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Bioresource Technology 102 (2011) 8828–8834

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Enhancing the solid-state anaerobic digestion of fallen leaves through


simultaneous alkaline treatment
Lo Niee Liew, Jian Shi, Yebo Li ⇑
Department of Food, Agricultural, and Biological Engineering, The Ohio State University/Ohio Agricultural Research and Development Center, 1680 Madison
Ave., Wooster, OH 44691-4096, United States

a r t i c l e i n f o a b s t r a c t

Article history: Previous studies have shown that alkali pretreatment prior to anaerobic digestion (AD) can increase the
Received 2 May 2011 digestibility of lignocellulosic biomass and methane yield. In order to simplify the process and reduce the
Received in revised form 28 June 2011 capital cost, simultaneous alkali treatment and anaerobic digestion was evaluated for methane produc-
Accepted 6 July 2011
tion from fallen leaves. The highest methane yield of 82 L/kg volatile solids (VS) was obtained at NaOH
Available online 14 July 2011
loading of 3.5% and substrate-to-inoculum (S/I) ratio of 4.1. The greatest enhancement in methane yield
was achieved at S/I ratio of 6.2 with NaOH loading of 3.5% which was 24-fold higher than that of the con-
Keywords:
trol (without NaOH addition). Reactors at S/I ratio of 8.2 resulted in failure of the AD process. In addition,
Anaerobic digestion
Dry fermentation
increasing the total solid (TS) content from 20% to 26% reduced biogas yield by 35% at S/I ratio of 6.2 and
Alkali pretreatment NaOH loading of 3.5%. Cellulose and hemicellulose degradation and methane yields are highly related.
Biogas Ó 2011 Elsevier Ltd. All rights reserved.
Leaves

1. Introduction (Taherzadeh and Karimi, 2008). Alkaline pretreatment greatly im-


proves the digestibility of lignocellulosic biomass through lignin
Due to concerns about the sustainability of petroleum supplies, solubilization, removal of hemicellulose, disruption of interlinking
the research community is evaluating alternative resources for ester bonds, and neutralization of structural carboxylic acids
fuels and energy production. Lignocellulosic biomass, such as en- (Mosier et al., 2005). In addition, alkalis help to prevent a drop of
ergy crops, agricultural residue and municipal solid waste, is a pH during the subsequent acidogenesis process and increase the
promising renewable resource because it is widely available and efficiency of methanogenesis (Hashimoto, 1986; Pavlostathis and
can be converted to various forms of fuel and energy. Biogas, which Gossett, 1985). However, alkaline pretreatment performed at low
contains about 60–70% methane, can be obtained from the anaer- moisture and ambient temperature is particularly attractive. In a
obic digestion (AD) of organic materials. However, due to the recal- study conducted by Pang et al. (2008), a 48.5% increase in biogas
citrant structure and composition of lignocellulosic biomass, such was achieved from corn stover pretreated with 6% NaOH at 80%
as lignin that interlinks cellulose and hemicellulose layers, the con- moisture content for 3 weeks at ambient temperature. In a parallel
version efficiency is limited (Noike et al., 1985). Hydrolysis of lig- study, a 72.9% increase in total biogas yield was achieved with low-
nocellulosic biomass is rate-limiting because of the low er NaOH loading (2%) and shorter pretreatment time (3 days),
cellulolytic activity and low specific growth rate of cellulolytic mi- when pretreatment moisture content was increased to 88% (Zheng
crobes in anaerobic digesters (Lu et al., 2007). Therefore, pretreat- et al., 2009). Recently, Zhu et al. (2010) reported that anaerobic
ment is often required to overcome biomass recalcitrance in order digestion of alkaline pretreated corn stover produced 37% more
to facilitate the access of hydrolytic enzymes to degradable carbo- biogas compared with untreated corn stover. The pretreatment
hydrates to improve sugar release and biogas production. was carried out with 5% NaOH at 53% moisture content for 1 day
AD efficiency of lignocellulosic biomass can be improved by at ambient temperature. These studies indicate that alkaline pre-
applying several pretreatment methods including steam, acid, treatment of lignocellulosic biomass is feasible with lower mois-
alkaline, and biological treatments (Penaud et al., 1999; Frigon ture content. However, pretreatment effectiveness is greatly
et al., 2011). Alkaline pretreatment is often favored for anaerobic affected by moisture content, NaOH loading, and pretreatment
digestion and sodium hydroxide (NaOH) was found to be one time.
of the most effective alkalis for improving biogas production Solid-state anaerobic digestion (SS-AD) refers to an AD process
operated at total solids (TS) content of 20–55%. It has been used
⇑ Corresponding author. Tel.: +1 330 263 3855. to digest the organic fraction of municipal solid waste in Europe
E-mail address: li.851@osu.edu (Y. Li). (Bolzonella et al., 2003). SS-AD is well suited to handle

0960-8524/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.07.005
L.N. Liew et al. / Bioresource Technology 102 (2011) 8828–8834 8829

lignocellulosic biomass and problems encountered in liquid AD, Table 1


such as floating and stratification of solids, can be avoided in Characteristics of leaves and inoculum.

SS-AD (Chanakya et al., 1993). Compared to liquid AD (TS less than Parameter Leaves Inoculum
15%), SS-AD has advantages such as less energy needed for heating, Total solids (%) 91.6 ± 0.0 6.2 ± 0.0
finished materials with higher TS content (20%), and no moving Volatile solids (%) 85.1 ± 0.0 4.0 ± 0.0
parts in the digester (Li et al., 2011). However, it requires large Total carbon (%) 45.4 ± 0.2 2.7 ± 0.0
amounts of inoculum, longer retention time, and nitrogen supple- Total nitrogen (%) 0.9 ± 0.0 0.5 ± 0.0
Carbon to nitrogen (C/N) ratio 51.9 ± 1.8 5.5 ± 0.2
mentation when lignocellulosic biomass is used (Jewell et al., pH 6.8 ± 0.1 8.0 ± 0.0
1993; Li et al., 2011). Furthermore, pretreatment is generally Alkalinity (g CaCO3/kg) 3.5 ± 0.0 8.9 ± 0.1
required for lignocellulosic biomass to improve the efficacy of Total volatile fatty acid (g/kg) 1.5 ± 0.1 3.3 ± 0.1
SS-AD (Li et al., 2011). Pretreatment methods, such as alkaline Water soluble extractives (%) 25.7 ± 0.4 N/D
Ethanol soluble extractives (%) 7.3 ± 0.3 N/D
treatment prior to the AD process, have previously been established
Cellulose (%) 11.1 ± 0.4 N/D
to increase the digestibility of lignocellulosic biomass and methane Hemicellulose (%) 11.5 ± 0.1 N/D
yield in SS-AD systems (Zhu et al., 2010). However, to our knowl- Lignin (%) 22.7 ± 0.6 N/D
edge, no successful results have been reported on the simultaneous
ND, not determined.
alkaline treatment and SS-AD of lignocellulosic biomass.
Simultaneous alkaline treatment and digestion offers several
benefits compared with alkaline pretreatment followed by diges-
tion. It can simplify the operation by eliminating a separate reactor 2.2. Solid-state anaerobic digestion with simultaneous NaOH
required for alkaline pretreatment and reducing material handling. treatment
Additionally, the increase in alkalinity may help prevent a drop in
pH during acidogenesis, which can create a more stable environ- Oven-dried and ground leaves were mixed thoroughly with an
ment for the methanogenic bacteria (Pavlostathis and Gossett, appropriate amount of inoculum effluent and NaOH pellets (pre-
1985). However, excessive NaOH loading may inhibit anaerobic dissolved in effluent) to achieve three S/I ratios (on VS basis) at
digestion either due to high pH or sodium ion toxicity (Rinzema 4.1, 6.2, and 8.2, with NaOH concentrations of 2%, 3.5%, and
et al., 1988). A recent study by Zhu et al. (2010) tested simulta- 5%(on basis of dried leaves) for each S/I ratio (a total of 9 condi-
neous NaOH treatment and SS-AD of corn stover at a C/N ratio of tions). Reactors without any NaOH addition were run in parallel
18 and NaOH loading of 5%. However, no significant improvement at each S/I ratio as controls. The C/N ratios were 18, 22, and 25,
in biogas production was observed compared with untreated corn at S/I ratios of 4.1, 6.2, and 8.2, respectively. Deionized water was
stover. Appropriate NaOH loading needs to be established such then added, when necessary, to obtain a TS content of 20%. Mixed
that it is sufficient for delignification while not inhibiting the AD materials were loaded into 1-L glass reactors. Reactors were sealed
process. Furthermore, as the amount and activity of inoculum with a rubber stopper, and placed in a walk-in incubator for
greatly affect methane yield and retention time for SS-AD (Raposo 30 days at a constant temperature of 37 °C and without agitation.
et al., 2006; Li et al., 2010), NaOH loading needs to be adjusted with Biogas generated was collected using a 5-L gas bag attached to
substrate-to-inoculum (S/I) ratio during simultaneous alkaline the outlet of the reactor (CEL Scientific Tedlar gas bag, Santa Fe
treatment and SS-AD. Fallen leaves (leaf litter) are potentially a Springs, CA, USA) and biogas composition and volume were mea-
low cost feedstock for SS-AD because a tipping fee is normally sured daily for the first 15 days and every 2 days afterwards. Dupli-
charged for collection and hauling of such wastes from residential cate reactors were run at each condition.
or commercial areas. The objectives of this study were to deter-
mine the effect of NaOH loading and S/I ratio on daily and cumula- 2.3. Analytical methods
tive methane production during SS-AD of leaves. Changes in total
volatile fatty acids (VFA), alkalinity, and pH were measured and The extractive content of leaves and materials taken from the
correlated to methane yield. In addition, degradation of cellulose reactor at the beginning and end of the AD process was measured
and hemicellulose during SS-AD was investigated and compared according to the NREL Laboratory Analytical Procedure (Sluiter
to methane yield to verify the effect of NaOH treatment. et al., 2008). Extractive-free solid fractions were further fraction-
ated using a two-step acid hydrolysis method based on NREL Lab-
2. Methods oratory Analytical Procedure (Sluiter et al., 2010). Monomeric
sugars (cellobiose, glucose, xylose, galactose, arabinose, and man-
2.1. Feedstock and inoculum nose) in the acid hydrolysate were measured by HPLC (Shimadzu
LC-20AB, Columbia, MD, USA) equipped with a Biorad Aminex
Fallen leaves were collected from the campus of the Ohio Agri- HPX-87P column and a refractive index detector (RID). Deionized
cultural Research and Development Center (OARDC) in Wooster, water at a flow rate of 0.6 ml/min was used as the mobile phase.
OH, USA (40°480 3300 N, 81°560 1400 W) in October 2009. Leaves were The temperatures of the column and detector were maintained at
dried at 40 °C for 72 h in a convection oven (Shel Lab FX28-2, Shel- 80 °C and 55 °C, respectively.
don Manufacturing, Cornelius, OR, USA) to achieve a moisture con- The TS and VS contents of leaves, inoculum, and digestate were
tent of less than 10% before storing in an air tight container. Prior measured at the beginning and end of the AD process according to
to use, oven-dried leaves were ground through a 9 mm sieve with a the Standard Methods for the Examination of Water and Wastewa-
grinder (Mighty Mac, MacKissic Inc., Parker Ford, PA, USA). Effluent ter (APHA, 2005). Total carbon and nitrogen contents were deter-
from a mesophilic liquid anaerobic digester, which was fed food mined by an elemental analyzer (Elementar Vario Max CNS,
processing waste and operated by quasar energy group (Wooster, Elementar Americas, Mt. Laurel, NJ, USA). Total volatile fatty acids
OH, USA), was used as the inoculum for SS-AD. Due to the low TS (VFA) and alkalinity were measured using a 2-step titration meth-
content, the effluent was dewatered by centrifugation. TS content od (McGhee, 1968). Samples for pH, total VFA, and alkalinity mea-
increased from 3.9% to 6.1% after dewatering. Characteristics of surement were prepared by diluting a 5-g sample with 50 ml of
leaves and inoculum are shown in Table 1. Structural carbohydrate deionized water and subsequently filtering it using cheese cloth.
and lignin contents of leaves are based on dry matter, whereas the The filtrate was then analyzed using an auto-titrator (Mettler
rest of the values are based on total weight. Toledo, DL22 Food & Beverage Analyzer, Columbus, OH, USA).
8830 L.N. Liew et al. / Bioresource Technology 102 (2011) 8828–8834

The total VFA/alkalinity ratio was calculated to determine the risk 3.5% NaOH loading. Increasing the NaOH loading from 3.5% to 5.0%
of acidification, a measure of the process stability (Lossie and Pütz, resulted in decreased methane yield. The most significant
2010). The volume of biogas collected in a Tedlar bag was mea- improvement in total methane yield was at S/I ratio of 6.2 with
sured with a drum-type gas meter (Ritter, TG 5, Bochum, Germany) an increase in NaOH loading from 2.0% to 3.5%. When no NaOH
and the composition of biogas (CO2, CH4, N2 and O2) was analyzed was added, increasing the S/I ratio from 4.1 to 6.2 resulted in upset
using a GC (Agilent Technologies, HP 6890, Wilmington, DE, USA) of the AD process with about 3.0 L/kg VS of total methane pro-
equipped with a 10-ft stainless steel column 45/60 Molecular Sieve duced. Addition of NaOH at loading rates of 2.0%, 3.5%, and 5.0%
13X and a Thermal Conductivity Detector. Helium gas at a flow rate significantly improved biogas yield and the total methane yield
of 5.2 ml/min was used as a carrier gas. The temperature of the was increased by 9-, 24-, and 21-fold, respectively, compared to
detector was set at 200 °C. The temperature of the column oven the control. The maximal enhancement (24-fold) in biogas yield
was initially programmed at 40 °C for 4 min, elevated to 60 °C at was achieved with 3.5% NaOH loading at which a total methane
20 °C/min, and held for 5 min. The sodium ion (Na+) concentration yield of 72.6 L/kg VS was obtained. However, it was not signifi-
in the digestate was analyzed by Inductively Coupled Plasma-Mass cantly different (P > 0.05) from that with 5.0% NaOH addition
Spectrometry (ICP-MS) (Agilent 7500, Agilent Technologies, Wil- (63.6 L/kg VS). When the S/I ratio was increased to 8.2, SS-AD failed
mington, DE, USA). Samples for ICP-MS analysis were prepared to produce methane at 0%, 2.0%, and 3.5% NaOH loading. Although
by digestion using a microwave digester (MARSXpress™, CEM Cor- a methane yield of 37.3 L/kg VS was obtained at 5.0% NaOH load-
poration, Matthews, NC, USA) programmed with a 15-min ramp- ing, it was much lower than that at S/I ratios of 4.1 and 6.2. This
up time to 200 °C and was then maintained at 200 °C for 15 min. indicates that simultaneous NaOH treatment not only improves
methane yield but also helps to mitigate the risk of process failure
2.4. Statistical analysis caused by high S/I ratios. Zheng et al. (2009) also observed a signif-
icant increase in methane yield with NaOH addition at higher corn
Statistical significance was determined by analysis of variance stover loading.
(ANOVA) using SAS software (Version 8.1, SAS Institute Inc., Cary, Daily methane yields during SS-AD of leaves at S/I ratios of 4.1
NC, USA) with a threshold p-value of 0.05. and 6.2 are shown in Fig. 2. At S/I ratio of 4.1, the control showed
no clear peaks and daily methane yields remained at a level of
3. Results and discussion 3–5 L/kg VS during the initial 20 days. However, daily methane
production for reactors subjected to 2.0% and 3.5% NaOH loading
3.1. Biogas production demonstrated obvious maximal peaks of 9.5 L/kg VS at day 3 and
8.4 L/kg VS at day 6, respectively. However, at 5.0% NaOH loading,
Fig. 1 demonstrates the effect of simultaneous NaOH treatment peak methane yield of 9.4 L/kg VS did not occur until day 15.
on total methane yield during 30-day SS-AD at different S/I ratios. Although, high NaOH loading helped to enhance the digestibility
The S/I ratio is a critical factor affecting SS-AD performance. In gen- of leaves, it is speculated that high levels of sodium ions and lignin
eral, SS-AD requires higher inoculum levels than liquid AD. Reduc- degradation compounds may inhibit metabolic activity of microor-
ing the amount of inoculum allows better reactor efficiency; ganisms, especially methanogens (Rinzema et al., 1988). For liquid
however, it may result in an increase in the accumulation of VFA AD, the inhibitory Na+ concentration was reported in a range of 3 to
and lead to reactor upset (Li et al., 2011). For SS-AD without NaOH 6.5 g Na+/L (Rinzema et al., 1988). The Na+ concentration in this
addition, only S/I ratio of 4.1 gave good total methane yields among study ranged from 1.0 g/kg at 1% NaOH loading to about 6.7 g/kg
the three tested S/I ratios, while at S/I ratios of 6.1 and 8.1, total at 5.0% NaOH loading. Although the inhibitory Na+ level for
methane yields were very low, indicating failure of the AD process. SS-AD has not been reported previously, inhibition due to high so-
In general, simultaneous NaOH treatment improved total methane dium ions concentration was likely to occur for reactors operated
yield for anaerobic digestion of leaves at all S/I ratios. at 5.0% NaOH. The lag phase of methane production with 5.0%
At S/I ratio of 4.1, NaOH additions of 2.0%, 3.5%, and 5.0% caused NaOH addition is probably caused by the high initial pH and high
an increase in methane yield of 11.7%, 21.5%, and 4.0%, respec- concentration of sodium salt of fatty acid due to the fast conversion
tively. The highest methane yield of 81.8 L/kg VS was attained with of carbohydrates.

Fig. 1. Effect of S/I ratio and NaOH loading on total methane yield (digestion time: 30 days, TS: 20%).
L.N. Liew et al. / Bioresource Technology 102 (2011) 8828–8834 8831

Fig. 2. Effect of NaOH loading on daily methane yield at S/I ratios of (a) 4.1 and (b) 6.2 (digestion time: 30 days, TS: 20%).

As presented in Fig. 2b, daily methane yield at S/I ratio of 6.2, significantly decreased methane yield especially at low NaOH load-
shows different patterns compared with S/I ratio of 4.1 (Fig. 2a). ings. Methane yield in control reactors was less than 3.0 L/kg VS for
Overall, much lower daily yields were achieved for reactors with both 20% and 26% TS. Fig. 3 also shows that simultaneous NaOH
S/I ratio of 6.2. The control reactor without NaOH addition had very treatment in SS-AD improved methane yield; however, at 26% TS,
low methane yields during the 30-day period indicating reactor the methane yield was much lower than that at 20% TS. A highly
failure. Simultaneous alkaline treatment at different NaOH load- acidic environment (pH 5.5–6.6, data not shown) caused by VFA
ings improved methane production, although a long lag phase accumulation may have inhibited the methanogenic bacteria at
was observed for all reactors especially for those with 3.5% and high TS contents. Similar results were reported indicating that
5.0% NaOH loadings. The peak for daily methane production was methane yield decreased about 17% when TS increased from 20%
delayed to between day 11 to 15 for 3.5% and 5.0% NaOH loading, to 30% during anaerobic digestion of the organic fraction of muni-
respectively, while the methane yield for reactors with 2.0% NaOH cipal solid waste (OFMSW) (Fernandez et al., 2008).
loading only peaked on day 27. We speculated that the accumula-
tion of VFA in reactors with S/I ratio of 6.2 created a highly acidic 3.2. Variation of pH, total volatile fatty acids (VFA) and alkalinity
environment (pH < 6, Fig. 4a) inhibiting the methanogenic bacteria
and causing failure of the reactor (Penaud et al., 1999). The delay in Imbalances of hydrolytic, fermentative, acetogenic, and metha-
methane production at NaOH loading of 3.5% and 5.0% could also nogenic functions during anaerobic digestion can lead to reactor
be a result of the dynamic transition of methanogen populations failure and low methane yield. For example, accumulation of VFA
to adapt to acidic conditions (Delbès et al., 2001; Hori et al., 2006). could result in a dramatic drop in pH, subsequently inhibiting
We also investigated the effect of total solid (TS) loading on methanogenic bacteria and disrupting the performance of anaero-
methane yield. Fig. 3 shows that increasing TS from 20% to 26% bic digestion. Thus, pH and total VFA are common stress indicators
8832 L.N. Liew et al. / Bioresource Technology 102 (2011) 8828–8834

final pH dropped to 5.3 and 6.6 (below 7.4) for reactors at no or


2% NaOH loadings, respectively. This observation indicated failure
in the AD process, which is in agreement with data shown in Fig. 1
that the biogas production was low at no or 2% NaOH loadings. It is
also noted that at S/I ratio of 6.2, the final pH of the digestate at 5%
NaOH loading was lower than that of the digestate at 3.5% NaOH
loading, probably due to the higher total VFA in the digestate.
Not surprisingly, the final pH for all reactors operated at S/I ratio
of 8.2 was below 7.4, which was associated with SS-AD process
failure as indicated by no or low biogas production as shown in
Fig. 1.
In addition to pH measurement, both total VFA and alkalinity
were determined since pH is not a sole indicator of AD failure (Ahr-
ing et al., 1995; Lahav and Morgan, 2004). The stability criterion for
anaerobic digestion is often expressed by the ratio of total VFA to
the buffering capacity measured as alkalinity – total VFA/alkalinity
Fig. 3. Effect of NaOH loading and TS content on total methane yield (digestion
time: 30 days, S/I ratio: 6.2).
ratio (Koch et al., 2010). Although the optimal total VFA/alkalinity
ratio of each AD reactor is unique, a ratio of 0.3–0.4 is generally
regarded as optimal for liquid AD and a ratio exceeding 0.6 is
used for monitoring AD operation (Ahring et al., 1995; Lahav and regarded as indicative of overfeeding (Lossie and Pütz, 2010). As
Morgan, 2004). Fig. 4a shows the initial and final pH of batch mode shown in Fig. 4b, the initial total VFA/alkalinity ratio during
reactors during 30-day SS-AD. The initial pH values of all reactors, start-up of all reactors was approximately 0.5. The initial total
which ranged from 7.5 to 9.1, were above the operational pH of 7.4 VFA/alkalinity ratio of reactors without alkali addition was found
recommended by Lahav and Morgan (2004). Fig. 4a also shows that to be higher (ranging from 0.7 to 1.0) compared to reactors with
pH was maintained above 7.4 during SS-AD at S/I ratio of 4.1 which NaOH addition. Final total VFA/alkalinity ratios of all healthy reac-
indicates a ‘‘healthy’’ AD system. However, at S/I ratio of 6.2, the tors (with total methane yield above 60.0 L/kg VS) were however at

(a)

(b)

Fig. 4. Initial and final (a) pH and (b) total VFA/alkalinity ratios for reactors with different NaOH loading and S/I ratio (digestion time: 30 days, TS: 20%).
L.N. Liew et al. / Bioresource Technology 102 (2011) 8828–8834 8833

(a)

(b)

Fig. 5. Effect of NaOH loading on reduction of (a) cellulose and (b) hemicellulose (digestion time: 30 days, TS: 20%, S/I ratio: 6.2).

or below 1.6 in this study which was higher than the limit of 0.6 for Cellulose and hemicellulose reduction was negligible for the con-
liquid AD. At S/I ratio of 8.2, total VFA/alkalinity ratios measured, at trol, which was in line with the very low methane yield observed
the end of 30-day SS-AD were substantially higher than the recom- at this condition. Substantial cellulose and hemicellulose degrada-
mended ratio, which indicates failure of SS-AD. The failure was tion were observed for reactors with 2.0%, 3.5%, and 5.0% NaOH
likely caused by accumulation of organic acids due to overfeeding. loadings. However, not much difference was observed between
Simultaneous NaOH treatment at 3.5% and 5.0% NaOH not only 3.5% and 5.0% NaOH loading. The highest cellulose degradation
helped to improve the digestibility of leaves but also increased of 36.0% and hemicellulose degradation of 34.9% were observed
the buffering capacity of the digester to maintain suitable pH and at 3.5% NaOH loading, and were in agreement with the highest
total VFA/alkalinity ratio, thus leading to higher biogas production methane production at this condition. Lignin degradation in
compared with no or low NaOH loadings. leaves was not significant (P > 0.05) for the control and 2.0%
NaOH reactors but was significant in reactors with 3.5% and
3.3. Degradation of cellulose and hemicellulose 5.0% NaOH loading (data not shown). The higher delignification
of lignocellulosic biomass at these conditions was correlated with
Table 1 shows the composition of leaves. Compared with other the higher methane yield and degradation of cellulose and
lignocellulosic biomass, such as corn stover, leaves have extractive hemicellulose.
content of about 33.0% of the TS. Lignin content (22.7%) of the
leaves was comparable to other typical biomass; however, the cel- 4. Conclusions
lulose (11.1%) and hemicellulose (11.5%) contents were lower com-
pared to corn stover as reported elsewhere (Zhu et al., 2010). Due NaOH addition not only contributes to the delignification of lig-
to the relatively low cellulose and hemicellulose contents, the nocellulosic biomass but also improves the buffering capacity of
methane potential (81.8 L/kg VS) of leaves obtained in this study SS-AD by increasing the alkalinity. The highest methane yield of
was lower than corn stover (Zhu et al., 2010). 81.8 L/kg VS was obtained at S/I ratio of 4.1 with 3.5% NaOH load-
Fig. 5 illustrates cellulose and hemicellulose degradation dur- ing, which was in agreement with the highest cellulose (36.0%) and
ing 30-day SS-AD at S/I ratio of 6.1, comparing the initial and final hemicellulose (34.9%) degradation observed at this condition. At
compositions. In general, higher methane yield was obtained in S/I ratio of 4.1, methane yield was not significantly (P > 0.05) im-
reactors having higher cellulose and hemicellulose degradation. proved by the NaOH addition. However, enhancement of methane
8834 L.N. Liew et al. / Bioresource Technology 102 (2011) 8828–8834

yield of 9- to 24-fold was observed with NaOH addition at S/I ratio Lahav, O., Morgan, B.E., 2004. Titration methodologies for monitoring of anaerobic
digestion in developing countries – a review. J. Chem. Technol. Biotechnol. 79,
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Li, L., Yang, X., Li, X., Zheng, M., Chen, J., Zhang, Z., 2010. The influence of inoculum
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