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Methane Generation Potential
Methane Generation Potential
Methane Generation Potential
review-article2018
WMR0010.1177/0734242X17753532Waste Management & ResearchPark et al.
Review Article
model: a review
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).
(Continued)
4 Waste Management & Research 00(0)
Sormunen et al.
degradable compounds (fibers, humic, and fulvic acids) (Batstone
References
(2013)
(2011)
can be estimated using the following general equation (Raposo
et al., 2011):
component specific CH4 generation
B0 = 415 × %Carbohydrates +
(3)
Waste composition and waste-
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)
18–20
123.9
115
100
76
95
87
L0a
B0 × BF
L0 = (4)
1+ w
–
–
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.
et al., 2009).
–
–
–
as follows:
–
–
–
21 landfills
Landfill A
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.
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)
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)
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)
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
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)
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)
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.
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.
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 8. Schematic of the sample preparation process prior to BMP test (Kim and Townsend, 2012).
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
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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