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Short Communication
Simple and rapid methods to evaluate methane potential and biomass yield for
a range of mixed solid wastes
P. Shanmugam *, N.J. Horan
Public Health and Environmental Engineering, School of Civil Engineering, University of Leeds, Leeds, LS2 9JT, UK
a r t i c l e
i n f o
Article history:
Received 13 December 2007
Received in revised form 30 May 2008
Accepted 5 June 2008
Available online xxxx
Keywords:
Empirical formula
Biochemical/stoichiometric methane
potential
C/N ratio
Adenosine tri-phosphate
Biomass yield
a b s t r a c t
This paper describes rapid techniques to evaluate the methane potential and biomass yield of solid
wastes. A number of solid wastes were mixed to provide a range of C:N ratios. Empirical formulae were
calculated for each waste based on the results of chemical analysis and these formulae were used to estimate the COD equivalent and stoichiometric methane potential (SMP). The actual COD and biochemical
methane potential (BMP) were determined experimentally for each waste and for both parameters there
was a good agreement between the empirical and experimental values. The potential of adenosine triphosphate (ATP) to act as an indicator of biomass yield (mg VSS mg1 COD removed) was determined
during the anaerobic digestion process. The biomass yield determined from ATP analysis was in the range
0.010.25 mg VSS mg1 COD removed which corroborated well with previously reported studies. Empirical formula based SMP together with ATP measurement were shown to provide rapid methods to replace
or augment the traditional BMP and VSS measurements and are useful for evaluating the bioenergy and
biomass potential of solid wastes for anaerobic digestion.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
The techniques used in UK for disposing of solid wastes are
changing rapidly and largely as a result of the Landll Directive,
biodegradable waste is now being diverted away from landll. This
Directive requires that by July 2010 biodegradable municipal
waste (BMW) going to landll shall be reduced to 75% of its
1995 tonnage, rising to 35% of this by 2020 (Defra, 2007). Diversion
is also being aided by increases in land ll tax, currently around
22/T. Other drivers that contribute to this change include climate
change and the potential scal rewards from the Renewable Obligation Certicates (ROCs). As a result a large tonnage of biodegradable waste stream previously sent to landll now requires dealing
with by other means. The opportunity to convert this waste to energy is obviously an attractive one and current technologies for
achieving energy from waste focus on biological and thermal options. The biological route is essentially the application of anaerobic digestion (AD) which is able to reduce the amount of volatile
solids in a waste feed by up to 70%, whilst at the same time generating a source of renewable energy as methane. The Department of
Environment, Food and Rural affairs (Defra, 2007), has estimated
that the potential annual market for anaerobic digestion is 400
0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.06.027
Please cite this article in press as: Shanmugam, P., Horan, N.J., Simple and rapid methods to evaluate methane potential and biomass yield
for ..., Bioresour. Technol. (2008), doi:10.1016/j.biortech.2008.06.027
ARTICLE IN PRESS
2
2. Methods
2.1. Characterisation of solid wastes
A number of solid waste sources were used in this study. Municipal solids waste (MSW) was collected in bulk and autoclaved at
130 C to permit storage without deterioration. Leather eshing
(LF) and primary chemically treated sludge (LS) were collected
from the tannery efuent treatment plant at Holmes Hall tannery
in Hull. The leather eshing was minced and homogenised with
a commercial blender to 6 mm diameter before feeding to the digester. Wastewater treatment sludge included primary sedimentation tank sludge (PST), mixed liquor from a sequencing batch
reactor (SBR), and surplus activated sludge (ASP) were collected
from the Knostrop wastewater treatment plant at Leeds. The characterisation of total solids (TS), and volatile solids (VS) were carried
out using Standard Methods (APHA, 1998). Elemental analysis of
carbon, hydrogen, nitrogen and sulphur was undertaken using
CHNS analysers Model Thermo Flash EA 1112 series. Samples were
oven dried at 103 C and then combusted at 1800 C in the CHNS
analyser in a steam of helium with measured amount of oxygen.
This produces N2, CO2, H2O, and SO2 which are then separated
and quantied by gas chromatography using a 5 mm diameter
steel (length of 2 m) packed column, helium carrier gas with a ow
rate of 40 mL/min, detected with a Propack model TCD.
2.2. Development of empirical formula for stoichiometric methane
potential (SMP)
From the calculated values of C, H, N, and O an empirical formula
was computed for each solid waste following the procedure developed by Rittmann and McCarty (2001) and Hansen (2005). This formula was used to determine the COD equivalent of which permitted
the calculation of the stoichiometric methane potential (SMP).
2.3. Biochemical methane potential (BMP) assessment
The BMP was determined in anaerobic batch reactors of 500 ml
capacity Duran bottles with hermetically sealed stoppers and con-
Please cite this article in press as: Shanmugam, P., Horan, N.J., Simple and rapid methods to evaluate methane potential and biomass yield
for ..., Bioresour. Technol. (2008), doi:10.1016/j.biortech.2008.06.027
ARTICLE IN PRESS
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Leather eshings
ASP sludge
SBR sludge
Leather sludge
PST sludge
MSW
1.
2.
3.
4.
5.
6.
7.
8.
21.9
81.3
35.5
9.4
11.2
25.3
0.6
18.7
0.9
70.3
37.6
5.7
7.0
20.1
0.5
29.7
0.4
62.0
28.3
5.1
4.2
24.5
0.8
38.0
21.5
81.5
39.9
6.4
3.5
31.6
1.3
18.5
3.8
60.3
28.7
4.6
2.4
24.7
0.5
39.7
41.7
63.0
27.5
3.8
1.3
30.5
0.4
37.0
Table 2
Empirical formula, and anaerobic process evaluation for a range of solid wastes
Solid waste
Empirical formula
C:N
Leather eshing
ASP sludge
SBR sludge
Chemical sludge
PST sludge
MSW
C4H11NO2
C6H11NO2
C8H17NO5
C13H26NO8
C14H26NO9
C25H41NO21
3.2
5.4
6.7
11.4
14.0
21.6
3540
4147
4266
2722
3490
4371
9163
6039
7997
7477
5703
6821
1296
241
466
999
305
414
0.09
0.14
0.14
0.01
0.12
0.25
stance poor VS removal efciency and low biogas yield are often
associated with low C/N, high NH3N, high VFA and low digester
buffering capacity (Haandel and Lettinga, 1994; Anderson et al.,
2003). In addition, the concentration of ATP is known to indicate
both the cell viability and the metabolic status of a microorganism
and it has been used to predict biomass levels in anaerobic digestion (Chu et al., 2001; Yu et al., 2002; Kim et al., 2007). In order to
establish the potential of ATP as a simple performance monitor,
ATP concentration was measured over the duration of the BMP
test, together with a number of physical parameters that indicate
reduced performance. By monitoring a range of solid waste types
with differing C/N ratios it was hoped that a clear picture would
emerge as to the status of ATP, as an indicator of reactor stability
and performance. C/N ratio was selected as the variable parameter
because it determines both the NH3N and VFA concentration observed in the digester. Increasing NH3N helps to raise the pH,
whereas by contrast an acid pH is governed by VFAs which neu2
tralise HCO
and acetate ions. However ammonia can be
3 , CO3
toxic: Callaghan et al. (2000) and Salminen and Rintala (2002) have
reported the tolerance level of NH3 in anaerobic digesters acclimatised to treat high protein wastes as 11.6 g L1 and 6.0 g L1,
respectively.
Of the six solid wastes evaluated, the cumulative biogas yield
after 28 days was highest for MSW and the lowest for leather eshing, in line with the C:N ratios for these wastes (Fig. 1 and Table 2).
The maximum NH3N concentration of 1296 mg L1 was also recorded for the leather eshing but this is well below the concentration reported as inhibitory. Alkalinity was in the range of 3800
9700 mg L1 and the maximum alkalinity was coincident with high
NH3N levels (Table 2). The VFA was observed to peak at around 8
days for SBR, ASP and MSW wastes, whereas for LF it was as late as
20 days suggesting that a much longer digester retention time
would be required for this waste (Fig. 2). The late decrease in
VFA was also coincided with high alkalinity. ATP was measured
at a concentration in the range of 2.018.43 mg L1 and similar values have been reported by others, for instance Hwang and Hansen
(1998), Yu et al. (2002), and Chen (2004). The ATP level for LF, ASP,
SBR, LS, PST, and MSW were 2.01, 4.21, 3.22, 2.12, 3.22, and 8.43,
respectively, and observed as linear with respect to cumulative
methane yield measured during the BMP test (Table 2), thus demonstrating the potential value of this parameter. Standard BMP test
can be used to estimate biokinetics design constants. Future work
Please cite this article in press as: Shanmugam, P., Horan, N.J., Simple and rapid methods to evaluate methane potential and biomass yield
for ..., Bioresour. Technol. (2008), doi:10.1016/j.biortech.2008.06.027
ARTICLE IN PRESS
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References
3000
Biogas (N mL)
2500
SBR
ASP
PST
Chemical Slud
Leather Fl
MSW
2000
1500
1000
500
0
0
10
20
30
Days Elapsed
40
9000
SBR Sludge
ASP sludge
PST Sludge
Chemical Sludge
MSW
LF
8000
VFA (mg/L)
7000
6000
5000
4000
3000
2000
1000
0
0
10
20
30
Elapsed time (Days)
40
Fig. 2. The volatile fatty acids (VFA) levels at elapsed time during the BMP test.
Anderson, G.K., Sallis, P., Uyanik, S., 2003. Anaerobic treatment processes. In: Mara,
D.D., Horan, N.J. (Eds.), Handbook of Water and Wastewater Microbiology.
Academic Press, New York, pp. 391423.
APHA, 1998. Standard Methods for the Examination of Water and Waste Water,
20th ed. American Public Health association, American Water Works
Association Water Pollution control Federation, Washington, DC.
Chen, H., 2004. ATP content and biomass activity in sequential anaerobic/aerobic
reactors. J. Zhejiang Univ. Sci. 5 (6), 727732.
Chung, Y.C., Neetheling, J.B., 1988. ATP as a measure of anaerobic sludge digester
activity. J. Water Pollut. Control Fed. 60 (1), 107112.
Chu, C.P., Lee, D.J., Chang, B.V., Liao, C.S., 2001. Using ATP bioluminescence
technique for monitoring microbial activity in sludge. Biotechnol. Bioeng. 75
(4), 469474.
Callaghan, F.J., Wase, D.A.J., Thayanithy, K., Forster, C.F., 2000. Continuous codigestion of cattle slurry with fruit and vegetable wastes and chicken manure.
Biomass Bioenerg. 27, 7177.
Chung, Y.C., Neethling, J.B., 1989. Microbial activity measurement for anaerobic
sludge digestion. J. Water Pollut. Control Fed. 61 (3), 343349.
Defra, 2007. Department of Environment Food Rural affair and Agriculture. UK
Waste Strategy.
Davidsson, A., Christopher Gruvberger, B., Thomas, H., Christensen, C.T., Lund
Hansen, C., Jes, L., Cour, J.C., 2007. Methane yield in sourcesorted organic
fraction of municipal solid waste. Waste Manage. 27, 406414.
Environment Agency, 2005. Guidance on Monitoring MBT and Other Pretreatment
Processes for the Landll Allowances Schemes. UK (England and Wales)
Erickson, L.E., 1978. Application of Mass and energy balance regularities to product
formation. Biotechnol. Bioeng. 20, 15951621.
Erickson, L.E., 1980. Biomass elemental composition and energy content.
Biotechnol. Bioeng. 21, 451456.
Gosset, J., Belser, R., 1982. Anaerobic digestion of waste activated sludge. J. Env. Eng.
108, 11011120.
Haandel, A.C., Lettinga, G., 1994. Anaerobic Sewage Treatment A Practical Guide
for Regions with Hot Climate. John Wiley and Sons.
Han, S.K., Kim, S.H., Kim, H.W., Shin, H.S., 2005. Pilot-scale two stage process: a
combination of acidogenesis and methanogenesis. Water Sci. Technol. 52 (12),
131138.
Hansen, T.L., 2005. Quantication of environmental effects from anaerobic
treatment of sourcesorted organic house hold wastes, Ph.D. Thesis
September 2005. Institute of Environment & Resources, Technical University
of Denmark, Lyngby.
Hwang, S., Hansen, C.L., 1998. Evaluating a correlation between volatile suspended
solid and adenosine 50 tri phosphate levels in anaerobic treatment of high
organic suspended solid wastes water. Bioresour. Technol. 63, 243250.
Kim, K., Lee, C., Shin, S.G., Hwang, S., 2007. Correlation of microbial mass with ATP
and DNA concentrations in acidogenesis of whey permeates. Biodegradation.
Online.
Lin, J.G., Ma, Y.S., Chao, A.C., Huang, C.L., 1999. BMP tests on chemically pretreated
sludge. Bioresour. Technol. 68, 187192.
Mendez, M.S., Lema, J.M., 1993. Methanogenic and non-methanogenic activity tests.
Theoretical basis and experimental set up. Water Res. 27 (8), 13611376.
Owen, W.F., Stuckey, D.C., Healy, J.B., Young, L.Y., McCarty, P.L., 1979. Bioassay for
monitoring biochemical methane potential and anaerobic toxicity. Water Res.
13, 485492.
Rittmann, B.E., McCarty, P.L., 2001. Environmental Biotechnology Principles and
Applications, second ed. McGraw Hill Publications.
Salminen, E.A., Rintala, J.A., 2002. Semi-continuous anaerobic digestion of solid
poultry slaughterhouse waste: effects of hydraulic retention time and loading.
Water Res. 36, 31753182.
Shelton, D.R., Tiedje, J., 1984. General method for determining anaerobic
biodegradation potential. Appl. Environ. Microb. 47 (4), 850857.
Tchobanoglous, G., Burton, F.L., David Stensel, H.D., 2005. Waste water engineering
treatment and reuse. In: Metcalf, Eddy (Eds.), Civil Engineering Series, fourth ed.
McGraw Hill. International editions..
Wook, K.W., Hwang, S., 2000. Mechanical pre-treatment of waste activated sludge
for anaerobic digestion process. Water Res. 34 (8), 23622368.
Yu, Y., Hansen, C.L., Hwang, S., 2002. Biokinetics in acidogenesis of highly suspended
organic wastewater by adenosine 50 triphosphate analysis. Biotechnol. Bioeng.
78 (2), 147156.
Please cite this article in press as: Shanmugam, P., Horan, N.J., Simple and rapid methods to evaluate methane potential and biomass yield
for ..., Bioresour. Technol. (2008), doi:10.1016/j.biortech.2008.06.027