 (2009)
Branches 62.6
Old newsprint 74.3
Cardboard 152.3
Office paper 217.3
Phone books 74.3
Books 217.3
Old magazines 84.4
3rd Class mail 150.8
Mixed paper 103.7
Food waste 300.7
USA Household waste 0.16-0.20 0.50 0.5 74.7-93.4 Manfredi et al.
Kitchen organics 0.10-0.12 0.64 59.8-71.7 (2009)
Newspapers 0.36-0.44 0.20 67.2-82.2
Office paper 0.30-0.36 0.88 246.5-295.8
Cardboard 0.30-0.38 0.45 126.1-159.7
Wood 0.40-0.45 0.23 85.9-96.6
Hokkaido, Japan Paper BMP test 214.4 Ishii and
Kitchen waste 126.7 Furuichi (2013)
Thailand Food waste 0.15 0.5 0.65 45.5 Wangyao et al.
Papers 0.40 121.4 (2010)
Wood 0.43 130.5
Textiles 0.24 72.8
Denmark Shredder Laboratory test 6.2-9.1 Mou et al.
Street cleaning 7.2-7.4 (2014)
Mixed bulky 5.4-7.0
Sludge 52.0-70.0
USA Yard waste BMP test 49.0 Yazdani et al.
(2012)
Korea Food wastes Stoichiometric 0.36 0.68 1.0 117.1 Jeon et al.
Organic carbon 0.33 0.73 (2007)
Paper Stoichiometric 0.72 0.70 239.1
Organic carbon 0.79 0.63
Wood Stoichiometric 0.56 0.44 116.0
Organic carbon 0.57 0.43
Textile Stoichiometric 1.00 0.45 215.8
Organic carbon 0.89 0.51
Misc. Stoichiometric 0.39 0.59 109.3
organics Organic carbon 0.40 0.58
Sludge Stoichiometric 0.14 0.29 19.1
Organic carbon 0.12 0.33
Italy Mechanically sorted organic Laboratory test 115.1±4.2 De Gioannis
residues et al. (2009)
Mechanically-aerobically 9.2±1.5
pretreated waste
Italy Mechanically-aerobically 12 Di Maria et al.
pretreated waste (2013)
England Mechanically-aerobically 49.5 Siddiqui et al.
pretreated waste (2013)
Germany Mechanically-anaerobically- 17.7
aerobically pretreated waste

It may be said that BF and ζ have a similar meaning. ζ is typi- degradable organic carbon may be dissimilated (Bingemer and
cally of the order of 0.5 (Bogner and Matthews, 2003), and Mor Crutzen, 1987). However, this value was obtained in ideal con-
et al. (2006) suggested a value of 0.58. ζ increases with tem- ditions, so it is not likely that the value in real landfills exceeds
perature, and can be as high as 0.8. At 35°C, almost 80% of the 0.7 (Mor et al., 2006):
6 Waste Management & Research 00(0)

α t = ζ 1.87AC0 ke-kt Secondly, there are many international and national standards
(6)
available on how to perform a BMP test, but they differ in the
experiment set-up, and are frequently modified and adapted to
where αt is the LFG formation at a certain time (m3 yr−1), ζ is the
the specific researcher’s purpose (Raposo et al., 2011). Due to
dissimilation factor, k is the degradation rate constant (yr−1), A is
this, it is often difficult to evaluate results from different studies,
the amount of waste deposited (Mg), C0 is the amount of degra-
as the values and level of information can substantially differ.
dable organic carbon in the waste (kg Mg−1) at the time of deposi-
Many studies demonstrate the importance of considering the
tion, t is the time elapsed in years since deposition (yr), and the
temperature, pressure, particle size, origin of inoculum, inocu-
factor 1.87 has the dimensions m3 kg−1.
lum-to-substrate ratio, and mixing rate when performing BMP
Measuring the elemental composition and organic carbon is
test (Angelidaki et al., 2009; Strömberg et al., 2014; Walker et al.,
very fast, taking only a few hours. But, it should be noted that the
2009).
application of results obtained from these methods to a full-scale
Finally, the L0 value obtained via the BMP test is greater than
landfill remains difficult, because the methods simulate only
that obtained from a lysimeter experiment and full-scale data. A
average landfill conditions, and do not account for variations
lysimeter is a simulate form of sanitary landfill in the sense of
brought about by climatic and operational events.
control device (Rafizul et al., 2012). Generally, lysimeters are
smaller, more self-contained and better monitored than landfills.
Experimental methods Their small scale allows their location in a laboratory, where it is
convenient to perform extensive monitoring (Stessel and Murphy,
L0 values have been measured by BMP test, lysimetry, and field- 1992).
scale experiments. The L0 value from full-scale landfills would The lysimeter experiments use a few kilograms of sample.
be the best indicator. However, such data are very limited, if not Therefore in contrast to the BMP test, the lysimeter experiment
non-existent, and are difficult to acquire, given the complexity of uses sample amounts that are more representative of the mixed
biochemical interactions within a landfill, the lack of uniform waste without segregation, and so provides more reliable and
and reliable data collection protocols, the inherent uncertainty of valid data. However, the lysimeter experiments are limited, since
gas collection methods employed at various sites, and the matu- a very long time is required (e.g., a number of years) to collect
ration stage at which a landfill might be during a monitoring acceptable data (Cho et al., 2012).
period (El-Fadel et al., 1997). In contrast, laboratory experiments The CH4 generation for wastes in the lysimeter would be low,
are better controlled, and employ operating procedures to enhance due to the larger size of the tested sample, and restricted mass
microbial activity. For these reasons, laboratory experiments pro- transfer of the substrate and nutrients in the lysimeter, compared
duce more predictable result, compared to field monitoring stud- with those in the case of the BMP test (Cho et al., 2012). Thus,
ies (Fei et al., 2016). Cho et al. (2012) suggested
In order to determine L0, several authors have used the BMP
n
value of mixed waste based on the weighted average of waste
components (Cho et al., 2012; Jeon et al., 2007; Tolaymat et al.,
L0,landfill = f × ∑ (L
i =1
0 ,i , BMP × ( wt. fraction)i ) (7)

2010). BMP assay is described by Owen et al. (1979), and has


been modified by some researchers (Shelton and Tiedje, 1984; which means that the L0 obtained from BMP test (L0,i,BMP) needs
Strömberg et al., 2014). The L0 from landfill depends on the com- to be corrected using a correction factor (f), based on the BMP
position of waste (Cho et al., 2012). It should be noted that it is assay and lysimeter study.
not possible to predict L0 for landfills with inaccurate waste com- Sil et al. (2014) published correction factors to estimate CH4
position data (Amini et al., 2013). emission using the LandGEM model. The correction factors are
The BMP value can be used as an index of the anaerobic bio- 0.94, 0.13, and 0.74 for food waste, mixed un-segregated MSW,
degradation potential. The BMP is the experimental value of the and vegetable wastes, respectively.
maximum quantity of CH4 produced per gram of volatile solid. With respect to hydraulic conductivity, the disadvantage of
For this reason, BMP test also involves certain problems related the lysimeter test is the hydraulic retention time (HRT). The HRT
to obtaining acceptable data for determining the L0. of a lysimeter may not allow for sufficient residence time for
Firstly, DOC and BMP values are closely related (Machado carbon degradation in leachate (Park et al., 2012a). In contrast,
et al., 2009). DOC is the organic carbon in wastes that is accessible previous studies reported that less than 4% of the total input car-
to biochemical decomposition under anaerobic conditions, which bon is emitted through leachate in landfills (IPCC, 2006; Lornage
includes the biochemical processes in a cell or organism. In other et al., 2007; Kim et al., 2011; Manfredi et al., 2009; Valencia
words, DOC is the amount of organic carbon that is ultimately et al., 2009). The low proportion of DOC emitted through lea-
degraded under optimal anaerobic conditions. Similarly, the BMP chate can be explained by the low hydraulic conductivities of
assay measures the quantity of anaerobically degradable organic compacted MSW, which impedes water flow. The literature
carbon present in a sample under optimal conditions (Lesteur et al., review shows that the hydraulic conductivities of waste at land-
2010; Mou et al., 2015a, 2015b; Wang et al., 1994). fills range from 1.36 × 10−3 to 1.03 × 10−7 cm s−1 (Petrovic, 2016).
Park et al. 7

It should be noted that carbon emitted via leachate needs to be Decomposable degradable organic carbon (DDOCm) is the part
considered to determine L0 using a lysimeter. of the organic carbon that will degrade under the anaerobic con-
ditions in landfill. DOC is the organic carbon in waste that is
accessible to biochemical decomposition. DOCf is the fraction of
Model fitting and regression analysis DOC that can decompose. MCF is the CH4 correction factor for
The LFG generation models may rely on some site-specific data aerobic decomposition. F is the CH4 volume concentration in the
on CH4 recovery, emission, and oxidation, which are all impor- gas, 16/12 is the molecular weight ratio of CH4 and C, and 0.714
tant to calibrate or validate the LFG models. Thus, L0 and k can is the CH4 density (0°C, 1 atm)
be determined on the basis of the experimentally determined val-
ues in the landfill, and their feasibility can be determined by com- DOC. Previously research reported that DOC in MSW ranges from
parison of the modelled CH4 generation with the CH4 recovery or 8% to 30% (Bingemer and Crutzen, 1987). It is interesting to note
CH4 generation (Sormunen et al., 2013). This methodology ena- that for the CH4 emission source of landfill in Japan, tsunami sedi-
bles more precise CH4 generation estimates compared with mod- ment is included in that of landfill. Part of the tsunami sediment
els based only on the recovered CH4. generated by the Great East Japan Earthquake, which occurred on
Generally, the Gompertz and logistic models fit better than 11 March 2011, is finally disposed of. Since disposed tsunami sedi-
the first-order equation for experimental values (Nielfa et al., ment includes organic matters, CH4 emissions from this source are
2015). Ware and Power (2017) argued that when actual experi- estimated using the emission factor for wood by expert judgement.
mental data of a CH4 production are available, sigmoidal mod- The carbon content of tsunami sediment (4.5%) is calculated by
els (Gompertz, Richards, Stannard, and logistic models) should multiplying the fraction of organic matter in tsunami sediment by
be applied in order to determine the model of best fit. Park et al. the fraction of carbon contents in the organic matter; assuming the
(2012b) developed two models obtained by differentiating the fraction of organic matter in tsunami sediment finally disposed of is
Modified Gompertz and Logistic models to determine L0 and k 10%, and 45.2% of the fraction of carbon content for wood is sub-
values. The L0 and k values can be determined by regression stituted for tsunami sediment (GIO et al., 2016).
analysis using the two models and actual LFG collection data. Total carbon can be measured with a CHN analyzer. Götze
However, the models need long-term LFG data from landfill to et al. (2016) present an overview of physicochemical waste char-
determine the L0 and k values. Faour et al. (2007) argued that acterization data for individual waste material fractions available
the exponential rise in the gas volume curve is often delayed, in the literature. Figure 1 shows box–whisker plots and the cor-
perhaps as a result of the acclimation of microorganisms, non- responding quantiles for carbon content (Götze et al., 2016). The
optimal gas recovery, or lack of landfill cover. Therefore, the largest data variation for carbon content is found in combustibles
mixed-effects model is developed to account for this lag. There (textiles, rubber, leather, sanitary products, and wood), plastic,
are three parameters in the mixed-effects model, k, L0, and the and food waste.
specific volume of CH4 collected at the end of the lag phase. To measure organic carbon in total carbon, it is necessary to
However, it should be noted that if collected gas data with distinguish between organic carbon and inorganic carbon. Thus,
changing gas collection efficiency over time, rather than gener- sample should be acid washed to eliminate inorganic carbon prior
ated gas data, is used to perform regression analysis, different to analysis (Wang et al., 2015a). This is particularly important for
L0 values can be reached. Furthermore, CH4 emission model- paper samples, because some paper products (e.g., copy paper)
ling has been carried out using LFG extraction data and assump- contain inorganic carbon in the form of CaCO3 as fillers (Wang
tions for extraction efficiency and CH4 oxidation, resulting in et al., 2015a). Mou et al. (2014) used the assumption that 2 mL of
major uncertainties being introduced (Scharff and Jacobs, sulfurous acid (5% H2SO3 solution) was added to approximately
2006). 0.5 g of powder to remove inorganic carbon. An alternative
method for determining organic carbon is the total organic car-
bon (TOC) analyzer. There are numerous methods and variations
IPCC method
of the alternative methods for the quantitation of TOC. The wet
The IPCC (2006) model uses characteristics of the waste (DOC oxidation method is a commonly used approach to determine
and DOCf) and the landfill site (MCF and F) to prediction CH4 TOC content. Among the low-cost and easy-to-use alternative
generation. In the IPCC (2006) model, L0 can be calculated using TOC determinations, spectroscopic techniques such as near-
infrared (NIR) and mid-infrared (MIR) spectroscopy are very
DDOCm = DOC × DOCf × MCF attractive (Wang et al., 2012). In addition, it is necessary to dis-
(8)
tinguish between fossil carbon and biogenic carbon to measure
the DOC. The fossil carbon comes from petroleum-derived prod-
16 ucts such as plastics and synthetic textiles. Biogenic (biodegrad-
DDOCm × F ×
12 (9) able) carbon originates from vegetative and animal matter (e.g.,
L0 =
0.714 food and yard waste, paper, and wood) (De la Cruz et al., 2013;
8 Waste Management & Research 00(0)

is calculated by equation (11), which assumes that waste is a two-


component mixture of modern biogenic carbon with a 14C value
of 115.2±3.5 pMC, and a fossil contribution of 0 pMC. It is based
on fossil fuels having zero radiocarbon, whereas biogenic materi-
als are enriched in 14C, and reflect the 14CO2 abundance of the
ambient atmosphere. The fraction of carbon can be determined
by carbon dating by accelerator mass spectrometry, after convert-
ing the organic carbon in the samples to graphite. The DOC can
be calculated using the following equations:

Fbc ×115.2 + Ff ( 0 ) = Measured pMC value (12)

DOC = TOC × Fraction of biogenic C (13)


Figure 1. Box–whisker plots and data points for carbon
contents in different waste material fractions reported in the
literature (Götze et al., 2016) (C: carbon, TS: total solid). where Fbc represents the fraction of biogenic carbon, Ff repre-
sents the fraction of fossil carbon, and Fbc + Ff = 1.
It should be noted that the 14C contents calculated from Fellner
Moora et al., 2017). The biogenic carbon that is not degraded is and Rechberger (2009) are only used for biogenic waste fractions
stored within the landfill. in 2009. In the future, the radiocarbon content of biogenic matter
Theoretically, the DOC value of waste fractions must be lower will decline, due to a steady decrease of the atmospheric 14CO2
than the TOC value because some organic carbon, such as fossil level. Thus, the 14C contents of biogenic waste fractions gener-
carbon, is non-degradable (De la Cruz et al., 2013). Recently, two ated in the future should be calculated.
different approaches have been established to determine the frac-
tion of biogenic carbon. One of the approaches derives the frac-
DOCf
tion of biogenic carbon from the BMP result (Mou et al., 2014;
Methods for determining DOCf. The parameter DOCf is the
Puyuelo et al., 2011). The DOC can be calculated using (Mou
fraction of DOC that will actually degrade in the landfill. With
et al., 2014):
respect to the DOCf, IPCC (2006) recommends 0.5 of DOCf as
CH 4 recovery = (BMP ×10−3 ) / a default value including lignin, indicating that 50% of the DOC
(10) in the waste is released as gases. In contrast, laboratory studies
(TOC × F ×16 / 12) ×100%
of solid waste decomposition from the United States, Germany,
where BMP is determined via batch tests and presented as kg-CH4 and Italy have shown that the DOCf ranges from negligible to
Mg−1 waste, TOC is presented as % (kg-OC kg−1 waste), F is the a maximum of 0.17–0.47 (Bogner and Matthews, 2003; Bogner
volume fraction of CH4 in generated gas, and 16 and 12 are the and Spokas, 1993; Lornage et al., 2007).
molar masses of CH4 and carbon, respectively, and The DOCf value is dependent on many factors, such as tem-
perature, moisture, pH, and composition of waste. It should be
noted that for laboratory experiments, there are certain difficul-
DOC = CH 4 recovery × TOC (11)
ties in reproducing the real conditions of landfilling (Machado
et al., 2009).
where DOC is presented as % (kg-C kg−1 waste, wet weight). Two different approaches have been established to determine
The other approach is a modern carbon analysis method that the DOCf. In one of the approaches, the extent of decomposition
uses the decay of the radioactive isotope carbon-14 (14C, half- is the measured CH4 yield divided by the yield calculated assum-
life: 5370 years). Biogenic carbon is that which has been recently ing 100% conversion of the cellulose (Cel) and hemicellulose
derived from CO2 in the atmosphere via photosynthesis. Because (H) (and protein in the case of food waste) to CH4 and CO2
14C is present in the atmosphere as a result of the cosmic ray
(Eleazer et al., 1997). The content of cellulose and hemi-cellu-
bombardment of nitrogen, photosynthesis results in the incorpo- lose of waste is well correlated with L0 (Fei et al., 2016).
ration of some 14C into organic matter. While fossil fuel derived According to Wang et al. (2015a), the extent of carbon conver-
organic materials contained 14C at the time of their formation, it sion can be calculated based on carbon loss through the anaero-
has decayed to negligible levels over time. Fellner and Rechberger bic experiment test. The extent of carbon conversion is defined
(2009) suggest a method to determine the 14C content of biogenic as the fraction of the organic carbon converted to CH4 and CO2,
matter in waste, resulting in the radiocarbon content of MSW of which is equivalent to the DOCf as used by the IPCC. The other
115.2±3.5 pMC (percent modern carbon). Thus, De la Cruz et al. approach can be quantified using the ratio of cellulose plus
(2013) carried out a modern carbon analysis method to calculate hemicellulose to lignin (L). Typically, cellulose and hemicellu-
the fraction of biogenic carbon. The fraction of biogenic carbon lose are the major degradable components of MSW (Baldwin
Park et al. 9

et al., 1998). This indicator of decomposition decreases as mate-


rials degrade, due to the biodegradation of cellulose and hemi-
cellulose, and the recalcitrance of lignin under anaerobic
conditions. Lignin is known to be non-degradable in anaerobic
environments, since its initial fragmentation requires molecular
oxygen (Komilis and Ham, 2003). Equation (14) is based on the
assumption that lignin is recalcitrant under anaerobic condi-
tions, thus the amount of lignin is constant over time, i.e.,
MinitialLinitial = MfinalLfinal (Wang et al., 2013b):

DOCf = (M initial Xinitial − M final X final ) / ( M initial Xinitial ) (14)

where Minitial or final is the weight of the initial or final sample and Figure 2. Biogenic carbon content and biogenic carbon
Xinitial or final represents the ratio of cellulose plus hemicellulose decomposition normalized to sample weight as a function of
content (%) in the initial or final excavated sample. (Cel+H)/L (data replotted from De la Cruz et al., 2013) (Cel:
cellulose, H: hemicellulose, L: lignin).
De la Cruz et al. (2013) argued that when normalized to the
initial sample mass, the amount of biogenic C decreases with
decreasing (Cel+H)/L, as shown in Figure 2. A higher (Cel+H)/L DOCf in relation with lignin and moisture. Table 3 pre-
indicates waste with relatively more biodegradable carbon, and sents a literature overview of the DOCf values for individual
also represents fresher waste. As (Cel+H)/L decreases, more of components of MSW. Food waste and grass have a high DOCf,
the biogenic carbon is present as lignin, whereas at high whereas paper, and in particular wood, have a low DOCf within
(Cel+H)/L, more of the biogenic carbon is cellulose and hemicel- the landfill. CH4 generation occurs predominantly from cellulose
lulose. This is because lignin is recalcitrant under anaerobic con- and hemicellulose (Bareither et al., 2012). In contrast, lignin is
ditions that exist in landfills, and therefore limits the bioavailability not easily degraded under anaerobic conditions. Several studies
of cellulose and hemicellulose, which are structurally associated have demonstrated that lignin inhibits cellulose decomposition in
with lignin (De la Cruz et al., 2014). waste, and lignin concentration has been related to both the rate
The cellulose and hemicellulose can be measured based on and extent of cellulose plus hemicellulose degradation (Baldwin
enzymatic neutral detergent fiber (ENDF) and acid detergent et al., 1998; Barlaz, 2006; De la Cruz et al., 2014; Eleazer et al.,
fiber (ADF). ENDF and ADF are gravimetric techniques that 1997; Wang et al., 1994). The higher lignin content in newsprint,
have been used to characterize fiber from a nutritional perspec- which is generally made from mechanical pulp, resulted in the
tive (Barlaz, 2006). The sum of cellulose, hemicellulose, and lowest CH4 yield (Wang et al., 2015a). Greater decomposition
lignin can be determined in accordance with ENDF. The sum of of copy paper with lower lignin content relative to newsprint has
cellulose and lignin fraction can be determined by ADF (Ximenes also been reported in field study (Wang et al., 2013b). Lignin
et al., 2008). However, the gravimetric technique is likely to interferes with the digestion of cell-wall polysaccharides by act-
include some non-cellulosic material as cellulose, and thus may ing as a physical barrier to microbial enzymes (Moore and Jung,
give artificially high results (Barlaz, 2006). A technique is devel- 2001).
oped using high-pressure liquid chromatography (HPLC). The Figure 3 shows that there is a relationship between lignin and
basic procedure is hydrolysis of a solid sample in 72% (w/v) DOCf, although the lignin may be more inhibitory in other compo-
H2SO4, followed by a secondary hydrolysis in 3% (w/v) H2SO4. nents than grass (Barlaz, 2006). For grass, lignified grass tissues
The hydrolyses convert cellulose and hemicellulose to their can be digested to leave only thin-walled indigestible residues
respective monomeric sugars, glucose, xylose, mannose, arab- (Moore and Jung, 2001). Jung and Vogel (1986) demonstrated that
inose, and galactose, which are quantified by HPLC equipped the relationship of lignin with forage digestibility is curvilinear,
with a pulsed electrochemical detector. The eluents are water, and and the inhibiting effect of lignin declined at higher lignin concen-
a solution containing 200 mM sodium hydroxide and 60 mM tration. Additionally, it has been reported that there is an inverse
sodium acetate (Wang et al., 2013b, 2015a). Klason lignin is the relationship between (Cel+L) and the biodegradability of several
most common method utilized to determine lignin. Klason lignin organic wastes (Buffiere et al., 2006). As a consequence, although
is determined by loss on ignition (2 h, 550°C) of the solids it is difficult to draw a definitive conclusion, the lignin content
remaining after the acid hydrolysis. In the Klason lignin method, could be used as an abatement indicator for the DOCf of individual
any organic material that does not dissolve in sulfuric acid will be MSW components.
counted as lignin. However, this method assumes that all non- Most studies have concluded that the most critical factor
cellulosic organic material is lignin, which is not perfectly accu- in landfill decomposition is the amount of moisture in the
rate. Plastics and rubber are likely to be counted as lignin in this waste; if sufficient moisture is not available, then gas forma-
method (Barlaz, 2006). tion will not proceed, and in some cases will not start at all
10 Waste Management & Research 00(0)

Table 3. Literature overview of the DOCf value of each waste.

Reference Wang et al. Wang et al. (2013b) Wang et al. Wang and Eleazer Ximenes
(2011) (2015a) Barlaz (2016) et al. (1997) et al. (2008)
Method The ratio of cellulose plus The ratio of carbon loss from cellulose and hemicellulose
hemicellulose to lignin
MSW – – – – 0.58 –
Grass – – – – 0.76–0.94 –
Leaves – – – – 0.28 –
Branch – – – – 0.28 –
Food – – – – 0.84 –
Hardwood 0.19 0.08–0.19 0.02 – 0.171–0.285 – 0.00–0.17
Softwood 0.05 0.00–0.02 0.12 – 0.000–0.095 – 0.00–0.18
Oriented strand board 0.50 0.08–0.39 0.08–0.38 – – –
Plywood 0.00 0.15–0.19 0.00–0.08 – – –
Particleboard 0.02 0.00–0.14 0.00–0.18 – – –
Medium-density fiberboard 0.00 0.00–0.19 0.00–0.21 – – –
Newsprint – 0.59–0.81 0.69–0.81 0.21–0.29 0.31 –
Corrugated containers – 0.70–0.96 – – 0.54 –
Coated paper – – – – 0.39 –
Copy paper – 0.71–0.95 – (eucalyptus fiber) 0.55 –
0.24
(acacia fiber) 0.96
Magazine Chemical pulp – – – 0.82 – –
Mechanical fiber 0.28

(Baldwin et al., 1998; Hartz and Ham, 1983; Meima et al.,


2008; Micales and Skog, 1997). At low moisture content, which
means below 16%, the biological activities will decrease to zero
(Hartz and Ham, 1983; Meima et al., 2008). Thus, Meima et al.
(2008) presented that the water function is defined as a straight
line, with a water factor (f(w)) of 0.0 at 16%, and a water fac-
tor of 1.0 at complete saturation, which is usually at a water
content (w) of approximately 50%. The water factor can be
calculated using

f ( w ) = 2.76w - 0.44 (15)

The CH4 production rate and maximal cumulative CH4 pro-


duction appear to be linearly correlated to the moisture content Figure 3. Relationship between lignin and DOCf for individual
(Mora-Naranjo et al., 2004; Pommier et al., 2007). Consequently, components of MSW (data replotted from De la Cruz and
there is a linear relationship between the moisture content and Barlaz (2010), Wang and Barlaz (2016), and Wang et al.
(2015a)).
cumulative CH4 production, and the CH4 production has been
predicted based on this linear relationship. Therefore, in order to
This relation is valid up to Tw = 324.6 K, which is the optimum
evaluate DOCf, equation (14) can be used to translate an equation
temperature value for anaerobic thermophilic bacteria. For higher
that is given by DOCf = 2.76w − 0.44 (Chong et al., 2016).
values of up to Tw = 353.15 K, ω is the biodegradable carbon con-
The biogas production depends on the waste temperature.
tent, which practically coincides with the TOC content (Manna
Manna et al. (1999) applied an equation whereby the relation
et al., 1999). However, not considered in detail are the nutrient
between the organic carbon fraction and the total available organic
and inhibitor concentrations, which may also be significant.
carbon fraction is strictly linked to temperature values, as follows:
Inhibitors and nutrients would accumulate and continuously affect
the biochemical reaction processes, causing their effect on the
ω = [0.014 × ( Tw − 273.15 ) + 0.28]ωt (16)
CH4 generation to be overestimated.

where Tw is the absolute temperature value (K), ω is the biode- MCF and F. MCF is defined as the portion of organic materials
gradable carbon content of the waste, and ωt is the TOC content that decompose anaerobically. The default value of MCF for
of the waste. semi-aerobic landfills is set as 0.5, which implies that 50% of
Park et al. 11

organic matter is decomposed aerobically and the remaining 50% should be considered to be lower than 0.5. In contrast, Jeong et al.
is decomposed anaerobically. This means that a semi-aerobic (2015) emphasized that the actual meaning of F is the fraction of
landfill emits just one-half of CH4, compared to an equal size CH4 in the generated gas by the breakdown of organic matter in
anaerobic landfill. Matsufuji et al. (1997) carried out a compari- the absence of oxygen, which implies that the F value for semi-
son of solid waste stabilization between semi-aerobic landfill and aerobic landfill is 0.5.
anaerobic landfill. The results gave the ratio of generated gases to
leached contaminants of 8:2 for the semi-aerobic, and 4:6 for the
anaerobic. Thus based on this result, IPCC (2006) recommend Methods for determining k
MCF of 0.5 as a default value.
Matsuto et al. (2015) emphasized that when considering a
Characteristics of the k value
semi-aerobic landfill as an aerobic landfill technology, the layout The k value is the biodegradation half-life value in years−1 for
of the pipe network should be designed with respect to the pos- landfilled waste. There have been efforts to estimate k value, as
sible air flow paths. Both the leachate collection pipe and the this parameter governs the rate at which CH4 is produced.
passive gas vents are key elements in a semi-aerobic landfill, Although the organic part of each waste type is considered to
because the former functions as a conduit supplying air to the have different decay rates (Thompson et al., 2009), most models
landfill, while the latter functions as an exit for the heated air. assume a single overall value for k.
Thus, it is not necessary to connect the gas vents to the leachate The k value is found to increase with higher moisture contents
collection pipe, because the connection only increases the air and higher temperature (Baldwin et al., 1998; Ishii and Furuichi,
flow through the pipe, and this has little effect on aeration. Jeong 2013). However, Amini et al. (2012) reported similar k values for
et al. (2015) insist that validation of the MCF default value using the wet cell (0.10 yr−1) and traditional landfill (0.08 yr−1), because
field measurement is necessary. A semi-aerobic landfill site can all the study landfills were located in Florida, which has rela-
be in an anaerobic condition when the outflow port of the lea- tively high annual precipitation rates. Barlaz et al. (2010) showed
chate collection system is swamped, the system is full of water, it that there is no apparent relationship between k and the wet
holds retention of leachate, or the leachate collection/gas extrac- weight water content. This is likely due to the heterogeneity of
tion system is not properly extended (GIO et al., 2016). water content in the varying material fractions of waste, as well
The MCF accounts for the factor whereby an unmanaged as uneven wetting due to channelized flow, resulting in a wide
landfill produces less CH4 from a given amount of waste than an range of water contents over the lateral and vertical dimensions
anaerobic landfill (IPCC, 2006). The MCF ranges from 0.4 to of a landfill.
1.0, depending on the landfill condition. Wangyao et al. (2010) The value of k reflects the rate of degradation, and is affected
established that the best fitting values of the CH4 correction fac- by waste depth, density, pH, climate, and moisture content (Levis
tor are 0.65, 0.20, 0.15, and 0.1 for deep landfills, shallow land- and Barlaz, 2011; Machado et al., 2009; Sormunen et al., 2013).
fills, deep dumpsites, and shallow dumpsites, respectively. The The DOCf is also affected by these conditions. Figure 4 shows
MCF values are thus lower than the IPCC default values. the k values associated with DOCf for each waste. The labora-
Govindan and Agamuthu (2014) use 0.8 of MCF, because a study tory-scale k values of MSW components translate into field-scale
landfill is categorized as unmanaged landfill with an amount of k values (Wang and Barlaz, 2016). The field-scale k values are
deep buried waste (more than 5 m depth), and with high water average rates estimated for a traditional landfill scenario (k =
content within the waste. 0.04 yr−1). There is no relationship between k and DOCf.
Most landfill generates a gas with approximately 50% CH4. However, it is interesting to note that grass, which is highly ligni-
Thus, IPCC (2006) suggests that the parameter F refers to the fied, has a high k value and DOCf, whereas office paper with the
fraction of CH4 in generated LFG. However, the fraction of CH4 lowest lignin has a low k value. This suggests that the lignin con-
in generated LFG should not be confused with the measured CH4 centration does not correlate well with the decay rate, presuma-
in gas emitted from the landfill. Losses of CO2 by leachate have bly due to the impact of lignin arrangement and structure on
to be considered, because CO2 is much more soluble in water cellulose bioavailability. This phenomenon can be explained by
than CH4 (IPCC, 2006, Kjeldsen and Fisher, 1995). Absorbed the moisture content of waste. For example, the moisture con-
CO2 might have deposited as carbonates in the drainage layer, tents for food waste and grass are 70% and 60%, respectively (De
since carbonate concentrations in solid, liquid or gas phases are la Cruz and Barlaz, 2010), indicating that high moisture content
dependent on the chemical equilibrium governed by the pH of the may promote the biodegradation process. Moisture provides the
system (Rittmann et al., 2003; Valencia et al., 2009; VanGulck basis for the hydrolysis of organic carbon. According to the pro-
et al., 2003). cesses of degradation and solubilization of organic compounds,
Semi-aerobic landfill does not provide the waste body with an hydrolysis can be regarded as the rate-limiting step within the
adequate delivery of oxygen, which results in only a partial reduc- bio-degradation processes (El-Fadel et al. 1989; Sanders et al.,
tion of methanogenesis. CH4 concentration in LFG from semi- 2000; Trzcinski and Stuckey, 2012).
aerobic landfills decreases to 10–30% (Matsufuji et al.,1993; Another possibility is that the high contents of slowly hydro-
Huang et al., 2008), which means that F for semi-aerobic landfill lysable compounds may delay the whole biodegradation process,
12 Waste Management & Research 00(0)

The US EPA (2004) provides default values based on an


emission factor, which is a k of 0.04 yr−1 above 25 inches (635
mm) of precipitation for emission inventories that are consid-
ered more representative of MSW landfills where no leachate
recirculation is occurring (Faour et al., 2007). On the other
hand, research in some cases has found the US EPA (2004)
default decay rate to be substantially lower (Amini et al. 2012;
Wang et al., 2013a, 2015b). Wang et al. (2013a) maintained
that there is no relationship between annual precipitation and
k value.

Laboratory simulations. Several studies have presented CH4


yield measurements for individual components of MSW to deter-
Figure 4. Relationship between k and DOCf for individual mine their k values (De la Cruz and Barlaz, 2010; Mou et al.,
components of MSW (data replotted from De la Cruz and 2015; Wang and Barlaz, 2016). Mou et al. (2015) suggest that
Barlaz (2010) and Wang and Barlaz (2016)). assuming the organic carbon in the waste follows the FOD
equation,
consequently reducing the k value (Haarstrick et al., 2001). Grass
does not contain a slowly hydrolysable carbon fraction, whereas N t = N0 × e− kt (18)
the slowly hydrolysable carbon fractions are approximately 31%,
45%, and 82% of the total solid carbon in food waste, mixed
the k value can be calculated by
paper, and branches (Komilis, 2006). Barlaz (2006) referenced
that newspaper ink covered cellulose fiber, and reduced its
bioavailability. k = − ln ( N t / N0 ) / t (19)

Classification of methods for where Nt is the quantity (g) of degraded organic carbon (DOC)
determining k after a period of time (t), N0 is the initial quantity (g) of DOC, and
t is the organic carbon degradation time (yr).
The literature describes various methods to measure the k value of Laboratory k values are orders of magnitudes higher than
solid waste. Table 4 presents ranges of k values from solid waste field k values because laboratory conditions are more ideal
landfill, and methods for determining k. In general, k values have (Lamborn, 2012; Fei et al., 2016). Therefore, it is necessary to
been determined by a number of methods: determination of decay develop a correction factor that can be used to adjust lab-scale
rates based on precipitation rates (Kumar and Shama, 2014; k values to match field-scale values (De la Cruz and Barlaz,
Thompson et al., 2009; US EPA, 2004); laboratory simulations 2010; Karanjekar et al., 2015). De la Cruz and Barlaz (2010)
(De La Cruz and Barlaz, 2010; Mou et al., 2015; Wang and Barlaz, presented a correction factor (f) to translate the laboratory-
2016); samples excavated from landfills (Ishii and Furuichi, 2013; scale decay rates (klab,i) of MSW components into field-scale
Kim and Townsend, 2012); and model fitting or regression analy- rates (kfield,i). It is assumed that the weighted average decay rate
sis using actual gas data (Amini et al., 2012, 2013; Machado et al., for a waste mixture is equal to the bulk MSW decay rate. The k
2009; Tolaymat et al., 2010; Wang et al., 2013a). value of waste (kfield,MSW) can be calculated from the weighted
Table 5 presents k values for individual components of MSW. average of the k of each biodegradable component (klab,i), as
Grass and food waste showed a high k value, whereas paper, described in
wood, and low-organic wastes showed a low k. In particular, the
n
low-organic wastes showed lower k values in comparison to the
default k values in the IPCC (Mou et al., 2015). Thus, long-term
k field , MSW = f × ∑k
i =1
lab ,i × ( wt. fraction)i (20)

emissions from landfills are probably attributable to the slowly


degrading paper and wood fraction (Donovan et al., 2010; Pan
k field ,i = f × klab,i (21)
and Voulvoulis, 2007).

Precipitation rates. Garg et al. (2006) indicate that precipitation where i is the ith waste component.
is the most important parameter to estimate the k value. Thus, the Karanjekar et al. (2015) published a multiple linear regres-
k value for a bulk waste can be calculated based on precipitation sion (MLR) equation from laboratory data for estimating a cor-
rates (US EPA, 2004): rection factor. The MLR equation is considered the effect of
annual rainfall and ambient temperature for estimating the k
( )
k = 3.2 ×10−5 × annual precipitation in mm + 0.01 (17) value.
Park et al. 13

Table 4. k values at landfill level taken from the literature, and corresponding determination methods.

Landfill site Method k (yr−1) References


Metropolitan center landfill in Salvador, Model fitting with 0.200 Machado et al.
Brazil calculated L0 (2009)
Outer Loop landfill, USA 0.060 (traditional landfill) Tolaymat et al.
0.110 (bioreactor) (2010)
Jeram landfill, Bulk waste approach 0.080 Govindan and
Selangor, Waste composition 0.090 Agamuthu (2014)
Malaysia approach
USA 9 landfills Model fitting with SSE 0.090–0.170 Wang et al. (2013a)
2 landfills minimization at varied 0.040
L0
USA 9 landfills Model fitting with SSE 0.070–0.190 Wang et al. (2015b)
2 landfills minimization 0.040
USA 3 landfills Model fitting with 0.050–0.350 Barlaz et al. (2010)
Smiths Creek Septage bioreactor assumed L0 0.296 Zhao et al. (2013)
landfill in Leachate bioreactor 0.082
Michigan, USA
Landfills in Florida, USA Model fitting with 0.080 (traditional landfill) Amini et al. (2012)
R2 maximization at 0.100 (bioreactor)
Landfills, USA A calculated L0 0.060 Amini et al. (2013)
B 0.090
C 0.040
Shanghai landfill, China Aged-defined 0.060 Youcai et al. (2001)
North Central Alachua County waste samples and 0.470 Kim and Townsend
Florida, USA Southwest landfill regression (bioreactor) (2012)
New River Regional 0.210
landfill (bioreactor)
Sudokwon landfill site 1, Korea Nonlinear regression 0.100–0.140 Park et al. (2012b)
Wet landfills Three landfills using field data 0.280 Faour et al. (2007)
SSWMC 0.210
Landfill A 0.110
CSWMC 0.120
21 landfills 0.300
Canada British Columbia Annual precipitation 0.048 Thompson et al.
Alberta rate 0.023 (2009)
Ontario 0.037
Quebec 0.042
Nova Scotia 0.056
23 metro cities, India 0.030–0.080 Kumar and
Sharma (2014)

Aged-defined waste samples and regression. This approach is (Kim and Townsend, 2012). Second, sampling of age-defined
to collect samples of landfilled waste, and then measure their bio- wastes from the study landfill site is conducted. The waste com-
degradability of waste as a function of waste age (Ishii and position, moisture, volatile matter and ash contents, and meth-
Furuichi, 2013; Kim and Townsend, 2012). As biodegradability ane generation potential are analyzed, as shown in Figure 6. In
is a surrogate for landfilling age, lower biodegradability would the third step, the k values for each type of wastes are estimated
be expected in older samples. The biodegradability of waste is using time series data on the methane generation potential (Ishii
typically evaluated using the BMP. An advantage to this approach and Furuichi, 2013). The methane generation potential of waste
compared to using gas collection data is that the efficiency of the is Pt at t years after landfilling, which means that the remaining
in-place gas collection system does not influence the results (Kim methane generation potential of waste can be described by the
and Townsend, 2012). This approach consists of three steps, as FOD equation:
shown in Figure 5.
First, working reports of the landfill site are investigated to Pt = P0e− kt (22)
predict the composition of the landfilled waste, the annual
amount of landfilled waste, and the distribution of landfilled where Pt is the methane generation potential of waste at t years
waste over space and time (Ishii and Furuichi, 2013). Sample after landfilling, P0 is the methane generation potential of waste
age can be estimated from landfill waste placement records at 0 years after landfilling, and k is the methane generation rate
14 Waste Management & Research 00(0)

Table 5. k values for individual waste components taken from the literature.

Country Component Method k (yr−1) References


Hokkaido, Paper Aged-defined waste samples 0.050 Ishii and
Japan Kitchen waste and regression 0.062 Furuichi (2013)
France Paper-cardboards 0.110 Francois et al.
(2006)
4 landfills, Combustible Half-life time using lab test 0.024–0.025 Mou et al.
Denmark Shredder 0.016–0.017 (2015)
Sludge 0.16–0.19
Mixed bulky 0.013–0.014
Street cleansing 0.070
USA Textile Multiplying the laboratory- 0.015–0.088 De la Cruz and
Wood scale rates with a correction 0.007–0.045 Barlaz (2010)
Food waste factor 0.072–0.432
Leaves 0.085–0.512
Grass 0.149–0.895
Branches 0.007–0.045
Miscellaneous organics 0.066–0.393
Newspaper 0.017–0.099
Office paper 0.015–0.088
Coated paper 0.061–0.365
Corrugated containers/ 0.010–0.059
Kraft bags
Mixed paper 0.016–0.094
USA Hardwood 0.027–0.048 Wang and
Softwood 0.000–0.127 Barlaz (2016)
USA Yard waste Model fitting with calculated L0 0.082 Yazdani et al.
by minimizing the SSE (2012)
France Paper and cardboard Evolutions of organic fractions 0.200 Lefebvre et al.
with age (2007)
Thailand Food waste Model calibration with 0.347 Wangyao et al.
Papers calculated L0 using IPCC 0.069 (2010)
Wood default values 0.035
Textiles 0.069
Italy Mechanically-biologically Linear regression using a two- 0.039 De Gioannis
pretreated waste stage model et al. (2009)
Italy Mechanically-biologically Linear regression using a two- 0.308 Di Maria et al.
pretreated waste stage model (2013)

constant (year−1). Figure 7 shows the curve-fitted lines obtained it is predominantly soil, this fraction’s contribution to overall
using equation (22) to determine the k value. CH4 yield can be considered.
A disadvantage of this approach is the relatively heterogene- Biodegradability-test methods that are based on the use of
ous nature of MSW samples collected in the field. Furthermore, aerobic respiration indices have been recently reviewed for
given that biodegradable waste components (e.g., food waste, waste biodegradability assessment. In contrast to the BMP test,
paper) typically become reduced in size as waste stabilization the aerobic biodegradability tests do not assess the ultimate
progresses, simple separation of the fine fraction to remove soil methane yield of a sample, but rather its activity. Thus, these
prior to the BMP may be problematic (Kim and Townsend, aerobic biodegradability tests could not determine the L0 value
2012). For this reason, Kim and Townsend (2012) suggest the of a sample. The basic principle of the test for the biodegradabil-
procedure presented in Figure 8. Identifiable biodegradable ity estimation is the amount of carbon that can be mineralized.
components can be processed and analyzed separately from Accordingly, aerobic biodegradability tests have been proposed
large, non-biodegradable components and soil, thus providing a to overcome the limits of anaerobic biodegradability tests. These
more accurate and repeatable measurement of this important aerobic biodegradability tests measure the respiration activity
fraction. The intermediate fraction (0.042–0.475 cm), often rich using the oxygen (O2) consumption or the amount of carbon
in degraded organic wastes (similar to compost), can similarly dioxide (CO2) that is released under aerobic conditions. Although
be homogenized without the interference of soil or other non- these tests are conducted under aerobic conditions, they are cur-
biodegradable wastes. Finally, the fine fraction (<0.042 cm) can rently used to assess the methane production potential of waste
be tested, and although the CH4 yields are typically low because under anaerobic conditions. A good correlation has been found
Park et al. 15

Figure 7. Curve fittings for the methane generation potential


(Ishii and Furuichi, 2013).

Model fitting or regression analysis using actual gas data. The


k value can be determined on the basis of the experimentally
determined values in the landfill, and the feasibility of these val-
Figure 5. Schematic of aged-defined waste samples and ues can be determined by comparison of the modelled CH4 gen-
regression. eration with the measured CH4 recovery or CH4 generation
(Sormunen et al., 2013). Garg et al. (2006) suggest a fuzzy model
to estimate the k value. Four major parameters, of precipitation,
temperature, waste biodegradability, and landfill depth, are used
as inputs to the model. The model indicates that precipitation is
the most weighted parameter. However, the model does not con-
sider differences in waste composition.
Mathematical models are normally built to fit a wide range
of data and circumstances. These models need to be validated
with measured or observed data to verify the results generated.
For this reason, calibration of numerical values for k by site-
specific data is reported to be essential when applying FOD
models to estimate whole-site LFG generations (Amini et al.
2012; Scharff and Jacobs, 2006; Sormunen et al., 2013). To find
Figure 6. Changes in the methane generation potential (Ishii
the optimal set of gas generation parameters, error function
and Furuichi, 2013).
analysis is used. This entails the minimization of the difference
between the calculated gas generation rates and the actual rates
between the anaerobic and aerobic tests for the characterization to determine the optimal set of gas generation parameters, using
of the biodegradability of solid wastes (Binner and Zach, 1999). error function for statistical analysis (Wangyao et al., 2010).
The aerobic tests offer the advantage of lesser time consumption Estimation of k for a landfill can be carried out by the estimated
compared with the anaerobic tests, and they can be implemented L0 in conjunction with k value by curve fitting of the collected
with all kinds of waste (Kallel et al., 2003; Lesteur et al., 2010). LFG data with minimizing the sum of squared errors (SSE) or
However, complex organic matter including cellulose is not R2 near one for the modeled vs. measured data (Amini et al.,
taken into account in the aerobic tests (Lesteur et al., 2010). 2012, 2013; Tolaymat et al. 2010; Wang et al., 2013a, 2015b). It
The (Cel+H)/L ratio is often used to assess refuse decomposi- should be noted that when the k value is estimated using field
tion. This ratio is unaffected by the presence of inert material data, errors in the used L0 can significantly affect the estimates
(e.g., soil, ceramic, and glass), does not depend on visual identi- of k, as shown in Figure 10.
fication of waste materials, and decreases as waste degrades
(Bareither et al., 2012; Mehta et al., 2002; Wang et al., 1994;
Wang et al., 2013b). Fresh waste typically has a (Cel+H)/L ratio
of between about 3 and 4 (Barlaz, 2006). Figure 9 shows that the
Summary and conclusion
amount of biogenic carbon increases with increasing (Cel+H)/L. This review highlights current approaches for determining L0
A regression analysis of the (Cel+H)/L with waste age has a coef- and k values with their wide ranges from detailed experiments
ficient of determination (R2) of 0.55, and the R2 of biogenic car- conducted within bulk MSW and individual waste components.
bon is 0.67. In addition, the degradation coefficient for waste Tables 6 and 7 compare different methods for determining L0
sample is approximately 0.16 yr−1. and k.
16 Waste Management & Research 00(0)

Figure 8. Schematic of the sample preparation process prior to BMP test (Kim and Townsend, 2012).

Figure 9. (Cel+H)/L ratio and biogenic carbon content for


samples excavated from Outer Loop landfill (data replotted Figure 10. Effect of the assumed L0 on the estimated k value
from De la Cruz et al., 2013). (Tolaymat et al., 2010).

The L0 values in field settings are lower, because landfills do calculations are very fast, taking only a few hours, whereas the
not function as efficiently as anaerobic digesters or laboratory application of results obtained from these methods to a full-scale
experiments. Thus, the L0 should be used to refer to the CH4 yield, landfill remains difficult, because they do not account for varia-
i.e., the amount of CH4 produced per unit mass of waste under tions brought about by climatic and operational events.
actual anaerobic conditions within a landfill. L0 estimates in the Laboratory experiments are better controlled, and employ
literature are highly varied, and have been derived from theoreti- operating procedures to enhance microbial activity. For these rea-
cal stoichiometric calculations, laboratory experiments, or actual sons, laboratory experiments produce more predictable results,
field measurements from landfill. Theoretical stoichiometric compared to field monitoring studies. However, the BMP test
Park et al. 17

Table 6. Comparison of different methods for determining L0..

Method Description Advantages Drawbacks


Stoichiometric - use a stoichiometric - simple and easy to analyze -n o distinction between biodegradable and
methods equation based on the - take only a few hours non-biodegradable matter
chemical composition of -d o not account for variations brought about
the waste by climatic and operational events
- overestimate CH4 potential
Experimental -u
 se BMP value of mixed - provide a more predictable - BMP value is similar to DOC
methods waste based on the result, compared to field - overestimate CH4 potential compared to
weighted average of waste monitoring studies full-scale data
components - can determine L0 - require a correction factor
for individual waste - limited in reproducing the real conditions
components of landfilling
Model fitting -u
 se site-specific data - can determine accurate - need long-term LFG data
or regression on CH4 recovery and site-specific L0 - need assumptions for CH4 oxidation
analysis emission
IPCC method -u
 ses characteristics of the - s imple and easy to - needs to distinguish between fossil carbon
waste (DOC and DOCf) and determine L0 and biogenic carbon to measure DOC
landfill site (MCF and F) - needs to analyze DOCf for individual waste
components

Table 7. Comparison of different methods for determining k.

Method Description Advantages Drawbacks


Precipitation rate -u
 ses US EPA equation based - simple and easy to - does not account for differences
on precipitation rates determine k value in landfill conditions (waste
composition, temperature, cover soil)
Laboratory simulations -u se regression analysis of - can determine k values - overestimates k values compared to
obtained laboratory biogas for individual waste field k values
data components - need to adjust lab-scale k values
Aged-defined waste -u ses time series data on the - can determine site- - heterogeneous nature of MSW
sample and regression biodegradability of waste specific k value samples
Model fitting or - use curve fitting of collected - more accurate site- - need long-term LFG data
regression analysis LFG data specific k value -e  rrors in the used L0 can significantly
using actual gas data - can be validated with affect the estimates of k
measured LFG data

could not provide direct estimation of L0. The BMP value can be of DOC needs to distinguish between organic carbon and inorganic
assumed equal to the DOC, because the BMP value generally carbon, resulting from acid washed to eliminate inorganic carbon
represents the ultimate amount of CH4 produced under optimal prior to analysis. BMP or modern carbon analysis methods of
anaerobic conditions. waste components may be the most direct estimations of DOC.
The FOD model parameters are highly dependent on environ- The DOCf is the measured CH4 yield divided by the yield calcu-
mental conditions and the capture efficiency. Significant differ- lated assuming conversion of 100% of the cellulose and hemicel-
ences exist between the conditions in the laboratory experiments, lulose (and protein in the case of food waste) to CH4 and CO2. In
and the landfills. For this reason, if LFG collection data are avail- addition, the (Cel+H)/L ratio is often used to assess DOCf.
able, calculating site-specific L0 from model fitting or regression Although the content of lignin of waste is correlated with DOCf,
analysis is recommended as the best approach. However, most further studies are required to assess the relationship between
authors in the literature associate the problem with the lack of lignin and DOCf for individual waste components.
long-term LFG data. Thus, more data from full-scale landfills are In the literature, the k value has been determined by precipi-
needed with complete data sets that provide descriptions of gas tation rates, laboratory simulations, aged-defined waste sam-
collection systems, gas quality and quantity, waste placement ple, and model fitting or regression analysis using actual gas
rates, and moisture conditions. Moreover, data from the analyzed data. Precipitation is the most important parameter to estimate
sites should be updated, since currently very few sites have such the k value. Thus, the k value for a bulk waste can be calculated
data available. using the US EPA equation based on precipitation rates.
The IPCC model uses characteristics of the waste (DOC and However, this equation does not account for differences in
DOCf) and the landfill site to predict CH4 generation. Determination landfill conditions.
18 Waste Management & Research 00(0)

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Declaration of conflicting interests Chong YG, Park JK, Kim IH, et al. (2016) A study on the determination
The authors declared no potential conflicts of interest with respect to methodologies of fraction of degradable organic carbon (DOC) and frac-
tion of DOC decomposed (DOCF) for estimating methane emissions from
the research, authorship, and/or publication of this article.
solid waste landfills. Journal of Korea Society of Waste Management 33:
38–45.
Funding De Gioannis G, Muntoni A, Cappai G, et al. (2009) Landfill gas generation
The authors disclosed receipt of the following financial support for after mechanical biological treatment of municipal solid waste: estima-
tion of gas generation rate constants. Waste Management 29: 1026–1034.
the research, authorship, and/or publication of this article: This work
De la Cruz FB and Barlaz MA (2010) Estimation of waste component-
was supported by a National Research Foundation of Korea (NRF)
specific landfill decay rates using laboratory-scale decomposition data.
grant funded by the Korea government (MSIP) (grant number Environmental Science & Technology 44: 4722–4728.
2016R1A2B4011548). De la Cruz FB, Chanton JP and Barlaz MA (2013) Measurement of carbon
storage in landfills from the biogenic carbon content of excavated waste
samples. Waste Management 33: 2001–2005.
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Jin-Kyu Park https://orcid.org/0000-0002-6831-1054 ing anaerobic decomposition of hardwood, softwood, and old newsprint
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