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Environmental Technology
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Evaluation of pre-treatment processes for increasing

biodegradability of agro-food wastes
a

D. Hidalgo , E. Sastre , M. Gmez & P. Nieto

Centro Tecnolgico CARTIF, Valladolid, Spain

Accepted author version posted online: 13 Feb 2012.Published online: 16 Mar 2012.

To cite this article: D. Hidalgo , E. Sastre , M. Gmez & P. Nieto (2012): Evaluation of pre-treatment processes for increasing
biodegradability of agro-food wastes, Environmental Technology, 33:13, 1497-1503
To link to this article: http://dx.doi.org/10.1080/09593330.2012.665488

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Environmental Technology
Vol. 33, No. 13, July 2012, 14971503

8TH IWA SYMPOSIUM ON WASTE MANAGEMENT PROBLEMS IN

AGRO-INDUSTRIES-AGRO2011
Evaluation of pre-treatment processes for increasing biodegradability of agro-food wastes
D. Hidalgo , E. Sastre, M. Gmez and P. Nieto
Centro Tecnolgico CARTIF, Valladolid, Spain

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(Received 11 October 2011; nal version received 30 January 2012 )

Anaerobic digestion (AD) technology can be employed for treating sewage sludge, livestock waste or food waste. Generally,
the hydrolysis stage is the rate-limiting step of the AD processes for solid waste degradation. Therefore, physical, chemical
and biological pre-treatment methods or their combination are required, in order to reduce the rate of such a limiting step. In
this study, four methods (mechanical shredding, acid hydrolysis, alkaline hydrolysis and sonication) were tested to improve
methane production and anaerobic biodegradability of dierent agro-food wastes and their mixtures. The kinetics of anaerobic
degradation and methane production of pre-treated individual wastes and selected mixtures were investigated with batch tests.
Sonication at lower frequencies (37 kHz) proved to give the best results with methane productivity enhancements of over
100% in the case of pig manure and in the range of 1047% for the other wastes assayed. Furthermore, the ultimate methane
production was proportional, in all the cases, to the specic energy input applied (Es). Sonication can, thus, enhance waste
digestion and the rate and quantity of biogas generated. The behaviour of the other pre-treatments under the conditions
assayed is not signicant. Only a slight enhancement of biogas production (around 10%) was detected for whey and waste
activated sludge (WAS) after mechanical shredding. The lack of eectiveness of chemical pre-treatments (acid and alkaline
hydrolysis) can be justied by the inhibition of the methanogenic process due to the presence of high concentrations of sodium
(up to 8 g l1 in some tests). Only in the case of WAS did the acid hydrolysis considerably increase the biodegradability
of the sample (79%), because in this case no inhibition by sodium took place. Some hints of a synergistic eect have been
observed when co-digestion of the mixtures was performed.
Keywords: anaerobic digestion; batch assays; co-digestion; organic waste; pre-treatments

Introduction
The production of organic waste can be considered an
integral part of developed society. These wastes (solid or
semi-solid) are generated from agriculture, food processing, drinks manufacture or even in the form of domestic
wastes, and their quantities are appreciable. Over the years,
an array of ideas for the utilization of these wastes has been
put forward. However, anaerobic digestion (AD) of organic
wastes to produce energy in the form of biogas is the most
likely option to be of commercial interest, provided that
the economics are favourable [1,2]. The degradation rate of
complex particulate organic matter in anaerobic digesters is
generally controlled by the rate of the rst, and usually limiting, step: the hydrolysis, where the cell wall is broken, thus
allowing the organic matter inside the cell to be available
for biological degradation. In order to increase the waste
degradation rate and methane production, the pre-treatment
options, such as physical, chemical or even thermal ones,
have yielded promising results [3,4].
Pre-treatment breaks down the complex organic structure into simpler molecules that are more susceptible to
microbial degradation. Alkaline pre-treatment destroys cell
walls by hydroxyl anions and causes natural shape loss
Corresponding

author. Email: dolhid@cartif.es

ISSN 0959-3330 print/ISSN 1479-487X online

2012 Taylor & Francis
http://dx.doi.org/10.1080/09593330.2012.665488
http://www.tandfonline.com

of proteins, saponication of lipids and hydrolysis of

RNA (ribonucleic acid). Many alkalis have shown their
eectiveness in waste solubilization, with an eciency of
(NaOH > KOH > Mg(OH)2 and Ca(OH)2 ). However, too
high concentrations of Na+ or K + may cause subsequent
inhibition of AD [5]. It has been used to solubilize various
substrates, such as lignocellulosic materials, waste activated sludge (WAS) or food waste [69]. The addition of
alkali increases the mineral content of digested waste [10].
Acidication to solubilize wastes has been suggested and
shown in the laboratory to be a possibility [1114]. The
conditions for achieving this scenario are very intensive in
terms of extreme pH values: 0.51.0 gH2 SO4 /gTSS [15].
Devlin et al. [16] showed that chemical oxygen demand
(COD) and volatile solids (VS) reduction and gas production were enhanced when wastes were pre-treated with HCl.
However, one concern with acidication is the need to add
alkalinity. Ultrasonic disintegration is a well-known method
for breaking-up microbial cells to extract intracellular material [17,18]. There are two mechanisms associated with
ultrasonic treatment: cavitation, which is favoured at low
frequencies, and chemical reactions due to the formation of
radicals at high frequencies [19]. The hydrolysis of cellular

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1498

D. Hidalgo et al.

membranes can also be achieved by mechanical rupturing

techniques (i.e. shredding, grinding, etc.). Mechanical pretreatment is generally based on the disruption of mechanical
cell walls by shear stress. This method has also been shown
to improve the anaerobic digestibility of wastes [20,21].
As previously mentioned, many studies have investigated pre-treatment of waste, mainly activated sludge, for
AD and also dealt with a single pre-treatment method in
comparison with non-pre-treatment. However, few reports
have been published on various pre-treatment methods for
AD [22], and even fewer have been applied to other typologies of waste apart from activated sludge. For this reason,
an in-depth study of the anaerobic biodegradability of six
dierent wastes from four agro-food industries and their
mixtures was undertaken, with special emphasis placed on
the hydrolysis step. Dierent approaches were attempted:
mechanical (shredding and sonication) and chemical (acid
and base addition) pre-treatment to improve methane production. To show the comprehensive eciency of the
pre-treatment methods, the kinetics of anaerobic degradation and methane production was examined with batch
tests.
Materials and methods
Waste selection
Six dierent types of wastes from four agro-food industries dairy (cheese production), jam and sauce production,
candy manufacturing and swine farming were chosen
for this project, namely: whey (WH), fresh cheese (FC)
waste, physical-chemical sludge (PCS) from dairy wastewater treatment, sauce and jam (SJ) waste, WAS from candy
wastewater treatment and pig manure (PM). The selection
criteria relied upon aspects such as the relative geographical
distance between each producer and theoretical information related to biomethane generation/kg of organic waste.
Four mixtures of four selected individual wastes among
the above-mentioned ones were prepared, considering those
with more diculties to be used directly as sub-products in
other industrial processes. Table 1 shows the content of each
waste in the selected mixtures. Results are presented on a
VS percentage basis.
Chemical analysis
Solid concentrations (total and volatile), pH and total
phosphorus were determined following standard methods
Table 1.

Composition of the waste mixtures.

Waste

M1 (%)

M2 (%)

M3 (%)

M4 (%)

WAS
PCS
SJ
PM

25
25
25
25

15
15
55
15

15
55
15
15

35
15
15
35

(APHA, 1998) recommendations. C, N, H and S contents

were determined by UNE-CEN/TS 15104 EX with a LECO
Truspec CHN(S) elemental determinator. Oxygen content
was not measured directly, but was estimated assuming that
no other elements (apart from the measured C, H, N, S and
P) were present in the wastes.

Biochemical methane potential tests

Batch experiments were run in glass serum bottles with
a liquid volume of 300 ml (1000 ml of total volume).
Anaerobic sludge from a municipal wastewater treatment
plant (WWTP) with a concentration of 12 gVS l1 was
used as inoculum for the anaerobic test. The concentration of the inoculum in all the assays was 5 g l1 .
Substrate/inoculum (S/X) ratios in the range of 0.30 to
0.50 gVSwaste gVS1
inoculum were performed in triplicate
for all the wastes. A set of triplicate blank assays without any waste (only inoculum) was also performed for
endogenous methane production determination. To avoid
acidication of the assay, NaHCO3 was added as a buer
(5 g NaHCO3 l1 ). The pH was adjusted to 7.5 in all
cases by the addition of HCl or NaOH. After the set-up
of each reactor, the headspace was ushed with nitrogen
for 3 minutes in order to remove the oxygen. All the
experiments were carried out at 35 1 C in a thermostatic room and constant agitation was provided by a stirrer
table.
Biogas production was measured manually by a pressure transducer (Druck, PTX 1400, range 1 bar) in the
head space of each reactor. To avoid reaching overpressure,
biogas in the head space was periodically released. Pressure dierences were converted to biogas volume, using
the ideal gas law and standard conditions (P = 1 bar and
T = 0 C). Biogas composition was measured before each
release with a Varian CP-4900 Micro-GC with a Thermal
Conductivity Detector. Methane production was calculated
by subtracting the amount of the methane produced by
the blank assay from the methane production of each
assay.

Theoretical methane potential

Analysis of the elemental composition of the waste provides
information about its potential anaerobic degradation and
composition of the biogas [23], by a stoichiometric conversion to methane and carbon dioxide, using Buswells
equation (1). This equation assumes methane production
from the complete degradation of a certain waste with
a given elemental composition, where Cn Ha Ob Nc represents the chemical formula of the biodegradable organic
compound subjected to the anaerobic degradation process,
and the production of methane considered herein is the
maximum stoichiometrically possible. For a Cn Ha Ob Nc
compound, the theoretical methane potential (at standard

Environmental Technology
Table 2.

1499

Pre-treatment conditions.

Experiment 1
Pre-treatment
Shredding
Sonication

Alkaline hydrolysis
Acid hydrolysis

Operating conditions
Power (kW)

Frequency (kHz)

Bath volume (l)

Time (min)

850
200

37

0.5
0.5

1.5
60

pH

Solution

Time (min)

12
2

5 g l1 NaOH
30 ml l1 H2 SO4

60
60

Sample
Raw waste
Raw waste
Sample
Raw waste
Raw waste

*Raw waste: WH, FC, WAS, PCS, SJ and PM

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Experiment 2

Operating conditions

Sonication

Power(kW)

Frequency (kHz)

Bath volume (l)

Time (min)

Assay 2A
Assay 2B
Assay 2C
Assay 2D

200
200
1500
2500

37
37
40
40

0.5
0.5
35
35

60
30
60
60

Sample
Waste mixture
Waste mixture
Waste mixture
Waste mixture

* Waste mixture: WAS, PCS, SJ and PM in %: M1 (25/25/25/25); M2 (15/15/55/15); M3 (15/55/15/15);

M4 (35/15/15/35)

conditions for temperature and pressure) is:



n a b 3c
+
22.4
2 8 4
8
|=|
B0,Th =
12n + a + 16b + 14c

(P), ultrasonic time (t), total volume (V ) and total solid

concentration (TS):
L CH4
g VS

Es =

(1)
where the parameters n, a, b, c refer to the stoichiometry
index of C, H, O and N, respectively.
Biodegradability factor

The eciency of the pre-treatments can be calculated using

the biodegradability factor (BF) as methane potential of
the pre-treated sample (PreT ) to methane potential of the
sample not pre-treated ratio (Non-PreT ) (Equation (2)), the
BF being a measure of ultimate biodegradability extent:
BF =

(ml CH4 /g VS)Pr eT

(ml CH4 /g VS)nonPr eT

Pt
kJ
|=|
V TS
g TS

(3)

Since sonication was the method showing the best results

during the rst experiment, the second approach was to
study the pre-treatment of selected waste mixtures under
dierent ultrasonic irradiation conditions in order to nd
out the preferential ones. Pre-treatment conditions for both
experiments are summarized in Table 2.
Before entering the biochemical methane potential
(BMP) test, samples proceeding from acid and alkali pretreatments were neutralized with NaOH and H2 SO4 , respectively, in order to avoid extreme pH values inside the batch
tests.

(2)

Pre-treatment conditions
Two experiments were carried out. The rst was designed
to determine the pre-treatment method giving the highest biodegradability enhancement when the raw wastes
were individually analysed. Four methods (mechanical,
acid hydrolysis, alkaline hydrolysis and sonication) were
tested. For mechanical treatment a domestic shredder was
used. The ultrasonic irradiation of wastes was performed in
two systems (Elmasonic S 40H and Tierra Tech SET 1500)
that emit 37 and 40 kHz, respectively. For each sonication
test, a 100 ml sample was lled in a beaker and then placed
in the equipment water bath. The specic input energy (Es)
(Equation (3)) was dened as a function of ultrasonic power

Results and discussion

Waste composition
Lumped parameters as TS, VS, COD, total organic carbon (TOC) and total Kjeldahl nitrogen (TKN) are the most
frequently analysed, since they are the key when determining treatment optimization. Furthermore, analysis of the
elemental composition provides information about the theoretical methane potential of a given waste. Table 3 gathers
the results obtained from the characterization of the selected
raw wastes.
The B0,Th values for the degradation of the six waste
streams under study were calculated on the basis of
Buswells equation (1), where the specic content in C,
H, O and N of each waste is the origin of the dierences in
the theoretical methane potentials calculated.

1500

D. Hidalgo et al.

Table 3.

Wastes characterization.
Elemental compositiona

Physico-chemical parameters
Waste pH- TS g l1 VS g l1 VS/TS-

%C

%H %N %P %S %Ash %Ob

WH
FC
PCS
SJ
WAS
PM

46.5
47.0
60.4
44.9
46.4
34.5

5.0
7.1
8.9
5.9
6.4
4.7

a%

5.0
5.2
5.1
3.9
6.5
7.7

49.1
364.5
445.2
194.4
25.6
44.9

43.6
256.4
427.8
179.3
23.1
30.7

0.9
0.7
1.0
0.9
0.9
0.7

3.3
2.0
6.9
1.6
6.9
2.8

1.1
0.8
4.0
0.7
0.5
0.4

0.4
0.3
0.4
0.2
0.4
0.7

11.2
29.7
3.9
7.8
9.8
31.6

32.5
13.1
15.5
38.9
29.6
25.3

B0,Th mLCH4 gVS1

504
835
782
480
523
516

dry-matter weight basis.

b %O estimated.
c Calculated assuming

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Theoretical methane potentialc

a Ca Hn Ob Nc composition (S and P neglected)

From the theoretical point of view, in accordance with

Buswells equation, FC and PCS give wastes with the highest methane potential, as shown in Table 3. These two types
of waste are also expected to have the highest lipid content.
Lipids are one of the most energetic organic compounds,
with a high specic biogas potential. Consequently, addition of wastes with a high lipid content into a biogas reactor
can result in signicant increase of the biogas production.
Eect of pre-treatments
Pre-treatment of raw waste
The eect of sonication, shredding, acid hydrolysis and
alkaline hydrolysis pre-treatment was evaluated by comparing the experimental results obtained, in terms of the extent
of biogas production, when BMP assays for pre-treated
and non-pre-treated samples were run. Table 4 shows the
biodegradability factors for the six wastes selected and the
four pre-treatment methods assayed. These data refer to ultimate biodegradability and the behaviour of the tests during
the incubation time is not reected here.
Comparison of the biogas production after 1.5 minutes
shredding the wastes shows that the inuence of mechanical
pre-treatment on anaerobic biodegradability under the conditions assayed is not signicant. Only a slight enhancement
of biogas production was detected for WH and WAS. The
maximum values of the biodegradability factor for these
wastes were, respectively, 1.11 and 1.10, while for the other
samples this factor remained close to the unit.
The acid and alkaline pre-treatments were carried out
at pH 2 and 12, respectively, using NaOH and H2 SO4 as
pH modiers. In these cases, a lack of eectiveness was
Table 4.

Biodegradability factor for raw wastes.

Sample

Pre-treatment

WH

FC

PCS

SJ

WAS

PM

Shredding
Sonication
Alkaline hydrolysis
Acid hydrolysis

1.11
1.31
0.67
0.60

1.05
1.10
0.59
0.50

1.00
1.27
0.37
0.38

1.02
1.24
1.01
0.40

1.10
1.47
0.94
1.79

1.00
2.54
0.05
0.00

observed with a decrease in methane productivity in most

of the assays, clearly due to inhibition processes related to
the nature of the chemicals used during pre-treatment. Only
in the case of WAS did the acid hydrolysis considerably
increase the biodegradability of the sample.
Sonication pre-treatment was performed at the frequency of 37 kHz and 60 minutes of sonication time. The
best results were obtained with this method, improving the
AD by a factor of 1.102.54. Better results were obtained
for waste samples with less TS content (PM and WAS).
This is an indication that the degree of waste disintegration
is directly related to the specic energy input expressed as
the amount of energy consumed in relation to the total solids
content.
In conclusion, from the rst experiment it can be
assessed that methane productivity was enhanced by sonication pre-treatment in all the cases. Meanwhile, methane
productivity remained constant regardless of the shredding
pre-treatment (only a slight enhancement was detected).
It would seem that shredding favours particle deagglomeration without achieving the destruction of bacteria cells.
On the other hand, the lack of eectiveness of alkali and
acid pre-treatments, with decrease of methane productivity in some cases, can be justied by the inhibition of the
methanogenic process due to the presence of high concentrations of sodium of up to 8 g l1 in some cases. According
to Chen et al. [24], sodium concentrations ranging from 3
to 16 g l1 cause 50% inhibition in AD processes. Although
sulfuric acid was also added during both pre-treatment
processes, no competition between sulfate-reducing and
methanogenic bacteria was observed, since the presence of
H2 S in the biogas was not detected. In the case of WAS, the
positive eect of the acid hydrolysis might be due to the fact
that the acidication of WAS required a smaller amount of
acid and, consequently, a smaller amount of alkali for later
neutralization. As a consequence, non-inhibition by sodium
took place.
Eect of ultrasonic treatment on co-digestion
Four mixtures of four selected individual wastes were prepared as indicated in Table 1. Figure 1 shows the average

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Environmental Technology

1501

Figure 1. Cumulative specic methane production curves of the waste mixtures (M1, M2, M3 and M4) at dierent conditions (2A, 2B,
2C, 2D and non-pre-treatment). All data are seed-blank corrected.

cumulative specic methane production of the wastes at the

dierent conditions assayed (2A, 2B, 2C, 2D), where AN-P
refers to non-pre-treatment conditions. All the biodegradability assays were conducted in triplicate and the maximum deviation reported was 10 mlCH4 gSV1 for every
assay set.
It can be observed that the results obtained with
pre-treated samples, no matter the conditions applied,
always show higher methane generation potential than
non-pre-treated samples. Focusing on the tests carried out
with non-pre-treated samples, it can be observed that experimental values obtained from the biodegradability tests after
600 hours operation (Figure 1) are always lower than the
theoretical ones obtained by applying Buswells equation
(in mlCH4 gVS1 : B0,Th (M1) = 575, B0,Th (M2) = 537,
B0,Th (M3) = 658, B0,Th (M4) = 553), which could mean
that the maximum theoretical conversion has not been
reached during the experimentation, but also (more probable) that with Buswells equation neither the use of
substrate nor other routes of conversion of organic matter are taken into consideration for the production of

bacterial biomass. Furthermore, it is known that in the

presence of specic inorganic donors (such as nitrate, sulfate or sulte) the production of methane can decrease.
During the reported period, as expected, the mixture with
the highest percentage of high theoretical methane yield
waste (M3 with 55% PCS content) also shows, in general,
higher specic methane potential than the other mixtures
(M1, M2 and M4), with a lower percentage of high theoretical methane yield wastes (25%, 15% and 15% of
PCS, respectively). This behaviour is common to pretreated and non-pre-treated samples. For the other mixtures, where the order of theoretical methane potential,
B0,Th is (B0,Th (M1) > B0,Th (M4) > B0,Th (M2)), the situation changes in the absence of pre-treatment, the experimental results obtained being B0,Th (M2) > B0,Th (M1) >
B0,Th (M4). Here a clear synergistic eect is observed when
co-digesting mixture M2, in accordance with Nieto et al.
[25], although this eect is not so evident when samples are
pre-treated.
Mechanisms of the ultrasonic process are clearly
inuenced by three factors: supplied energy, ultrasonic

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1502

D. Hidalgo et al.

frequency and nature of the treated material, as the experimental results show.
The optimal scenario assayed corresponds to 2A, closely
followed by scenarios 2B and 2D and, nally, 2C. The
assays without pre-treatment gave the worst results. The
ultimate methane production was proportional to the specic energy input applied, Es, in all the mixtures, but higher
specic methane potentials were found at lower frequency
(37 kHz, assays 2A and 2B) in accordance with Bourgrier
et al. [26]. The disintegration of samples was also most
eective at the lower frequency, as can be deduced from
the largest increase in turbidity, derived from the parallel increase in COD solubilization. The soluble COD ratio
(dened as soluble COD divided by total COD) increased
in all the cases from 15% to 38% for 37 kHz frequency and
only from 9% to 25% for 40 kHz. This can be explained
because low-frequency ultrasound creates large cavitation
bubbles that, upon collapse, initiate powerful jet streams
exerting strong shear forces in the liquid. The decreasing
disintegration eciency observed at higher frequencies is
attributed to smaller cavitation bubbles, which do not allow
the initiation of such strong shear forces. On the other hand,
methane generation increased with increasing sonication
time in M2 and M4. Here, short sonication times result in
particle deagglomeration without the destruction of bacteria cells, while longer sonication brought about the break-up
of cell walls. The waste particles are disintegrated and dissolved compounds release. However, in the case of M1 and
M3 (the mixtures with the highest composition of PCS),
the eect of the sonication times assayed on the cumulative
specic methane production is not appreciable, since the
gures for assays 2A and 2B are similar. It is possible that
a higher sonication time would have given better results
for this specic waste, which seems more resistant to disintegration. When maintaining the parameters frequency,
total volume (V ) and sonication time (t) constant during the
sonication pre-treatment, an increment in the same test on
the power input, P, positively aects the nal AD process
behaviour, resulting in an increment in the total methane
production, as shown when comparing assays 2C and 2D.
In absolute terms, M1 is the mixture most aected by
ultrasound pre-treatments, since it shows that the higher
cumulative methane production increases when this method
is applied in comparison with the non-pre-treated assays
(104%, 103%, 75% and 102% of increment for assays 2A,
2B, 2C and 2D, respectively).
Biogas composition
During the early stages of the assays, methane content in the
biogas was low, but it increased until reaching the amounts
shown in Table 5. Higher methane content was observed
in the biogas of the pre-treated samples as compared to
the control, due to the better biodegradation of disintegrated samples. Again the optimal scenario corresponds to
assay 2A.

Table 5.

Biogas composition.
Methane percentage
M1

Non-pretreatment
Assay 2A
Assay 2B
Assay 2C
Assay 2D

M2

M3

M4

62.2 1.5 60.0 1.8 62.0 1.2 63.8 1.0

70.4 2.0
70.2 1.9
68.7 1.6
68.0 1.6

67.5 1.5
66.6 2.1
68.0 1.5
66.8 1.7

70.6 1.5
70.4 0.9
69.7 2.4
70.4 1.0

67.8 1.3
66.4 1.6
66.4 1.9
66.4 1.9

Increase in the methane percentage of pre-treated

samples over untreated ones may suggest that waste
components with higher methane production potential
(polymeric material, such as lipids, proteins and carbohydrates) were the most aected in terms of disintegration
(conversion into smaller molecules) by pre-treatment activities. These substrates were solubilized in the media thanks to
pre-treatment actions and the bacteria present in the system
were able to access and transform them into methane, while
in un-treated samples, some of these substrates were able
to remain insolubilized and, thus, not contribute to biogas
generation. No inhibition of methane generation by ammonia metabolization proceeding from soluble proteins was
observed.

Conclusion
In this study, several pre-treatment methods (shredding,
sonication, acid hydrolysis and alkaline hydrolysis) applied
to dierent wastes and their mixtures were performed to
improve the AD eciency.
The results indicate that the digestion eciencies of
the wastes were consequently improved by ultrasonic pretreatment. Ultrasonic pre-treatment enhances the subsequent AD, resulting in increased production of biogas. It
has been shown that degradation of samples is more ecient
when using low frequencies and a correlation was found to
exist between gas production and energy applied. Results
also showed that the co-digestion of the mixtures does not
have a clear eect on AD eciency, although suggestions
of a synergistic eect have been observed, depending on the
waste mixture formulation.
The development and establishment of the pre-treatment
of wastes prior to AD in order to accelerate the hydrolysis step can make this technology potentially more feasible for all kinds of wastes. Pre-treatment can, thus,
enhance waste digestion and the rate and quantity of biogas
generated.
Acknowledgements
The authors gratefully acknowledge support of this work by the
Spanish Ministry of Science and Innovation (project CTM200914330).

Environmental Technology

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