i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 3 2 8 8 e1 3 2 9 5

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Effect of the initial total solids concentration and initial pH

on the bio-hydrogen production from cafeteria food waste
Carlos Ramos a,b, German Buitron a,*, Ivan Moreno-Andrade a, Rolando Chamy b
a

Laboratory for Research on Advanced Processes for Water Treatment, Unidad Academica Juriquilla, Instituto de Ingeniera,
Universidad Nacional Autonoma de Mexico, Blvd. Juriquilla 3001, 76230 Queretaro, Mexico
b
Biochemical Engineering School, Pontificia Universidad Catolica de Valparaso, General Cruz 34, Valparaso, Chile

article info

abstract

Article history:

In this paper, the influence of the initial pH and the total solids (TS) concentration on

Received 28 February 2012

hydrogen production from the organic fraction of cafeteria food waste at mesophilic

Received in revised form

conditions in batch reactors was determined. It was found that the yield and specific

13 June 2012

hydrogen production rate were influenced by the initial pH and the initial total solids

Accepted 15 June 2012

concentration. The highest hydrogen production rate, 2.90 mmolH2/d, was obtained at

Available online 15 July 2012

90 gTS/L and a pH of 5.5. Under this condition, the TS and chemical oxygen demand (COD)
removal were the lowest (10% as TS and 14% as COD). However, considering the specific

Keywords:

values, the highest specific degradation rate (192.2 mLH2/gVSremoved/d) was obtained with

Biological hydrogen production

the lowest TS concentration and an initial pH of 7.0. It was found that the influence of the

Initial pH

TS concentration on hydrogen production was more significant than that of the initial pH

OFUSW

for this type of residues.

Total solids concentration

Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights

Food waste

1.

Introduction

Currently, there is great interest in hydrogen (H2) production

as a clean fuel because, during its combustion, only water is
produced as a by-product and because hydrogen has a high
specific energy content (33.3e39.4 kWh/kg) compared with
those of other fuels [1]. Hydrogen is an alternative to
conventional fossil fuels, which can be produced by steam
reforming, electrolysis, gasification and biological processes.
Because fossil fuel processing and water electrolysis are
expensive, the biological production of hydrogen is more cost
effective, particularly when organic wastes can be used [2].
The application of the hydrolytic-acidogenic stage of the
anaerobic digestion process is a viable alternative to produce
hydrogen and to obtain an effluent rich in dissolved organic
matter composed of volatile fatty acids (VFA), primarily acetic,
propionic and butyric acid, lactate and solvents (acetone and

reserved.

ethanol). In this case, H2 production is an economically viable

process due to the possibility of using a wide variety of nonexpensive residues as the organic fraction of municipal
solids waste (OFUSW) [3e5].
The OFUSW include fruit- and vegetable-based market
waste, uneaten food and food preparation leftovers from
residences and restaurants and organic residues from industrial food production. The OFUSW is a significant environmental problem, particularly in large cities in developing
countries, where the typical disposal method is using a sanitary landfill or open dumping, due primarily to their simplicity
and low cost [6]. For this reason, the use of this waste can
reduce the environmental problem with the valorization of
products as hydrogen.
The initial total solids (TS) concentration affects hydrogen
production in several ways [7]. A high initial TS content can limit
the mass transfer between the substrate and microorganisms,

* Corresponding author. Tel.: 52 442 1926165; fax: 52 442 1926185.

E-mail address: gbuitronm@ii.unam.mx (G. Buitron).
0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.06.051

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which reduces the hydrogen production [8]. In addition, the

initial concentration of the substrate may result in inhibition of
H2-producing bacteria due to an increase in volatile fatty acids
production. It has been observed that hydrogen production from
OFUSW at mesophilic temperatures (34e37  C) is influenced by
the initial pH, initial total suspended solids and inoculum
characteristics [8e12].
The optimal initial TS concentration to obtain hydrogen
depends on the composition of the residue, the type and
configuration of the reactors and the activity of the biomass.
The initial TS values used by several authors varied from 1.3 to
50 g/L [9e16]. It has been reported that as the initial TS
increased, the hydrogen production also increased until
a variable maximal concentration was reached, which
depended on the residues characteristics [12e18]. However, it
was observed that the yield of hydrogen production varied
when different initial TS were used [12e17]. Relatively low TS
concentration have been reported for residues from cafeteria
[19] or they are used mixed with night soil sludge and sewage
sludge from a wastewater treatment plants [16]. Because
diluting OFUSW demands fresh water, it is worthwhile to
investigate the potential in using higher TS concentrations
than those that have already been studied and without the
addition of co-substrates.
Selecting a proper pH is also crucial to enhance hydrogen
production due to the effects of pH on the hydrogenase
activity or metabolic pathways. Fan et al. [20] and van Ginkel
et al. [21] have reported that the maximum hydrogen yield
occurred at a pH value of 5.5, whereas Lee et al. [22] reported
that the maximum hydrogen yield was achieved at an initial
pH of 9.0. Davila-Vazquez et al. [17] found that the maximum
hydrogen yield occurred with an initial pH of 7. These conflicting results seem to be due to a lack of buffering capacity
that would prevent the pH from decreasing. From a practical
point of view, it is important to investigate how the initial pH
influences the hydrogen production when no pH control is
used during fermentation.
In this study, the influence of the initial pH and high total
solids concentration on hydrogen production from the organic
fraction of cafeteria food waste at mesophilic conditions in
batch reactors was determined.

2.

Materials and methods

2.1.

Inoculum

Anaerobic granular sludge obtained from an upflow anaerobic

sludge blanket reactor treating brewery wastewater was used
as the inoculum after thermal conditioning as described
by [23].

2.2.

Waste characteristics

The OFUSW was obtained from the cafeteria at the JuriquillaUNAM campus. The waste was collected once a week and
refrigerated at 4  C for preservation. In each collection, bones
and inert material (paper and plastic) were discarded; only the
fermentable matter was preserved. After selecting the waste,
it was crushed and homogenized in a blender. Finally, the

waste was frozen until it was used. The characteristics of the

OFUSW used in this study are presented in Table 1.

2.3.

Experimental procedure

A batch reactor with a useful volume of 150 mL was used in

this study (glass Schott bottles, 300 mL of total volume). To
help purge the biogas, the reactors were mixed using an
orbital mixer (150 rpm) at a constant temperature of 36  C
during a reaction time of 2.1 d. Different total solids concentrations were used: 1, 5, 10, 40 and 90 g/L. To evaluate the
influence of the initial pH, each batch bottle was adjusted
using 0.1 N HCl or 0.1 N NaOH until an initial pH of 5.5, 6.0 and
7.0 was obtained. The pH was fixed at the beginning of the test
and decreased as fermentation in the batch reactors occurred.
It has been reported that alkalinity affects the hydrogen
production [24]. Thus, a nutrient stock solution containing the
following components (per liter) was used to ensure a proper
level of alkalinity: 200 g of NH4HCO3, 100 g of KH2PO4, 10 g of
MgSO47H2O, 1.0 g of NaCl, 1.0 g of Na2MoO42H2O, 1.0 g of
CaCl22H2O, 1.5 g of MnSO47H2O, and 0.278 g of FeCl2. A
nutrient stock solution with a volume of 0.5 mL was added to
the batch bottles. Each reactor was inoculated with 4 g of pretreated anaerobic sludge as inoculum; therefore, the initial
inoculum concentration in the reactor was 26.7 g/L of TS. The
chemical oxygen demand (COD) was quantified at the beginning of the test. During the experiments, the biogas produced
was measured at regular interval times. After the biogas
production ceased (2.1 d), the pH, biogas composition (H2, CH4
and CO2), total and dissolved COD, total solids, volatile solids,
sulfate, lactate and volatile fatty acid (acetic and propionic
acids) concentrations were quantified.

2.4.

Kinetic analysis

To evaluate the cumulative hydrogen production in response

to the different conditions, a kinetic analysis was conducted
using the modified Gompertz Equation (1) as described by [23].
The experiments were conducted in triplicate.



2:71828  Rmax l  t
1
Ht Hmax  exp  exp
Hmax

(1)

Here, H(t) (mL) represents the total amount of hydrogen

produced at time t (h); Hmax (ml) represents the maximal
amount of hydrogen produced; Rmax (mL/h) is the maximum
hydrogen production rate, and l (h) represents the lag time.

Table 1 e Characterization of the OFUSW used in this

study.
Parameter
Moisture, %
TS Wet basis, %w/w
VS Wet basis, %w/w
Density, g/L
NH3eN, g/L
CODtotal, g/L
pH
Average of five tests  standard deviation.

Value
79.12  0.19
20.88  0.24
19.48  0.22
805.04  0.20
0.65  0.15
140.55  11.78
4.6e5.0

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2.5.

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Analytical methods

Quantification of the biogas produced was achieved through

the use of an automated system for biogas measurement and
monitoring [25]. The equipment is based on manometric
measurements of the biogas produced during the fermentation of the test substances in closed bioreactors. After each
measurement, the system is purged, compensating the
reactor pressure to the atmospheric pressure. Hydrogen,
carbon dioxide and methane were analyzed with a gas chromatograph (Agilent 6890N) equipped with a thermal conductivity detector following the methodology reported in Ref. [23].
Lactate was determined by ion chromatography using a Dionex ICS-1500 chromatograph that used an REIC IonPac AS23
250  4 mm column. The eluent consisted of a mixture of
0.8 mM NaHCO3 and 4.5 mM Na2CO3 using an isocratic flow at
1 mL/min and 30  C. An anion suppressor current of 25 mA
was used. Ammonia (NeNH3) and the COD were quantified
with a HACH kit. The TS and volatile solids (VS), as
well as alkalinity, were determined according to standard
methods [26].

3.

Results and discussion

3.1.

Hydrogen production

Fig. 1A shows the molar hydrogen production as a function of

the total solids concentration of the OFUSW and the initial pH.
A clear, direct relationship was observed; the hydrogen
production increased as the substrate concentration
increased. In general, the highest hydrogen production was at
a pH of 7.0, except with a concentration of 90 g/L, where
1.21 mmol was produced.
The volumetric yields (YH2 ) were evaluated considering the
total solids added and the fraction of the removed VS, as presented in Fig. 1B and C, respectively. An inverse relationship
was found between the hydrogen yield and total solids
concentration. The highest values were observed for the lowest
TS concentration. However, this analysis does not represent
the potentially available substrate due to hydrolysis. Hydrolysis is normally rate-limiting if the substrate is in a particulate
form, which is the case for the OFUSW [27]. Thus, the availability of fermentable substrate for hydrogen-producing
bacteria will depend on the hydrolysis rate. When the data
are analyzed by removing the VS (Fig. 1C), two sets of results
depending on the initial TS concentration were observed: first,
for 1 gTS/L and second, for higher initial TS concentrations. In
the case of 1 gTS/L, a maximal yield of 25.3 mLH2/gVSremoved
was found. The increase in total solids concentration, from 1 to
5 g/L, produced a decrease in YH2 , which was similar for each
initial pH. However, the hydrogen production yield presented
a gradual increase as the TS concentration increased from 5 to
90 gTS/L; the trend was similar for the three pHs studied. The
highest hydrogen yield observed in the case of the lowest TS
concentration could be because there exists a good distribution
of the inoculum and the substrate, minimizing any local
shortages of nutrients and diluted potential toxins [28]. As the
concentration increased five-fold (5 gTS/L), the distribution of

Fig. 1 e Hydrogen production as a function of total solids

concentration of the OFUSW and pH. A) molar production,
B) volumetric yield considering the added TS and C)
volumetric yield considering the removed VS.

the inoculum-substrate was not as good as in the more diluted

TS concentration. However, as the TS concentration increased,
the availability of the substrate was higher, allowing the
reproduction of hydrolytic microorganisms and increasing the
bioavailability of the OFUSW for hydrogen-producing microorganisms. Thus, as the dissolved substrate increased, the
hydrogen yield increased [29].

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It has been reported that the yield obtained from several

agricultural wastes [30] showed large variations. For food
waste, YH2 can vary from 3 to 196 mL/gVS and depends on the
temperature, composition of the substrate, inoculums and the
type of process used.
It was observed that the increase in YH2 was not directly
related with the increase in the initial solids concentration. An
increment of 18-fold in the concentration (from 5 to 90 g/L)
only generated an increment of 7.6-fold in the YH2 (at pH 6.0).
For all cases except when 90 gTS/L was used, a greater amount
of hydrogen was produced with a high initial pH of 7.0, followed by 6.0 and 5.5. These results demonstrated that the YH2
depends on the solids concentrations and pH. This behavior
can be attributed to the consumption of hydrogen by homoacetogenic bacteria [31].

3.2.

Kinetics

To determine the hydrogen production rate, the kinetic coefficients of the Gompertz model were evaluated. Fig. 2 shows
an example of the fitted data obtained, and Table 2 summarizes the obtained values. In general, the model was in good
agreement with the experimental data (the regression coefficients, r2, were greater than 0.9). The maximum hydrogen
production rate was 64.92  3.37 mLH2/d (2.90  0.15 mmolH2/
d) and was obtained at 90 gTS/L and a pH of 5.5. No lag periods
were observed for the conditions of 1 and 5 gTS/L concentrations; however, a lag-time from 10 to 11.5 h was observed for
initial TS concentrations greater than 10 g/L (Table 2).
The specific hydrogen production rate (SHP) was evaluated
by dividing the Rmax by the total amount of removed VS or
COD for each test. Similar to the yield, the results can be
analyzed considering two sets of data. When the TS concentration was 1 g/L, the higher values for all the conditions
studied were obtained, irrespective of the pH value (Table 2). A
maximum value of 192.2  19.9 mLH2/gVSremoved/d (and
135.3  12.3 mLH2/gCODremoved/d) was obtained when the
initial pH was 7.0. From 5 to 90 gTS/L, the SHP varied from
8.7  1.0 to 66  3.8 mLH2/gVSremoved/d, respectively. The
highest SHP observed in the case of the lowest TS concentration could be because the good distribution of the inoculum
and the substrate. For all cases, the highest values for the SHP
were obtained when the initial pH was 7.0. No lag time was

13291

obtained at low initial TS concentrations. Nevertheless, a lag

time of 10e11.5 h was observed when the initial TS concentration was greater than 10 gTS/L. For all cases, the pH has no
influence on the lag phase.
Dong et al. [32] studied the hydrogen production from
seven varieties of individual components of OFUSW using
batch experiments at 37  C and observed that the SHP varied
from 49 to 112 mL H2/gVS/d. The difference in the specific
rates obtained in the present investigation and those obtained
by the other authors can be attributed to the complex nature
of the OFUSW and the inoculum used in each case.

3.3.

COD yield

In Fig. 3 (A), the SHP based on the VS removal was plotted

versus the SHP based on the COD removal, and the linear
regression was adjusted. The slope of the curve represents the
amount of COD removed per amount of VS removed. As discussed before, two clear sets of data were observed with an
excellent regression coefficient. The data obtained for 1 gTS/L
indicated that much more COD was removed per unit of VS
removed (0.142 gCOD/gVS) than for the other data
(0.041 gCOD/gVS) at the higher concentrations, which indicates that for lower concentrations, more organic matter is
available per unit of total solids, implying that hydrolysis
occurs more rapidly than in the cases with high initial TS
concentrations. This result can explain the higher hydrogen
yield observed for the initial TS concentration of 1 g/L.

3.4.

Hydrogen content

The hydrogen content of biogas at different TS concentrations

and initial pHs is shown in Fig. 3(B). For each total solids
concentration, the biogas was composed of only H2 and CO2,
with no methane detected for any case, indicating that the
pre-treatment was appropriate to avoid the growth of hydrogenotrophic and acetoclastic methanogenic microorganisms.
The higher content (26.8%) was obtained for 1 gTS/L at an
initial pH of 7.0. For higher TS concentrations, the content
decreased, and at TS concentrations greater than 10 gTS/L, the
percentages stabilized at approximately 15%, with no significant influence from the pH.

Fig. 2 e Kinetic data for selected values and the adjustment of the Gompertz model. A) Initial pH of 5.5 (1 and 5 gTS/L) and B)
Initial pH of 5.5 (40 gTS/L), 6.0 (90 gTS/l) and 7.0 (10 gTS/L).

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Table 2 e Initial conditions and Gompertz model parameters for the OFUSW as a function of TS and initial pH. The volume
values are at STP conditions.
Condition
TS, g/L
1.0
1.0
1.0
5.0
5.0
5.0
10.0
10.0
10.0
40.0
40.0
40.0
90.0
90.0
90.0

Initial pH
7.0
6.0
5.5
7.0
6.0
5.5
7.0
6.0
5.5
7.0
6.0
5.5
7.0
6.0
5.5

mL H2
2.65
1.36
1.52
3.56
2.24
1.34
8.71
6.25
3.80
12.98
10.75
10.97
23.18
27.09
25.07

Rmax

Hmax
mmolH2/d

 0.27
 0.15
 0.20
 0.16
 0.2
 0.15
 0.35
 0.42
 0.50
 0.38
 0.42
 0.35
 1.20
 1.4
 1.3

0.90
0.55
0.45
0.46
0.30
0.17
2.20
0.62
0.53
1.17
1.25
1.25
2.60
2.10
2.90

 0.09
 0.06
 0.05
 0.02
 0.01
 0.01
 0.09
 0.07
 0.06
 0.02
 0.03
 0.02
 0.13
 0.11
 0.15

mLH2/d

20.15  2.09
12.31  1.24
10.07  1.01
10.30  0.47
6.72  0.29
3.81  0.017
49.25  2.06
13.88  1.52
11.86  1.30
26.19  0.52
27.98  0.83
27.98  0.78
58.20  3.03
47.01  2.53
64.92  3.37

0.0
0.0
0.0
0.0
0.0
1.3
10.0
11.5
11.0
11.0
11.0
11.2
11.0
11.5
11.0

 0.0
 0.0
 0.0
 0.0
 0.0
 0.1
 0.1
 0.2
 0.2
 0.2
 0.3
 0.3
 0.1
 0.1
 0.1

SHP
mLH2/gVSremoved/d
192.2
107.4
89.1
22.6
14.9
8.7
58.8
19.0
20.5
23.8
18.8
18.3
66.0
66.0
49.4

 19.9
 11.2
 7.8
 1.0
 1.6
 1.0
 2.9
 8.0
 2.3
 0.7
 0.43
 0.45
 3.8
 3.7
 2.6

mLH2/gCODremoved/d
135.3  12.3
75.0  6.2
62.7  5.5
43.1  4.4
27.5  3.0
16.1  1.2
143.7  8.3
44.7  4.2
49.8  5.5
57.1  1.14
37.1  0.85
37.5  0.85
183.8  10.1
144.5  11.2
120.3  13.2

Average of three tests  standard deviation.

3.5.

Fermentation products

Acetic and lactic acids were monitored because it was found

that they were the principal fermentation products. Fig. 4(A)
shows the evolution of the acetic acid concentration as
a function of the total solids concentrations and initial pH. It
was observed that the increase in the initial TS concentration
produced an increase in the acetic acid concentration. A
considerable increase, greater than 1000 mg/L, was observed
when the initial TS concentration was greater than 10 g/L. The
highest value, 4016  98 mg/L, was obtained for 40 gTS/L at
a pH of 6. It is interesting to note that at 90 gTS/L and a pH of
7.0, the amount of acetic acid was greater than that when the
pH was 6; however, the SHP did not increase. This behavior
indicates that the acetic acid fermentation is not the only
reaction present in this case; homoacetogenic reactions are
also occurring that consume the produced hydrogen. It has
been shown that homoacetogenic bacteria as Clostridium aceticum can grow using H2 and CO2 to generate acetic acid and
water [33], where the optimum pH is 8.5. Thus, a pH of 7 could
create a more suitable environment for the reproduction of C.

aceticum. The aforementioned results indicate that hydrogen

production is associated with acetic acid production. The
lactate concentration increased proportionally to the total
solids concentration. The highest lactate value was observed
at 90 gTS/L and a pH of 7.0 (15.6 g lactate/L). It could be that the
hydrogen production was redirected to lactate, which could
possibly generate inhibition when its concentration becomes
greater than 3.4 g/L. This fact agrees with the increase of the
lag phases observed when the concentrations were greater
than 10 gTS/L. Other fermentation products were observed but
in lower concentrations, such as propionic (69e150 mg/L),
butyric (50e1000 mg/L), isobutyric (18e281 mg/L) and isovaleric (84e419 mg/L) acids, acetone (116e2419 mg/L) and
ethanol (26e487 mg/L). For these components, the higher
concentrations were observed at the higher TS concentration.

3.6.

Alkalinity and pH variation

It has been observed that alkalinity influences the hydrogen

production [19,24,34]. The OFUSW used in this study as feedstock had a relatively low alkalinity (<100 mg CaCO3/L).

Fig. 3 e (A) SHP based on VS removal as a function of SHP based on COD removal (all initial pH included) and (B) content of
hydrogen in biogas as a function of initial total solids concentration and pH.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 3 2 8 8 e1 3 2 9 5

13293

Fig. 4 e Effect of TS concentration and initial pH on acetic acid (A) and lactate (B) production.

However, the buffer capacity of the mixture, obtained after

the addition of the nutrients, increased the initial alkalinity to
1058  147 mg CaCO3/L. The alkalinity/COD ratio was calculated considering the initial total COD of the mixture. The ratio
varied from 0.0146  0.002 to 0.808  0.138 gCaCO3/gCOD, for
the initial TS concentrations from to 90 to 1 g/L, respectively.
This range is close to the value reported by Ref. [34] as the
optimum range (0.042e0.102 g CaCO3/g COD) for the conversion of sucrose into hydrogen in mesophilic conditions. Under
thermophilic conditions [24] a higher optimal alkalinity ratio
of 0.11 gCaCO3/gCOD has been suggested as needed to maximize the hydrogen productivity of organic solid waste. In our
study an elevated hydrogen production and yield was
observed for the elevated TS concentration, indicating that
such amount of alkalinity was sufficient to sustain the
hydrogen production. Directly adding chemicals for buffering
will inevitably increase the cost of hydrogen production. In
practice alternative cheap buffer sources could be considered
as municipal sewage sludge [19].
The pH was fixed at the beginning of the test and decreased
as the fermentation in the batch reactors occurred. The final pH
was conditioned by the acids concentration in the reactor. The
higher final pH values were obtained with lower total solids
concentrations. The influence of the TS concentration on the
final pH was more significant than the initial pH on each TS
concentration. Fig. 5 shows the average final pH for the three
different initial pHs for each initial TS concentration tested.
The increase in the solids concentration decreased the pH to
nearly 4.0 when the TS concentration was 90 g/L. The buffer
capacity of the mineral media maintained the pH at approximately 6.0 for the lower total solids concentrations (1e10 g/L);
however, the pH was less than 5.0 (nearly a pH of 4.0) when the
solids content was greater than 40e90 g/L. A high organic acid
production was the cause of such variations. Additionally, in
Fig. 5, the average pH variation (D pHinitial e pHfinal) was
computed for each TS concentration. For the high TS concentrations (40 and 90 g/L), the delta values were 2.1 and 2.3 and
significant acidification was not observed.

3.7.

found that the total solids and COD removal decreased as the
initial total solids concentration increased, indicating that the
highest levels of substrate transformation occurred at 1 gTS/L
(80% as TS and 50% as COD). It has previously been observed
that the hydrolytic-acidogenic phase during solids waste
degradation can be the limiting step because waste is often
particulate material [35]. For this reason, an appropriate
solubilization and organic matter transformation process is
required, which is affected primarily by the substrate
concentration. A compromise between the hydrogen
production and TS degradation must be achieved. It was
observed that with low TS concentrations, a high SHP was
produced and high TS and COD removal were also observed.
However, to achieve such a low concentration, the OFUSW
must be diluted. On the contrary, when the TS concentration
increased, the hydrogen production and SHP increased;
however, the TS removal was poor, i.e., the maximal capabilities for hydrogen extraction are presented here. To finish
the stabilization of the TS and the removal of COD, the predigested mixture can be treated in a methanogenic reactor
to produce methane in the biogas.

TS and COD removal

The TS and total COD removal as a function of the initial TS

concentration of the OFUSW are presented in Fig. 6. It was

Fig. 5 e Effect of the TS concentration on the final pH and

on the delta pH.

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Fig. 6 e Effect of the TS concentration and initial pH on TS and total COD removal.

4.

Conclusions

The influence of the initial pH and the initial total solids

concentration on hydrogen production from the organic
fraction of urban solids waste was investigated. The highest
hydrogen production rate (2.90 mmolH2/d) was obtained at
90 gTS/L with a pH of 5.5. Under this condition, the TS and
COD removal were the lowest (10% as TS and 14% as COD).
However, when the specific values were calculated considering the solids removal, a maximal specific degradation
rate of 192.2 mLH2/gVSremoved/d was obtained at the lowest
TS concentration tested at an initial pH of 7.0. At this
condition, a higher hydrolysis efficiency of the TS was
observed (0.142 gCOD removed per g of VS removed),
producing a higher hydrogen content in the biogas (23%).
The YH2 decreased as the solids concentration increased;
however, for TS concentrations greater than 5 g/L, the SHP
increased as the initial TS concentration increased. No
significant differences were observed on the SHP at the same
initial TS concentration when the initial pH ranged from 5.5
to 7. It was observed that higher final pH values were
obtained with lower total solids concentrations. High SHPs
were produced at high TS concentrations but with low TS
and COD removal. To finish the stabilization of the OFUSW,
the pre-digested mixture can be treated in a methanogenic
reactor, concomitantly generating methane in the biogas.

Acknowledgments
This research was supported by CONACYT (Project 100298)
and DGAPA-UNAM (PAPIIT IB100612). The authors acknowledge the technical help of Jaime Perez Trevilla.

references

[1] Edwards PP, Kuznetsov VL, David WIF, Brandon NP.

Hydrogen and fuel cells: towards a sustainable energy future.
Energy Policy 2008;36:4356e62.

[2] La Licata B, Sagnelli F, Boulanger A, Lanzini A, Leone P,

Zitella P, et al. Bio-hydrogen production from organic wastes
in a pilot plant reactor and its use in a SOFC. Int J Hydrogen
Energy 2011;36:7861e5.
[3] Zhu H, Parker W, Conidi D, Basnar R, Seto P. Eliminating
methanogenic activity in hydrogen reactor to improve biogas
production in a two-stage anaerobic digestion process codigesting municipal food waste and sewage sludge. Biores
Technol 2011;102:7086e92.
[4] Mohan SV, Mohanakrishna G, Goud RK, Sarma PN.
Acidogenic fermentation of vegetable based market waste to
harness biohydrogen with simultaneous stabilization. Biores
Technol 2009;100:3061e8.
[5] Chu C-F, Li Y-Y, Xu K-Q, Ebie Y, Inamori Y, Kong H-N. A pHand temperature-phased two-stage process for hydrogen
and methane production from food waste. Int J Hydrogen
Energy 2008;33:4739e46.
[6] Kanat G. Municipal solid-waste management in Istanbul.
Waste Manage 2010;30:1737e45.
[7] Maintinguer SI, Fernandes BS, Duarte ICS, Saavedra NK,
Adorno MAT, Varesche MB. Fermentative hydrogen
production by microbial consortium. Int J Hydrogen Energy
2008;33:4309e17.
[8] Gomez X, Cuetos MJ, Prieto JI, Moran A. Bio-hydrogen
production from waste fermentation: mixing and static
conditions. Renew Energ 2009;34:970e5.
[9] Fountoulakis MS, Manios T. Enhanced methane and
hydrogen production from municipal solid waste and agroindustrial by-products con-digested with crude glycerol.
Biores Technol 2009;100:3043e7.
[10] Shi Y, Zhao X-T, Cao P, Hu Y, Zhang L, Jia Y, et al. Hydrogen
bio-production through anaerobic microorganism
fermentation using kitchen wastes as substrate. Biotechnol
Lett 2009;31:1327e33.
[11] Wang X, Zhao Y-C. A bench scale study of fermentative hydrogen
and methane production from food waste in integrated twostage process. Int J Hydrogen Energy 2009;34:245e54.
[12] Liu D, Liu D, Zeng RJ, Angelidaki I. Hydrogen and methane
production from household solid waste in the two-stage
fermentation process. Water Res 2006;40:2230e6.
[13] Ma J, Ke S, Chen Y. Mesophilic biohydrogen production from
food waste. 2nd International Conference on Bioinformatics
and Biomedical Engineering 2008:2841e2844.
[14] Shin H-S, Youn J-H, Kim S-H. Hydrogen production from food
waste in anaerobic mesophilic and thermophilic
acidogenesis. Int J Hydrogen Energy 2004;29:1355e63.
[15] Kim S-H, Han S-K, Shin HS. Feasibility of hydrogen
production by anaerobic co-digestion of food waste and
sewage sludge. Int J Hydrogen Energy 2004;29:1607e16.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 3 2 8 8 e1 3 2 9 5

[16] Lay JJ, Lee YJ, Noike T. Feasibility of biological hydrogen

production from organic fraction of municipal solid waste.
Water Res 1999;33:2579e86.
[17] Davila-Vazquez G, Alatriste-Mondragon F, de LeonRodrguez A, Razo-Flores E. Fermentative hydrogen
production in batch experiments using lactose, cheese whey
and glucose: influence on initial substrate concentration and
pH. Int J Hydrogen Energy 2008;33:4989e97.
[18] Valdez-Vazquez I, Poggi-Varaldo HM. Hydrogen production
by fermentative consortia. Renew Sust Energ Rev 2009;13:
1000e13.
[19] Zhua H, Parker W, Basnar R, Proracki A, Falletta P, Beland M,
et al. Buffer requirements for enhanced hydrogen production
in acidogenic digestion of food wastes. Biores Technol 2009;
100:5097e102.
[20] Fan Y, Li C, Lay J-J, Hou H, Zhang G. Optimization of initial
substrate and pH levels for germination of sporing hydrogenproducing anaerobes in cow dung compost. Biores Technol
2004;91:189e93.
[21] van Ginkel S, Sung S, Lay JJ. Biohydrogen production as
a function of pH and substrate concentration. Environ Sci
Technol 2001;35:4726e30.
[22] Lee YJ, Miyahara T, Noike T. Effect of pH on microbial hydrogen
fermentation. J Chem Technol Biotechnol 2002;77:694e8.
[23] Buitron G, Carvajal C. Biohydrogen production from Tequila
vinasses in an anaerobic sequencing batch reactor: effect of
initial substrate concentration, temperature and hydraulic
retention time. Biores Technol 2010;23:9071e7.
[24] Valdez-Vazquez I, Poggi-Varaldo HM. Alkalinity and high
total solids affecting H2 production from organic solid waste
by anaerobic consortia. Int J Hydrogen Energy 2009;34:
3639e46.
[25] Moreno-Andrade I, Moreno G, Buitron G. Automated devise
for biogas production measurement during anaerobic
wastewater degradation. Biomass and Waste to Energy
Symposium. Venice 2006.

13295

[26] American Public Health Association/American Water Works

Association/Water Environment Federation. Standard
methods for the examination of water and wastewater. 21th
ed. Baltimore: Port city press; 2005.
[27] Vavilin VA, Rytova SV, Lokshina LY. A description of
hydrolysis kinetics in anaerobic degradation of particulate
organic matter. Biores Technol 1996;56:229e37.
[28] Zhang B, He P-J, Lu F, Shao L, Wang P. Extracellular enzyme
activities during regulated hydrolysis of high-solid organic
wastes. Wat Res 2007;41:4468e78.
[29] Nopharatana A, Pullammanappallile PC, Clarke WP. A
dynamic mathematical model for sequential leach bed
anaerobic digestion of organic fraction of municipal solid
waste. Biochem Eng J 2003;13:21e33.
[30] Guo XM, Trably E, Latrille E, Carre`re H, Steyer JP. Hydrogen
production from agricultural waste by dark fermentation:
a review. Int J Hydrogen Energy 2010;35:10660e73.
[31] Schiel-Bengelsdorf B, Durre P. Pathway engineering and
synthetic biology using acetogens. FEBS Lett 2012;586:
2191e8.
[32] Dong L, Zhenhong Y, Yongming S, Xiaoying K, Yu Z.
Hydrogen production characteristics of the organic fraction
of municipal solid wastes by anaerobic mixed culture
fermentation. Int J Hydrogen Energy 2009;34:812e20.
[33] Sim JH, Kamaruddin AH, Long WS, Najafpour G.
Clostridiumaceticumda potential organism in catalyzing
carbon monoxide to acetic acid: application of response
surface methodology. Enzym Microb Tech 2007;40:1234e43.
[34] Lin CY, Lay CH. Effects of carbonate and phosphate
concentrations on hydrogen production using anaerobic
sewage sludge microflora. Int J Hydrogen Energy 2004;29:
275e81.
[35] Hussy I, Hawkes FR, Dinsdale R, Hawkes DL. Continuous
fermentative hydrogen production from a wheat starch coproduct by mixed microflora. Biotechnol Bioeng 2003;84:
619e26.