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research-article2013

WMR32110.1177/0734242X13513827Waste Management & ResearchLiotta et al.

Original Article

Effect of moisture on disintegration kinetics


during anaerobic digestion of complex
organic substrates

Waste Management & Research


2014, Vol 32(1) 4048
The Author(s) 2013
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DOI: 10.1177/0734242X13513827
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Flavia Liotta1, Giuseppe dAntonio2, Giovanni Esposito1,


Massimiliano Fabbricino2, Luigi Frunzo3, Eric D van Hullebusch4,
Piet NL Lens5 and Francesco Pirozzi2

Abstract
The role of the moisture content and particle size (PS) on the disintegration of complex organic matter during the wet anaerobic
digestion (AD) process was investigated. A range of total solids (TS) from 5% to 11.3% and PS from 0.25 to 15 mm was evaluated
using carrot waste as model complex organic matter. The experimental results showed that the methane production rate decreased with
higher TS and PS. A modified version of the AD model no.1 for complex organic substrates was used to model the experimental data.
The simulations showed a decrease of the disintegration rate constants with increasing TS and PS. The results of the biomethanation
tests were used to calibrate and validate the applied model. In particular, the values of the disintegration constant for various TS and
PS were determined. The simulations showed good agreement between the numerical and observed data.
Keywords
Anaerobic digestion, wet digestion, moisture content, mathematical modelling, particle size, ADM1

Introduction
The use of anaerobic digestion (AD) for solid wastes treatment
has increased rapidly in Europe in the last few decades (De Baere
etal., 2010). AD can be considered as the major development
process in the field of solid waste treatment in Europe over the
last two decades (Le Hylaric etal., 2011). Among biological
treatments, AD of the organic fraction of municipal solid waste
(OFMSW) is the most cost-effective owing to the high energy
recovery linked to the process, and it has only limited environmental impact (Mata Alvarez etal., 2000). In fact, through AD it
is possible to reduce the chemical oxygen demand of waste,
obtaining the conversion of organic matter to biogas, which can
be used as bio-fuel in power generation systems to produce heat
and energy. Moreover, AD with energy recovery generates fewer
greenhouse gases than incineration or landfilling because
digested solid by-products can be composted (Edelmann, 2003).
In order to accurately predict the process efficiency at varying
operational conditions and to optimize the reactor design, it is
necessary to have mathematical models that can simulate the processes inside the reactor. Historically, AD is applied on wastewater treatment sludge and modelled as a multi-step process,
through the combined action of four types of anaerobic microorganisms: hydrolytic, fermentative, acetogenic and methanogenic bacteria. During this process the organic matter is
progressively converted into simpler and smaller-sized organic
compounds, obtaining biogas and digestate as final products. The

resulting digestate is rich in nutrients and microelements, thus


suitable for its utilization in agricultural contexts (Esposito etal.,
2012a, 2012b).
The limiting step of the AD process cannot be unequivocally
defined. Acetogenesis (Bryers, 1985; Costello etal., 1991a,
1991b; Hill, 1982; Siegrist etal., 1993) and methanogenesis
(Graef and Andrews, 1974; Moletta etal., 1986; Smith etal.
1988), as well as hydrolysis (Vavilin etal., 2001) and disintegration (Batstone etal., 2002; Esposito etal., 2008, 2011a, 2011b)
can constitute the rate-determining steps depending on the substrate to be digested and the AD reactor configuration used.

1Department

of Civil and Mechanical Engineering, University of


Cassino and the Southern Lazio, Italy
2Department of Civil, Architectural and Environmental Engineering,
University of Naples Federico II, Naples, Italy
3Department of Mathematics and Applications Renato Caccioppoli,
University of Naples Federico II, Naples, Italy
4Universit Paris-Est, Laboratoire Gomatriaux et Environnement
(LGE), Paris, France
5UNESCO-IHE Institute for Water Education (UNESCO-IHE), Delft, the
Netherlands
Corresponding author:
Flavia Liotta, Department of Civil and Mechanical Engineering,
University of Cassino and the Southern Lazio, Via Di Biasio, 43 03043 Cassino (FR), Italy.
Email: flavia.liotta@unicas.it

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Liotta et al.
When considering complex organic matter, the hydrolysis of
complex polymeric substances becomes the rate-limiting step
and modelling of this process has to be improved (Batstone etal.,
2002; Pavlosthathis and Giraldo-Gomez, 1991; Vavilin etal.,
1996, 1997, 1999). In particular, several models have shown that
the presence of OFMSW particles can be better described
with the introduction of a disintegration step. This step individuates the physical breakdown and transformation of the complex
organic matter into soluble organic particles, and represents the
rate-limiting step of the process (Batstone etal., 2002; Esposito
etal., 2008, 2011a, 2011b; Hills and Nakano, 1984; Sharma
etal., 1988).
Several authors investigated the rate of hydrolysis and disintegration as a function of different parameters such as pH, temperature, hydrolytic biomass concentration, type of particulate organic
matter and particle size (PS) (Esposito etal., 2008; Hill and
Nakano, 1984; Pavlostathis and Giraldo-Gomez, 1991; Sanders
etal., 2000; Sharma etal. 1988; Veeken and Hamelers, 1999; ).
However, it is less understood how the total solid (TS) content can
affect the hydrolysis and, in particular, the disintegration step of
complex organic substrates. There have been several attempts
made to model the effect of the moisture content on dry and semidry AD processes. In particular, Abbassi-Guendouz etal. (2012),
by application of the AD model no. 1 (ADM1) model, found a
decreasing first-order hydrolysis rate constant for carbohydrates
by increasing the TS content. This constant was calibrated using
batch experimental data with cardboard as initial substrate and
imposing the TS content in the range of 1530%. This finding is
in agreement with results presented by Bollon etal. (2011).
There have also been several attempts made to investigate the
effect of the TS content on the methane production by operating
specific methanogenic activity tests and simulating experimental
data using the Gompertz model (Lay etal., 1997a, 1997b, 1998;
Le Hyaric etal., 2011, 2012). These authors also suggested that a
high TS content could reduce substrate degradation, resulting in
less methanogenic activity. These results are consistent with several studies performed by Qu etal. (2009), Fernandez etal.
(2010), Forster-Carneiro etal. (2008) and Pommier etal. (2007),
who found a reduction in methane production with higher TS
concentration. All these studies showed that the moisture content
plays an essential role in biogas formation as the nutrients and
substrates for the microorganisms must dissolve in the water
phase before they can be assimilated. Furthermore, the moisture
content is also an important factor in low solids (wet, with 510%
TS) anaerobic digestion because it supports bacterial movement
and helps substrate and product diffusion through the porous
medium (solid waste) to bacterial sites (Lay etal. 1997a, 1997b;
Le Hyaric etal., 2012; Mora-Naranjo etal., 2004; Pommier etal.,
2007).
The aim of this work is, therefore, to assess the impact of the
moisture content on wet anaerobic digestion of carrot waste. To
better evaluate the impact of the water content on the AD performance, computer simulations using a new version of the ADM1
of complex organic substrates, proposed by Esposito etal. (2008,

2011b, 2012b), was applied. The model was used to describe the
experimental data and to define the dependence of the disintegration kinetic parameters on the PS and moisture content.
In more detail, the objectives of this work include:
proposing an experimental procedure for obtaining an inoculum at different moisture contents;
investigating the effect of the PS effect on the disintegration
step of the AD process of carrot waste;
investigation the effect of TS on methane production;
proposing a new mathematical modelling approach to
describe the effect of TS on the disintegration step of AD
using a new version of the ADM1 model proposed by
Esposito etal. (2008);
determining the surface-based kinetic constant for the cited
selected substrate, using the model proposed by Esposito
etal. (2008).

Materials and methods


Digester set-up and analytical
measurements
Biomethanation Tests (BMT) were performed on a small scale
under controlled and reproducible conditions in a 1000-ml glass
bottle GL 45 (Schott Duran, Wertheim am Mein, Germany). Small
amounts of Na2CO3 powder were also added to control the pH
value. Each bottle was sealed with a 5-mm silicone disc that was
held tightly to the bottle head by a plastic screw cap punched in the
middle (Schott Duran). All digesters were immersed up to half of
their height in hot water kept at a constant temperature of 308.15 K
by 200 W A-763 submersible heaters (Hagen, Tokyo, Japan).
Once a day, each digester was connected by a capillary tube to
an inverted 1000-ml glass bottle containing an alkaline solution
(2% NaOH). The inverted 1000-ml glass bottle was sealed in the
same way as the digesters. To enable gas transfer through the two
connected bottles, the capillary tube was equipped on both ends
with a needle sharp enough to pierce the silicone disc.
The weight, TS and volatile solids (VS) concentration of the
anaerobic sludge, as well as the dry matter, moisture organic matter and ash content of substrate, were determined according to
standard methods (APHA/AWWA/WEF, 1998). Temperature
and pH of all mixtures investigated were monitored at least once
a day with a TFK 325 thermometer (WTW, Weilheim, Germany)
and a pH meter (Carlo Erba, Pomezia, Italy) respectively
(Esposito etal., 2011b).

Preliminary tests: Drying procedure


In order to evaluate the effect of different moisture contents during AD, experiments at different TS contents are necessary. With
the objective to evaluate only the effect of the moisture content,
these experiments must be conducted using the same inoculum,
at the same operational conditions, varying only the TS content.
Therefore, fresh digestate was collected from a mesophilic AD of

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Waste Management & Research 32(1)

Table 1. Main characteristics of anaerobic sludge and carrot waste.


Substrate

Initial total
solid (%)

Initial volatile
solid (%)

Carbohydrate
(%)

Protein (%)

Lipids (%)

Wet anaerobic sludge


Carrot waste

2
12.7

1.2
11.4

2.1
0.121a

56
0.025a

41.9
0.006a

Buffire etal. (2006).

5000

CH4 (ml)

4000
3000
2000
1000
0

10

20

30
40
Time (days)

Thermal
Centrifugation

50

60

70

figure 2. Different particle sizes of carrot waste with


cylindrical shape.

Filtration
Untreated

Figure 1. Cumulative methane production of different drying


procedures.

a buffalo farm and stored in 10-l buckets at 4C and used as inoculum source. The initial inoculum characteristics in terms of TS,
VS, carbohydrates fraction, proteins fraction and lipids fraction
are listed in Table 1.
The inoculum was dried by testing three different procedures:
overnight drying of fresh digestate at 50C until constant weight,
centrifugation at 5040 G for 10 mins and membrane filtration
with a Kubota 203 microfiltration module. The selected drying
procedures were aimed at removing water from the inoculum,
obtaining a final value of 4% TS. In order to evaluate the effects
of different drying treatments, the concentrated inoculum was
reported at the initial TS content of 2% adding distilled water and
was compared with the untreated inoculum in terms of biomethane potential.
The aim of these tests was to individuate the drying procedure that
does not modify the inoculum characteristics in terms of biomass
activity and methane production. Therefore, the inoculum obtained
from each adopted drying procedure was used to carry out BMTs.
These experiments were performed using 2.63 g of pasta and 5.24 g
of cheese with known carbohydrate, protein and lipid concentrations.
The choice of the substrates was aimed at balancing the quantity of
carbohydrates, proteins and lipids in the digester influent.
The selected substrate, carrot waste, allows the development
of all microbial species involved in degradation of carbohydrates,
proteins and lipids in order to evaluate the pre-treatment effect on
all these species. The methane production is expressed under
standard conditions and considers the gas content variation in the
headspace of the reactor. The calculated methane production

accounts for the global methane production without the residual


endogenous methane production measured with the blank assay,
which represent the reactor filled only with digestate without
substrate addition (Figure 1).

Effect of PS on AD
Biomethanation experiments were performed using a selected
green grocery waste (i.e. carrot waste) as initial substrate with the
chemical composition in terms of TS, VS and concentrations of
carbohydrates, proteins and lipids reported in Table 1. This substrate was selected for modelling purposes owing to the ease to
obtain a cylindrical shape (Figure 2). That shape was obtained
using a cylindrical steel tube with a selected diameter. For each
particle, the same diameter and height was imposed in order to
obtain a ratio between area and mass equal to a particle with
cylindrical shape.
The tests were conducted using four different PS: 0.25 mm, 4
mm, 9 mm and 15 mm (Table 2). The selected ratio between
organic matter and anaerobic sludge was 0.5 organic matter/
anaerobic sludge (i.e. food/mass ratio). The selected digestate
was collected from a mesophilic AD of a farm treating buffalo
manure. The mass composition adopted for all tests is described
in Table 2. BMTs were operated in triplicate and a blank assay
was also carried out. In total, 15 BMTs were performed.

Effect of moisture content on AD


BMTs were performed using carrot waste with a cylindrical
shape and buffalo manure anaerobic digestate. A specific value of

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Liotta et al.

Table 2. Composition of the organic mixture in terms of food/mass (F/M) ratio, particle size, input substrate and inoculum for
the experiments T1T4.
Tests

F/M

Initial radius
(mm)

Carrots (g)

Anaerobic
sludge (g)

Na2CO3 (g)

T1
T2
T3
T4

0.5
0.5
0.5
0.5

15
9.0
4.0
0.25

48.2 ( 0.5)
48.2 ( 0.5)
48.2 ( 0.5)
48.2 ( 0.5)

500 ( 1)
500 ( 1)
500 ( 1)
500 ( 1)

0.300.40 ( 0.01)
0.300.40 ( 0.01)
0.300.40 ( 0.01)
0.300.40 ( 0.01)

Table 3. Mixture composition of tests T5, T6 and T7 in terms


of total solid (TS), volatile solid (VS) content, carrot waste and
dried anaerobic inoculum amount.
Test TS mixture VS mixture Carrot waste Dried anaerobic
(%)
(%)
amount (g)
sludge (g)
T5
T6
T7

11.3
7.5
4.98

8.57
4.6
3.7

40
40
40

120
245
320

dC
= K sbk a * C (2)
dt

where C is the concentration of the complex organic substrate in


the digester (kg m-3); A is the disintegration surface area [m2];
and M is the complex organic substrate mass (kg).
Assuming that all the organic solid particles have the same
initial size and cylindrical shape with h = 2R, that they are progressively and uniformly degraded, the a* equation is given by
the following equation:
n

a PS of 15 mm was selected in order to get the disintegration step


as the rate-limiting step.
The initial TS content of the fresh digestate was 2%, which
was dried by centrifugation in order to obtain the desired moisture contents. A fixed amount of substrate was defined, and only
the digestate volume was modified in order to obtain different
moisture contents. All the tests were performed imposing a
selected ratio between organic matter and anaerobic sludge of 0.5
organic matter/inoculum. All the tests were conducted in triplicate. Nine bottles were operated with three TS contents: 4.98%,
7.5% and 11.3%. The mixture composition of each BMT test is
reported in Table 3.
A further nine tests were conducted using only anaerobic
sludge as a substrate to estimate the volume of methane resulting
from the fermentation of the organics contained in the anaerobic
sludge. In total, 18 tests were performed.

Mathematical model
For a better understanding of the effect of TS and PS on the
anaerobic degradation of complex organic substrates, the anaerobic co-digestion model for complex organic substrates proposed
by Esposito etal. (2011b) was used. The model was calibrated
with the experimental data of the batch experiments to estimate
the kinetic constant of the surface based disintegration process,
Ksbk (ML-2T-1). The differential mass balance equations and the
process kinetics and stoichiometry, described in detail in Esposito
etal. (2011b), are based on the ADM1 approach.
The disintegration kinetic is based on the surface-based
kinetic expression proposed by Sanders etal. (2000) and reformulated by Esposito etal. (2008, 2011b) by including a*, which
characterizes the disintegration process:

a* =

A
(1)
M

a* =

A
i =1
n

M
i =1

=
i

3
nAi
=
nM i R (3)

where Ai is the disintegration surface area of the organic solid


particle i (m2); Mi is the mass of the organic solid particle i (kg);
n is the total number of organic solid particles (ad.); is the complex organic substrate density (kg m-3); and R is the organic solid
particles radius (m), assumed to be time-dependent according to
the following expression proposed by Sanders etal. (2000):

R = R0 K sbk

t
(4)

where R0 is the initial organic solid particle radius [m], specified


as the initial condition for model application.
The a* coefficient is different than the one proposed by
Esposito etal. (2011b, 2012b) as the solid particles have a cylindrical, instead of a spherical, shape.
Integration of the differential algebraic equations is performed
using a multi-step solution algorithm based on the numerical differentiation formulas in the software tool MATLAB.
Several simulations were performed to identify the best fitting between experimental and modelling data. In particular,
the disintegration kinetic constant Ksbk (ML-2T-1) was changed
several times in the model to estimate the value that permits the
fitting of experimental data. The calibration was performed by
comparing model results with experimental data of cumulative
methane production for a selected particle size and to define
the unknown parameter by fitting experimental data with
model results. The calibration procedure proposed by Esposito
etal. (2011b) was used. The comparison between experimental
data and model results was performed by applying the root
mean square error (RMSE) (Esposito etal., 2011b; Janssen and
Heuberger, 1995).

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Waste Management & Research 32(1)


3500
3000

CH4 (ml)

2500
2000
1500
1000
500
0

10

15

20

4.95%

Initial methane production rate


(mlCH4 grVSin-1 d-1)

Figure 3. Effect of particle size on the cumulative methane


production of carrot waste at a total solid content of 3%.

25
30
35
Time (days)
7.50%

40

45

50

55

11.50%

Figure 5. Effect of total solids on the cumulated methane


production from anaerobic digestion of carrot waste (particle
size = 15 mm).

70
60
50
40
30
20
0.05

0.1

0.15

0.2
0.25
1/D (mm-1)

0.3

0.35

0.4

Figure 4. Influence of particle size on initial methane


production rate of carrot waste.

Results and discussion


Effect of drying procedure
Figure 1 shows the cumulative methane production obtained
using the different inocula resulting from the different drying
procedures and the untreated inoculum. The biomethanation
potential is the same for all tests, but by only adopting the
centrifugation procedure it is possible to observe a similar
trend as for the untreated digestate. These results indicate that
all the tested methods are suitable drying procedures that do
not alternate the inoculum characteristics. For the following
experiments, centrifugation was selected as the drying procedure because it gives the minimum alteration of the inoculum
and it is the most simple and cheap method to apply in the
laboratory.

Effect of PS on AD performance
Figure 3 shows the cumulated methane production for the reactors operated at four different PS ranges during the whole experiments. Each curve represents the average of three replicates with
an SD equal to 0.05. The results clearly show a different initial
trend for the four curves, indicating a cumulative methane production rate inversely proportional to the PS. The cumulative
methane production rate was inversely proportional to the PS.
The results clearly show a different initial trend for the four
curves, related to the effect of different solid particle size on the
methane production rate. The methane yield of all curves is in the

range of 460(30) ml.gVS-1. There are no large differences as all


reactors were filled with the same amount of substrate.
Figure 4 shows a logarithmic relationship between PS and initial methane production rate for the substrate added, indicating a
strong impact of the PS on the kinetic rates and individuating the
disintegration process as the rate-limiting step for methane production. These results are consistent with the findings of previous
studies (Esposito etal., 2008, 2011b; Hills and Nakano, 1984;
Sharma etal., 1988). Hills and Nakano (1984), plotting the methane gas production relative to the parameter 1/sDm (where s
represent the sphericity of the particles and Dm the average particle diameter), found a linear correlation between these parameters. A similar correlation was implicitly considered in the model
proposed by Esposito etal. (2008, 2011b).

Effect of TS content on AD performances


Figure 5 shows the cumulated methane production for the reactors operated at three different TS contents during the whole
experiments. Each curve represents the average of three replicates with an SD equal to 0.045. Lag-phase and the initial methane production rate were inversely proportional to the TS content.
These results are consistent with previous studies performed by
Lay etal. (1997a, 1997b), who made batch tests in mesophilic
digesters at different pH values by testing the effect of the moisture content in the range of wet digestion.
The final methane yield, measured at the end of each experiment can be assumed for all tests coincident and equal to the
mean value of 450 ml gVS-1 with an SD of 14.23 (Table 4). This
is apparently not in agreement with the findings of AbbassiGuendouz etal. (2012), Fernandez etal. (2008) and Dong etal.
(2010), who found higher methane yields with lower TS in the
range of dry and semidry AD. The difference is due to the different moisture content range investigated, as the present experiments were carried out in wet conditions. The conversion of acids
to methane by methanogenic bacteria can thus be influenced by
the lack of water (Ghosh, 1985; Lay etal., 1997b) that can occur
at a higher TS content in the range of dry and semidry digestion
(Abbassi-Guendouz etal., 2012; Dong etal., 2010; Fernandez
etal., 2008).

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Liotta et al.
Table 4. Cumulative methane production of carrot waste with
a particle size of 15 mm.
TS mixture (%)

4.98

7.5

11.3

Cumulative methane
production (ml)
Cumulative methane
production of blank (ml)
Net cumulative methane
production (ml)
Methane yield (ml/gVSfeed)

3410

3210

2830

1340

1230

725

2070

1980

2105

455

430

460

TS: total solids; VS: volatile solids.

Figure 7. Calibration procedure for carrot waste with a


particle size of 15 mm: dependence of root mean square
error (RMSE) on Ksbk.

Initial methane production rate


(mlCH4 grVSin-1 d-1)

50
40

that the TS content, also in wet AD, has a strong effect on the
kinetic rates. In particular, at lower TS, owing to the increasing water content and better transport and mass transfer conditions, it seems plausible that the microorganisms are better
provided with soluble substrates (Mora-Naranjo etal., 2004).

IMPR=-740.3TS+84.34
R2=0.9987

30
20
10
0

8
TS (%)

Experimental data

10

11

12

Regression line

Figure 6. Influence of the total solids on initial methane


production rate of carrot waste.

Table 5. Results of the model calibration and validation


procedure of tests T1, T2, T3 and T4.
Test

PS (mm)

a*(m2 kg-1)

Ksbk (kg
m-2s-1)

RMSE

T1
T2
T3
T4

15
9.0
4.0
0.25

0.561
0.702
1.579
12.632

0.28
0.28
0.28
0.28

0.0830
0.0670
0.0627
0.0630

RMSE: root mean square error.

Table 6. Disintegration constant and index of agreement for


different total solids of carrot waste (particle size = 15 mm).
Test

a* [m2)kg(-1)]

Kdis (kg m-2s-1)

RMSE

T5
T6
T7

0.561
0.561
0.561

0.1
0.3
0.55

0.0084
0.0088
0.0087

Figure 6 indicates a linear relationship between the TS content and the initial methane production rate. Such a linear relationship was also observed for AD of selected dry organic
wastes, for example sludge cake, meat, carrot, rice, potato and
cabbage (Lay etal., 1997b), cellulose (Le Hyaric etal., 2012),
cardboard (Abbassi-Guendouz etal., 2012), for waste samples
excavated from landfill (Mora-Naranjo etal., 2004) and paper
waste (Pommier etal., 2007). The presented results confirm

Modelling results
Modelling the effect of particle size on AD. Model calibration
was used to estimate the kinetic constant of the surface-based
disintegration process, Ksbk (kgm-2d-1). Calibration was performed by comparing model results with experimental measurements of methane production and adjusting the unknown
parameters until the model results adequately fit the experimental
observations. The measured data of experiment T1 (Table 5)
were used, and a calibration procedure introduced by Esposito
etal. (2011b) was applied. Using the previously calibrated Ksbk
model, validation was performed by calculating the RMSE for
T2, T3 and T4 experiments.
The model calibration performed resulted in setting the kinetic
constant Ksbk equal to 0.28 kgm2s-1. Ksbk was the value that maximizes RMSE (Figure 7), which shows a single monotone reversal
trend, confirming the existence of one and only one solution to
the specific optimization problem.
In Figure 8(a, b), a good overlap between the simulated and
model data is shown. A small shift between experimental data
and model results was observed.
The results of experiments T2, T3 and T4 were used to validate
the mathematical model, assessing the agreement between simulated and observed data for the cumulative methane production
with the parameter RMSE. Figure 8(ch) shows very good agreement between the simulated and experimental data. This agreement is confirmed in Table 5, where the values of a* constant
evaluated for the different PS ranges investigated are also reported.
Modelling the effect of TS on AD. The mathematical model proposed by Esposito etal. (2008, 2011b) was calibrated to set different values of the kinetic disintegration constant Kdis (T-1) =
Ksbk a* for different TS contents. For a selected PS of 15 mm, the
value of a* constant was 0.561 m2 kg-1. The measured data of the
experiment were used, a calibration procedure introduced by

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Waste Management & Research 32(1)

Figure 8. Comparison of measured and simulated cumulative methane production for experiments with PS TS = 2.94%, PS
= 15 mm (a, b), TS = 2.94%, PS = 9 mm (c,d), TS = 2.94%, PS = 4 mm (e,f), TS = 2.94%, PS = 0.25 mm (g, h), TS = 4.98%, PS =
15mm (i, l), TS = 7.48%, PS =15mm (m, n) and TS = 11.34%, PS = 15mm (o, p): overlapping between measured and simulated
data (a, c, e, g, i, m, o); comparison between simulated and experimental data with line of perfect fit (b, d, f, h, l, n, p).

Esposito etal. (2011b) was applied, and the RMSE for T5, T6
and T7 experiments were evaluated.
The results (Figure 8ip) show good agreement between the
simulated and experimental data. This agreement is confirmed in
Table 6, where the values of the Kdis constant, evaluated for different TS, are also reported. In particular, the good fit between
simulated and experimental concentrations shows the capability

of the model to simulate the AD process of substrates with different initial TS.
Figure 9 indicates a linear relationship between TS and the
disintegration kinetic constant obtained with the model proposed
by Esposito etal. (2008, 2011b).
The linear correlation represented in Figure 6 can be expressed
using the following linear equation:

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Liotta et al.

results of a full model in case a rate-limiting step of the biological


process is clearly present.

Disintegration rate constant


(kg m2 s-1)

0.6
0.5
IMPR = -740.3 TS+84.34
R2 = 0.9987

0.4

Conclusions

0.3
0.2
0.1
0

8
TS (%)

10

11

12

Figure 9. Correlation between total solids content and


disintegration rate constant of carrot waste with a particle
size of 15 mm.
Table 7. Disintegration kinetic constants obtained with
equation (7) and with the mathematical model.
Test

Kdis (kg m-2s-1)a

Kdis (kg m-2s-1)b

T5
T6
T7

0.1
0.3
0.55

0.08
0.26
0.30

aFrom

Esposito etal. (2008, 2011b).


bUsing equation (7).

d [CH 4 ]0
dt

Funding
= 740.3 (TS %) + 84.34 (5)

d [CH ]4
dt

= K dis [C ] (6)

where [C] is the substrate concentration (ML-3).


By including the parameters l [angolar coefficient of the interpolation line (740.3)] and f [intercept value of the interpolation
line on the axis of the initial methane production rate (84.34)],
and integrating and making simplifications, it is possible to
obtain the following equation:

K dis =

Declaration of conflicting interests


The authors do not have any potential conflicts of interest to declare.

By considering the presence of a limiting step (i.e. disintegration


process), the rate of the overall AD process can be modeled by
one equation. If first-order kinetics are assumed for the disintegration process, the methane production rate can be expressed by
equation (6):

This study focused on the effect of TS content and PS on anaerobic digestion of complex organic substrates. A linear correlation
between the initial methane production rate and TS content was
also individuated. With regard to the particle size, an inverse correlation between this parameter and the specific methane production was found, and a linear relationship between 1/PS and the
initial methane production rate for the substrate added. This
result underlines a strong impact of the PS on the kinetic rates
and individuating the disintegration process as the rate-limiting
step for methane production.
The surface-based kinetic constant Ksbk for the disintegration
equation of carrot waste was determined. Also, the values of the
disintegration constant for different TS content were assessed.
Finally, a simple equation correlating TS and the disintegration
constant was proposed, that showed a good agreement with the
results of new version of the ADM1 of complex organic substrate
proposed by Esposito etal. (2008, 2011b).

ln(l (TS %) + f ) t
(7)
C0

where t is the integration time for the initial biomethane production rate evaluation (d) and Co is the initial substrate concentration (kg m-3).
In Table 7 the values of the disintegration constant, obtained
with equation (7) and with the mathematical model proposed by
Esposito etal. (2008, 2011b), are reported, showing a good
agreement of the results of the two methods. This confirms that a
simplified model (i.e. a one-equation model) can approximate the

This work was carried out with the support of the Erasmus Mundus
Joint Doctorate programme ETeCoS3 (Environmental Technologies
for Contaminated Solids, Soils and Sediments) under the EU grant
agreement FPA No 2010-0009 and by the French Ministry of Foreign
Affairs in the framework of MOY Programme under Moy Grant
N2010/038/01. This research is also in the framework of the project
Integrated system to treat buffalo slurry, aimed to recover water and
safe energySTABULUMfunded, in agreement with the
Decision of the European Commission No C(2010) 1261, 2 March
2010, by the Agriculture Department of the Campania Region in the
context of the Programme of Rural Development 20072013,
Measure 124 Cooperation for development of new products, processes and technologies in the agriculture and food sectors.

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