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Bioresource Technology 96 (2005) 169–180

A respirometric method for characterising the organic

composition and biodegradation kinetics and the
temperature influence on the biodegradation kinetics, for a mixture
of sludge and bulking agent to be co-composted
A. Tremier , A. de Guardia b, C. Massiani c, E. Paul d, J.L. Martel a

SUEZ Environment, Organic Effluents Division, CIRSEE, 38 avenue du President, Wilson 78230 Le Pecq, France
Cemagref, Livestock and Municipal Waste Management Research Unit, 17 av. de Cucille, CS 64427 35044 Rennes Cedex, France
Universite de Provence, Laboratory of Chemistry and Environment, Centre St. Charles, pl. Victor Hugo, 13331 Marseille Cedex 3, France
INSA Toulouse, Laboratory of Environmental Process Engineering (LIPE, EA833), 135 av. de Rangueil, 31 077 Toulouse Cedex 4, France
Received 28 May 2003; received in revised form 2 December 2003
Available online 28 July 2004

A respirometric method was set up to study kinetics of biological reactions involved in the treatment of organic wastes––sludge
mixed with pine barks––by composting. Oxygen consumption rates of this type of mixture were monitored during 10–20 days, using
a 10 l respirometric cell kept at constant temperature and moisture. Oxygen consumption kinetics were modelled and organic matter
composition was characterised as biomass, easily-biodegradable, slowly-biodegradable and non-biodegradable organic matter. The
influence of temperature on kinetics was tested. Results show that this respirometric method is a useful tool for the characterisation
of solid organic matter biodegradability and for the modelling of the biological kinetics of the composting process.
 2004 Elsevier Ltd. All rights reserved.

Keywords: Composting; Sludge; Respirometry; Organic matter characterisation; Biodegradation kinetics; Modelling; Biodegradability

1. Introduction metabolism. During the second phase of the composting

process, called the ‘‘curing phase’’, organic macromole-
Composting, or aerobic biological treatment of or- cules such as humic substances are synthesised. As we
ganic wastes, is an ancestral way to reduce wastes and to already mentioned, degrading reactions form the central
reuse organic matter. Among the range of existing or- phenomena of the ‘‘active phase’’ of the treatment. These
ganic wastes, sewage sludge composting with the use of reactions, based on numerous biological, thermal and
woody bulking agents, such as pine barks, enables the physico-chemical phenomena, involve oxygen con-
production of a quality product that may be used as a sumption, as well as heat, water and carbon dioxide
soil conditioner or as an organic fertiliser. However, the production. As all the above phenomena interfere with
quality of the end-product largely depends on the way to one another, they are quite difficult to characterise on the
perform the initial mixture and to manage reactions sole experimental basis obtained from composting trials.
occurring during the composting treatment. Thus, describing each phenomenon and all the pheno-
The composting process includes two major phases. mena interferences, thanks to mathematical equations
The first one, called the ‘‘active phase’’, mainly develops and, particularly, modelling the biological reactions of
degrading reactions: dissolved organic matter is used as the active phase of composting, should lead to a simu-
carbon and energy source by microorganisms for their lation of the behaviour of the substrates treated by this
process and then should allow a better understanding
and optimisation of the composting treatments.
Corresponding author. Knowing the kinetics of biological reactions and the
E-mail address: anne.tremier@cemagref.fr (A. Tremier). influencing environmental parameters is essential to

0960-8524/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
170 A. Tremier et al. / Bioresource Technology 96 (2005) 169–180

reach the objective of simulating biological degradation into account the influence of the solid matrix charac-
of organic matter, without consideration of any mass teristics of the substrate (moisture, granulometry, etc.).
transfer limitation. In such a case, the kinetics of the Thus, the results of stabilisation or biodegradation
organic matter degradation and the quantity of de- kinetics might be quite different when considering the
graded matter are directly linked with biomass growth treatment of a real waste.
kinetics (Bailey and Ollis, 1986): The first aim of this study was to develop a respiro-
1 metric method respectful of the real physical structure of
rX ¼ lX and rS ¼ lX samples and to apply it to the special case of a solid
mixture of sludge and bulking agent, in which homo-
with rX : biomass growth kinetics (mol O2 /kg/h), l: bio- geneous oxygen supply might be a problem. While using
mass specific growth rate (h1 ), X : microorganisms this method, two objectives were pursued: (1) To char-
concentration (mol O2 /kg), rS : substrate degradation acterise the initial organic composition of the mixture as
kinetics (mol O2 /kg/h), YX =S : biomass growth yield (–). biomass concentration and as easily-biodegradable or-
There is also a relationship between biomass growth, ganic matter concentration, as well as slowly-biode-
substrate degradation and oxygen consumption: gradable and non-biodegradable organic matter
concentration, thanks to the validation of a kinetic
rO2 ¼ ð1  YX =S ÞrS ¼ ½ð1  YX =S Þ=YX =S rX
model simulating the oxygen uptake rate by considering
with rO2 : oxygen consumption rate (mol O2 /kg/h). biomass growth and organic matter hydrolysis limita-
As biomass or substrate concentrations are difficult to tion; (2) To study the influence of temperature on the
measure, biological reactions can be studied through biodegradation kinetics at constant moisture.
respirometric methods by monitoring instantaneous
oxygen consumption rate and by knowing the biomass
growth yield. Indeed, respirometry is the measurement 2. Methods
and interpretation of the biological oxygen consumption
under well-defined experimental conditions (Spanjers 2.1. Respirometric device design
et al., 1998). Numerous respirometric methods are used
to characterise organic matter composition and biodeg- The respirometric device (Fig. 1) was set up on the
radation in liquid effluents (wastewater, slurries, etc.). basis of Aguilar-Juarez (2000). In order to model
Such methods have also been developed to study household wastes biodegradation kinetics during the
organic solid wastes, in order to provide a maturity or aerobic phase of a landfill cell exploitation period, Ag-
stability index. Ianotti-Frost et al. (1992), Ianotti et al. uilar-Juarez developed a 1.8-l closed respirometric cell.
(1994) evaluated compost stability through a gaseous This cell, filled with a representative sample of house-
dissolved oxygen measurement in a closed bottle. The hold wastes, was continuously aerated and the oxygen
AT4 (German index for respiration activity in 4 days) consumption rate within the substrate was recorded.
evaluates stability with regard to the cumulative quan- Considering the specificity of the studied substrate
tity of consumed oxygen measured for 96 h (Binner and (sludge and bulking agent), the respirometric device
Zach, 1999). The DRI (Dynamic Respiration Index), developed in this study was bigger than Aguilar-Juarez’s
proposed by Adani et al. (2001, 2002), considers, as a device so that the reacting medium would be compara-
stability index, the average instantaneous oxygen con- ble to a composting one. The proposed respirometer
sumption kinetics, measured on a sample for 24 h after consisted of a 10-l hermetically-closed glass cell, filled
the maximum respirometric activity has been reached. with the substrate mixture placed on a grid. Ambient air
Finally, stability has been studied by Lasaridi and was blown into the mixture through a pipe placed at the
Stentiford (1998) and Stentiford (2002), by placing bottom of the cell. The flow rate (Q) was maintained
compost in a liquid medium and by measuring the constant and precisely measured through a volumetric
maximal oxygen uptake rate (SOUR). Some authors, gas counter. In order to provide homogeneous aeration
such as Lasaridi et al. (1996), have also applied a res- conditions, a rapid recirculation of the gas in the cell
pirometric method to solid wastes so as to study organic was carried out. So, considering the solid organic sub-
matter biodegradation kinetics as a function of envi- strate, this device was a closed vessel reactor. Consid-
ronmental parameters such as temperature. ering the gas phase, the respirometric device could be
The most important limit concerning the previous used as an open reactor (continuous injection of ambi-
methods was the measurement of oxygen consumption ent air and continuous air exit) or as a closed reactor
on small quantities of solid sample (30–100 g). More- (only recirculation of the initial gas volume).
over, these samples were often ground and sometimes Temperature and moisture were kept constant during
they were suspended in aqueous solution before mea- each experiment, by placing the respirometric cell in a
surement. As a consequence, the result concerning sta- thermostatic water bath and by humidifying the
bility level or biodegradation kinetics would not take incoming air and condensing the water in the exhaust
A. Tremier et al. / Bioresource Technology 96 (2005) 169–180 171


Condenser Ambiant air


Thermostated water bath


Ambiant air entry

Recirculation Air exit

Fig. 1. Respirometric measurement device.

gas. Temperature was controlled by a Pt 100 probe • Dry matter content (DM): wet samples (three repli-
placed in the mixture. The oxygen consumption rate was cates of about 1 kg) dried at 80 C to constant weight.
obtained by measuring oxygen concentration both in the A higher temperature was not used because of the fire
incoming and exhaust gas, thanks to a paramagnetic hazard with this type of sample.
oxygen gas analyser. • Organic matter content (OM): dried ground samples
calcinated at 550 C using the standard method NF U
2.2. Substrates and respirometric measurements charac- 44-160 (AFNOR, 1985).
teristics • Total organic carbon content (TOC): dried ground
samples oxidised to CO2 and measurement of CO2
Mixtures of wastewater treatment sludge and pine by infrared spectrometry (SKALAR device), accord-
barks were used as substrates for the respirometric ing to the standardised method NF-EN-13137 (AF-
study. NOR, 2001).
Sludges were produced during the biological treat- • Chemical oxygen demand (COD): COD was deter-
ment of wastewater mainly from food processing mined by dichromate oxidation on 50 mg of dried
industries. They were directly sampled at the wastewater ground sample, according to an adaptation of the
treatment plant after centrifugation. Sludges were then standard method described in the norm NF T 90-
sub-sampled at the laboratory and stored by freezing 101 (AFNOR, 1971) for powdered samples.
them (1–10 kg) in order to work with constant substrate • Kjeldhal nitrogen content (TKN): TKN was quanti-
quality. Pine barks were used as bulking agent in the fied on 50 mg of dried ground sample by mineralisa-
mixture. They were sieved in order to remove large tion within a strong acid medium (sulphuric acid
pieces (longer than 10 cm and larger than 4 cm), which 98%), followed by steam distillation and then titri-
were too big for the respirometric cell. Mixtures were metric determination (adaptation of the standard
always performed on a 1/1 wet mass ratio in order to method NF ISO 11261 (AFNOR, 1995) for pow-
simulate a mixture to be composted. dered samples.
Twelve respirometric measurements were performed
with an average of 2.3 kg of wet mixture each time. The mean chemical characteristics of sludges and
Temperatures between 19.6 and 56.9 C were tested. tested mixtures, and the coefficient of variation are
Oxygen consumption rate was measured, as described summarised in Table 1.
above, for 10–20 days––until it became low and con- Dry matter content was also measured on the mixture
stant. at the end of the respirometric test.

2.3. Chemical analyses 2.4. Respirometric method validation

At the beginning of the experiments, sludge and In order to study and model the biodegradation
mixture were analysed according to the following kinetics, the respirometric measurement had to rely only
parameters: on the intrinsic parameters of the microbiological
172 A. Tremier et al. / Bioresource Technology 96 (2005) 169–180

Table 1
Mean characteristics of sewage sludge and sewage sludge and pine barks mixtures
DM (%) OM (% DM) COD (mg O2 /g DM) TOC (mg C/g DM) TKN (mg N/g DM)
Sewage sludge Mean value 17.1 83.9 1347 461 75.9
CVa (%) 1.5 0.1 1.6 4.9 3.6
Sewage sludge and Mean value 47.0 94.1 1439 510 15.4
pine barks mixtures CVa (%) 1.5 1.9 4.1 4.9 8.6
Coefficient of variation.

activity such as the biomass concentration, the bio- It is assumed that a solid organic substrate is a three
degradable organic matter concentration, etc. The phase matrix (De Guardia, 2002; Mustin, 1987). The
environmental conditions (temperature, moisture, etc.) first phase is a dry solid composed of mineral and or-
and the oxygen supply have to be as constant and as ganic matter. The second phase is the aqueous phase
homogeneous as possible in order not to influence formed by the moisture of the material, and composed
kinetics during measurement. Hence, the first step of the of mineral and organic soluble matter, where biological
following work was to check that the method was con- reactions take place. The heterotrophic biomass X is
trolled as far as the oxygen supply, temperature and contained in this phase. The third phase is the gaseous
moisture are concerned, and that it could be reproduced. phase due to the material porosity, which allows gaseous
The homogeneity of the aeration in the reacting cell exchanges between the aqueous phase and the environ-
and the airtightness of the cell were controlled through a ment. Within this matrix, the organic matter is to be
characterisation of the gas flow patterns in the respiro- described in three fractions: the easily-biodegradable
metric device. In this purpose, known amounts of fraction MB which is already soluble and which may be
methane were injected as a gas tracer in the respiro- immediately consumed by microorganisms; the slowly-
metric device closed on the gas recirculation loop. Four biodegradable fraction MH which is composed of solid
recirculation flow rates (3Q, 4.5Q, 6Q, 7.5Q where Q is or soluble macromolecules that are to be hydrolysed
the incoming air flow rate in case of trials with the open before biological consumption; the inert (or non-bio-
gas system) were tested. The evolution of the methane degradable) fraction MI which is not or very little con-
concentration was monitored through an infrared gas cerned by biological reactions according to the time
analyser. scale of the composting process active phase. Kinetic
The temperature and moisture maintenance was model’s equations are presented as follows.
verified by calculating their coefficient of variation
during each of the twelve respirometric measurements dX MBðtÞ
¼ lm X ðtÞ  bX ðtÞ ð1Þ
performed. dt KB þ MBðtÞ
Finally, measurement repeatability was tested by dMH X ðtÞ
comparing three experiments (A–C) carried out on ¼ Kh MHðtÞ X ðtÞ ð2Þ
dt þ KMH
identical substrate mixtures at comparable temperatures X ðtÞ

(around 37 C) and moistures (around 53.0%). Trials A dMB 1 MBðtÞ

¼  lm X ðtÞ
and B were performed at the same time. Trial C was dt Y KB þ MBðtÞ
carried out one month later. MHðtÞ
X ðtÞ
þ Kh MHðtÞ X ðtÞ ð3Þ
X ðtÞ
2.5. Conceptual approach of the biological oxygen con-
sumption ð1  Y Þ MBðtÞ
rO2 ðtÞ ¼ lm X ðtÞ
Y KB þ MBðtÞ
As mentioned in the introduction, the oxygen uptake þ bð1  f ÞX ðtÞ ð4Þ
rate measured in biological reacting systems is directly
linked with the biological activity and the organic mat- As described by Eq. (1), microorganisms use the
ter biodegradation. In the wastewater treatment field, easily-biodegradable fraction as a source of carbon and
the development of the activated sludge theory has led energy. Actually, a part of MB is transformed to give
to propose conceptual models (ASM) to simulate oxy- new biomass cells (Eq. (3)). The coefficient of biomass
gen uptake rate and characterise the organic matter growth yield (ratio between biomass formed and avail-
composition as a function of several biological processes able MB) is called Y . The other part (1  Y ) of MB is
(carbon oxidation, nitrification and denitrification) oxidised in presence of an electron acceptor, which is
(Henze et al., 2000). In the context of solid organic oxygen in the case of an aerobic process such as com-
matter biodegradation, only the concepts concerning posting (Eq. (4)). This oxidation supplies energy and
carbon oxidation by heterotrophic biomass were con- produces heat, water and carbon dioxide. The other
sidered as explained in the following. biodegradable organic fraction MH is reduced to simple
A. Tremier et al. / Bioresource Technology 96 (2005) 169–180 173

organic molecules, which become part of the fraction growth and hydrolysis periods of the experimental
MB, through enzymatic hydrolysis reactions as exposed curves. Then, the kinetics (l and Kh ) and the charac-
in Eq. (2) (Eliosov and Argaman, 1995). The biomass X , terisation of initial values (X0 , MB0 and MH0 ) were
which develops along with MB consumption is also lost obtained after fixing default values, based on literature
by decay. The dead biomass is partly transformed in references, for Y, f, b, KB , and KMH .
inert matter MI (fraction f ) and partly oxidised in
presence of oxygen (fraction (1  f )): it is the endoge-
nous respiration concept. As a consequence, oxygen 3. Results and discussion
consumption is proportional to the MB biodegradation
and the biomass decay (Eq. (4)). 3.1. Respirometric method validation
To sum up, the conceptual model of solid organic
matter degradation is composed of: 3.1.1. Homogenous aeration validation
Fig. 2 shows that whatever the flow rate, the evolu-
• three substrate active components: X , MH, MB
tion of the methane concentration in the reacting cell
expressed in mmol O2 /kg of substrate’s DM or mg
was identical. After a few seconds the gas analyser de-
O2 /g of substrate’s DM
tected methane. The concentration grew rapidly until it
• five kinetic parameters: lm (h1 ), KB (mmol O2 /kg of
reached a constant value. This constant value meant
substrate’s DM or mg O2 /g of substrate’s DM), b
that the closed gas respirometric device was perfectly
(h1 ), Kh (h1 ), KMH (–)
airtight: no loss of gas tracer could be established.
• two dimensionless stoichiometric parameters: Y , f
Moreover, this evolution was characteristic of the mixed
flow pattern (Levenspiel, 1999) with a little delay due to
2.6. Parameters estimation and model numerical solution the time required by the tracer to enter the cell just after
being injected. That is to say that the gas flow was
In order to estimate the values of the model para- perfectly homogeneous in the cell after a few minutes:
meters for the twelve experimental curves, the dynamic the concentration of the gas tracer in the gas phase
biological model was fitted to the experimental data. was the same everywhere in the respirometric device.
For each experiment, a computer program optimised Finally, the constant methane concentration made it
model parameters by calibrating the modelled oxygen possible to calculate the gaseous volume in the respiro-
consumption kinetics result with the experimental oxy- metric device. This volume was the same as the one
gen consumption kinetics, using a least square method. calculated thanks to the characteristics of the device and
To this purpose, coupled differential equations involved the porosity of the solid substrate. Therefore it demon-
in the model were solved with a SCILAB ODE’s pack- strated that no dead volume was detected in the system.
age on the basis of an initial set of parameters. An According to the above results, the respirometric device
identification procedure based on a structural identifi- allowed to supply homogeneous gas phase without any
ability study (Dochain et al., 1995; Sperandio and Paul, misbehaving in the flow (dead volume, short cut, etc.).
2000), was developed in order to estimate groups of Fig. 2 also shows that mixing time decreased along with
initial parameters, using linearisation hypothesis on increasing recirculation flow rate. It was decided to work



[CH4] ppm



300 Recirculation flow rate = 3*Q

Recirculation flow rate = 4.5*Q
200 Recirculation flow rate = 6*Q
Recirculation flow rate = 7.5*Q

0 50 100 150 200 250 300 350 400 450 500
Time (s)

Fig. 2. Gas flow behaviour inside the respirometric cell as a function of the recirculation flow rate.
174 A. Tremier et al. / Bioresource Technology 96 (2005) 169–180

at the fastest recirculation rate (7.5 times faster than the of consumed oxygen were exactly equal for trials A and
ambient airflow rate injected during trials with the open B, which were done at exactly the same temperature
gas system), which homogenised the gas phase within 2 (36.6 C). However this amount was higher for trial C
min. As a consequence, homogenization time concern- carried out one month later at a temperature higher of 3
ing the gas phase of the reacting cell was roughly five C (39.6 C), in spite of a comparable temperature im-
times higher than the injected air residence time in the posed in the water bath. One must keep in mind that
respirometric system. oxygen consumption is linked with the growth kinetics
and the death kinetics of microorganisms, which both
3.1.2. Temperature and moisture maintenance depend on temperature. Between trials A, B and trial C,
For ten of the twelve experiments, the coefficient of temperatures were slightly different. Then, the same
variation of the mean temperature value during the stage of organic matter biodegradation might have not
measurement was less than 5%. Only two higher coeffi- been reached exactly at the same date and it could partly
cients of variation (6.7% and 6.3%) were observed dur- explain the gap in cumulative oxygen consumption be-
ing experiments at low temperature. Indeed in these last tween the three experiments. Thus, considering the
two cases, temperature maintenance was much more natural physical heterogeneity of the mixture and the
influenced by ambient air temperature variation. Con- deviation in temperature, the validation of the mea-
cerning moisture maintenance during experiments, var- surement repeatability was accepted.
iation around an average value between the initial and
the final moisture content was always less than 4%. 3.2. Experimental respirometric curves and respirometric
3.1.3. Measurement repeatability
Fig. 3 displays the respirometric curves for trials A– Typical examples of respirometric curves are given on
C. Trials A–C were carried out on the same substrate Fig. 3. The proposed model leads to an interpretation of
mixture and the same water bath temperature. While the respirometric measurement as follows. After a time
trials A and B were carried out at the same date, trial C lag, biomass consumes oxygen in order to degrade the
was carried out one month later. most easily-biodegradable substrate and to sustain its
All curves presented the same behaviour. For the own growth requirements. With the increasing biomass,
three trials, the values of the maximum oxygen uptake the oxygen consumption accelerates until the whole of
rate showed a coefficient of variation of 8.2%. The val- the easily-biodegradable substrate is degraded. Conse-
ues of the total consumed oxygen amount, calculated quently, a break in the exponential growth is observed.
between the beginning of the experiment and the same The biomass keeps on developing by consuming the
measurement date (defined as the minimal duration substrate coming from the hydrolysis of the slowly-
necessary to observe a low and apparently constant biodegradable substrate. As a consequence, the oxygen
value of respiration rate in each case), presented a consumption rate decreases regularly down to the
coefficient of variation of 17.5%. In fact, total amounts complete disappearance of all the biodegradable sub-



mmol O2.h-1.kg DM-1

Oxygen uptake rate - Trial A
25 Oxygen uptake rate - Trial B
Oxygen uptake rate - Trial C



0 50 100 150 200 250 300 350 400
Time (h)

Fig. 3. Respirometric measurement repeatability.

A. Tremier et al. / Bioresource Technology 96 (2005) 169–180 175

strates. These phenomena are verified when no other varying between 9.4% and 27.1% of the experimental
limitation than the availability of the organic substrate value. At this stage of the work, this model precision
occurs. was considered as sufficient and the simplest model was
The simulations were performed for the twelve preferred.
experimental results. For each simulation, model
parameters were calibrated. Fig. 4 presents an example
3.3. Parameter estimation and biodegradable organic
of simulation result.
matter fractionation
Whatever the tested temperature, the simulation of
the growing phase was always quite representative. The
Stoichiometric parameters (Y ; f ) were initially esti-
maximum oxygen uptake rate obtained with simulation
mated on the literature basis (ASM values). The factor f
was sometimes higher than the experimental one but the
was kept constant (0.2) as its influence on simulation
difference did not have much influence on the total
results was very low. Y value was calibrated on experi-
amount of consumed oxygen. The decreasing phase was
mental results. A mean value of 0.68 was found with a
generally in accordance with the experimental data. The
coefficient of variation of 11.6%. This result is in con-
most difficult phenomenon to represent was the break
formity with the biomass growth yields (0.56–0.80)
phase. Indeed, the theoretical model can represent a
found for easily-biodegradable substrates such as glu-
sharp decrease for a little time after the maximum
cose or volatile fatty acids (Sperandio, 1998).
oxygen uptake rate, which corresponds to the beginning
The constant parameter KB (saturation constant for
of an exponential decreasing phase. Actually, such a
substrate MB) was set to 3 mmol O2 /kg DM (85 mg O2 /l
sharp break was not observed in each experimental case.
aqueous phase) which is equivalent to the recommended
Experimental break slopes were often more gradual and
value of the ASM (50–150 mg O2 /l). This value was not
as a consequence were quite difficult to simulate pre-
optimised because of its low influence on the simulation
results. KMH (hydrolysis saturation constant for the ratio
Such a difference between the experimental data and
MH/X ) was initially set to 6.5 (–). After optimization, a
the model result would perhaps be lowered by consid-
mean value of 6.54 ± 11.9% was found. No real reference
ering a model with several slowly-biodegradable frac-
may be found in the literature for this parameter, which
tions. These fractions would then have different
is quite new even in the activated sludge models (Henze
hydrolysis kinetics. Nevertheless, the simple model
et al., 2000).
proposed in this study made it possible to model the
Other kinetic parameters such as growth rate,
experimental curves with a mean error factor
hydrolysis rate and death rate varied with temperature.
0 1
  The growth rate (lm ) ranged from lows of 0.13 to highs
 rO2 expðiÞ  rO2 modelðiÞ 
B C of 0.34 h1 for temperatures varying between 19.6 and
@ A
rO2 expðiÞ 56.9 C. As a comparison, a typical value of 0.25 h1
at 20 C was found in the ASM models, in the case of



mmol O2.h-1.kg DM


25 Simulated oxygen uptake rate

Experimental uptake rate



0 50 100 150 200 250 300 350 400 450 500
Time (h)

Fig. 4. Example of simulation result (tested temperature: 39.6 C).

176 A. Tremier et al. / Bioresource Technology 96 (2005) 169–180

liquid substrates. Moreover, in its composting model in comparison with the typical one (<1), generally ap-
applied to vegetable substrates, Kaiser (1996) used a lm plied in liquid organic substrate treatment with activated
value of 0.2 h1 at 40 C, corresponding to the bacteria sludge processes. It explains the delay at the beginning
growth rate. In the same way, the hydrolysis rate (Kh ) of the biodegradation process in the case of solid wastes:
varied between values ranging from 0.10 to 0.20 h1 , X has to grow before significant oxygen consumption
which were in conformity with the typical ASM cited kinetics might be measured.
value of 0.125 h1 at 20 C. Death rates (b) were cal- The sum of MB0 and MH0 equals the total amount of
culated between 0.05 and 0.13 h1 . These results may be biodegradable organic matter in the given granulometric
compared to the ones reported by Henze et al. (2000), structure of the substrate and the time scale of the
which widely varied with substrate, and ranged from process. In this study, it only represented 6.5% of the
0.002 h1 for domestics sewage in the USA to 0.07 h1 total amount of organic matter (expressed as COD) of
for some food-processing wastes with no information this substrate. Such a result might be considered as
about the considered temperature. It is very interesting being very low in comparison with any other organic
to notice that kinetics concerning solid substrates substrates such as pig slurry. In this latter type of sub-
treatment and liquid substrates treatment are quite strate, the only easily-biodegradable organic fraction is
comparable. Then, the longer process durations ob- about 29% of the total COD (Andreottola et al., 1997).
served during biological solid wastes treatments seem to Two main facts must be considered in order to explain
depend more on the substrates intrinsic characteristics this difference. First, the studied substrate is a mixture of
differences (organic fractions quantities, initial biomass sludge and bulking agent. This bulking agent represents
content) than on the enzymatic hydrolysis rate and on a large part of the total COD but is much less bio-
the biomass growth and death kinetics. degradable than the sludge according to the considered
The oxygen uptake rate modelling enabled us to process time scale. Then, the biodegradable fraction
determine values of organic matter fractions: the initial represents a low fraction of the mixture total COD but
biomass content (X0 ), the initial easily-biodegradable would account much more if only the sludge total COD
organic matter content (MB0 ), the initial slowly-bio- was considered. Second, the mixture physical structure
degradable organic matter content (MH0 ). These values plays an important role here. This was previously
did not vary along with the temperature, as they repre- pointed out by Stentiford (2002), who observed that the
sent intrinsic characteristics of the organic substrates. maximum oxygen uptake rate measured on ground
The mean values and their coefficient of variation sample suspended in aqueous solution was higher than
calculated on the basis of the 12 trials are summarised in the one measured on the same substrate in its solid form.
Table 2. It can be immediately noticed that the biomass The originality of this respirometric modelling was
initial content could not be determined precisely (co- to allow the organic matter fractionation from a bio-
efficient of variation of 65.1%). Several causes for this degradability point of view, taking into account the
large variation must be stressed. In fact, X0 initial con- physical specificity of the substrate in the composting
tent partly depends on defrosting conditions of the treatment. As fractions are defined according to the
sludge sample. For example, the weight of the frozen biological reactions theory, and estimated through a
sample (1 or 10 kg) might lead to a different behaviour measurement of the biological activity (oxygen con-
of the biomass during defrosting. Moreover, X0 was so sumption rate), the comparison of biodegradability be-
low in comparison with the total organic content (ex- tween several substrates will be more reliable than with
pressed as COD) that any error on the oxygen con- other physico-chemical fractionation methods (for
sumption amount had a great influence on the X0 value example the comparison of COD content in water ex-
estimation. Thus, X0 , as determined by this method, has tract and extracted solid part of a substrate). Then, the
to be considered as a qualitative value with a large future uses of this method might be as follow: the
standard deviation. MB0 and MH0 were much better comparison of the biodegradability of substrates treated
estimated. The coefficients of variation on these values by composting in the physical way they are usually
(respectively 19.7% and 14.5%) were in conformity with processed, or the study of the influence of the physical
the one accepted for measurement repeatability. It must matrix characteristic (for example granulometry) for a
be pointed out that the MB0 /X0 ratio is very high (170) particular type of substrate.

Table 2
Organic matter fractionation for the studied substrate mixture
X0 (mg O2 /g DM) MB0 (mg O2 /g DM) MH0 (mg O2 /g DM)
Mean value 0.07 11.9 79.9
Coefficient of variation (%) 65.1 19.7 14.5
X0 : initial biomass content; MB0 : initial easily-biodegradable organic matter content; MH0 : initial slowly-biodegradable organic matter content.
A. Tremier et al. / Bioresource Technology 96 (2005) 169–180 177

3.4. Temperature influence on biodegradation kinetics This model makes it possible to determine an opti-
mum kinetic factor and the influence of the temperature
As presented above, simulation results showed that in function of three cardinal points: minimum, optimum
the growth kinetic factor (lm ), the hydrolysis kinetic and maximum temperatures. Figs. 5–7 present CTMI
factor (Kh ) and the death kinetic factor (b) varied sig- modelling results concerning the evolution of growth
nificantly with the temperature. Kinetics first increased (lm ), hydrolysis (Kh ) and death (b) kinetics as a function
with increasing temperatures. But beyond approxi- of temperature. CTMI model’s parameters are displayed
mately 40 C, kinetics started decreasing (Figs. 5–7). in Table 3.
These variations were well modelled with the CTMI Cardinal temperatures describe all types of groups of
model (Cardinal temperature model with inflection) typical microorganisms. Thus, the minimum tempera-
(Rosso et al., 1993). ture corresponds to psychrophilic microorganisms low
2 limits, the optimum temperature to mesophilic micro-
lm ðT Þ ¼ ðlopt ðT  Tmax ÞðT  Tmin Þ Þ=ððTopt  Tmin Þ
organisms optimal range and the maximum temperature
 ½ðTopt  Tmin ÞðT  Topt Þ  ðTopt  Tmax Þ to thermophilic microorganisms highest limits (Bailey
 ðTopt þ Tmin  2T ÞÞ and Ollis, 1986). This result confirms the biological



Experimental growth kinetic (µm)
Simulated µm




0.0 10.0 20.0 30.0 40.0 50.0 60.0
Temperature (°C)

Fig. 5. CTMI model for lm ¼ f ðT Þ.



Experimental hydrolysis rate (Kh)

Simulated Kh



0.0 10.0 20.0 30.0 40.0 50.0 60.0

Temperature (°C)

Fig. 6. CTMI model for Kh ¼ f ðT Þ.

178 A. Tremier et al. / Bioresource Technology 96 (2005) 169–180



Experimental death kinetics (b)
0.12 Simulated b






0.0 10.0 20.0 30.0 40.0 50.0 60.0
Temperature (°C)

Fig. 7. CTMI model for b ¼ f ðT Þ.

Table 3 ways optimal between 35 and 50 C. In the same way,

Parameters of the CTMI model for lm ¼ f ðT Þ, Kh ¼ f ðT Þ and Davis et al. (1992) demonstrated that, during pine barks
b ¼ f ðT Þ
composting, mesophilic microorganisms outnumbered
lm or Kh or b Tmin (C) Topt (C) Tmax (C)
thermophilic ones whatever the stage of the process.
optimum (h1 )
These two results confirm the positive trend of the
lm ¼ f ðT Þ 0.2836 0 38.5 67.8
optimum temperature (around 38.5 C) found in the
Kh ¼ f ðT Þ 0.1798 0 38.2 63.0
b ¼ f ðT Þ 0.0999 0 38.5 67.6 present study with sewage sludge and pine barks mix-
Thus, it should be concluded that our respirometric
method makes it possible to give a good picture of the
model hypothesis of a global biomass regardless of the
behaviour of microorganisms during the aerobic treat-
behaviour of particular microorganisms. One might be
ment of sewage sludge mixed with pine barks.
surprised by the rather low value of the optimum tem-
perature. Indeed, the highest temperatures usually de-
scribed during aerobic treatment of solid organic matter
through composting processes reach 60–70 C. Never- 4. Conclusion
theless, these temperatures do not correspond to the
optimum biological activity. Indeed, the reaction rates The respirometric system presented here is a validated
decrease at high temperature, but the phenomenon of and reproducible method to measure oxygen consump-
heat accumulation in the solid substrate produces a tion kinetics, while respecting the solid matrix charac-
further increase in temperature although biological teristics of the substrate, along with controlled
activity is already decreasing (Haug, 1993). Thus, the conditions of aeration and maintenance of temperature
determination of the optimum temperature has already and moisture.
been a much debated issue. Optimum temperatures from Thanks to this method, a kinetic model comparable
35 to 70 C were described, according to the solid sub- to the one proposed for wastewater treatment with
strate (Jeris and Regan, 1973; Nielsen and Berthelsen, activated sludge was calibrated. Such model enables us
2002) and the moisture level of this substrate (Liang to fractionate the organic content of the substrate and to
et al., 2003). Among studies describing the influence of estimate the kinetic parameters of the aerobic biode-
temperature on kinetics, several authors have already gradation reactions. In the case of the studied mixture
mentioned optimum temperatures around 40 C. For (sludge coming mainly from food-processing industry
example, McKinley and Vestal (1984) studied the wastewater treatment and pine barks), calculated
interactions between the temperature and the activity of kinetics are very closed to the ones generally observed
microbial communities in the composting of municipal during liquid effluents activated sludge treatment. The
sewage sludge. They showed that, whatever the com- main difference between the liquid and the solid treat-
posting time, microbial activities, measured as the rate ment, in term of duration, seems to be due to the organic
of acetate incorporation into microbial lipids, were al- matter composition. The biodegradable fraction of the
A. Tremier et al. / Bioresource Technology 96 (2005) 169–180 179

studied solid mixture was less than 10% of the total AFNOR, 1995. NF ISO 11261––Qualite du sol––Dosage de l’azote
COD. Moreover, this organic biodegradable fraction total––Methode de Kjeldahl modifiee.
AFNOR, 2001. NF EN 13137––Caracterisation des dechets––Dosage
was mainly composed of slowly-biodegradable organic du carbone organique total (COT) dans les dechets, boues et
substrate. This composition is probably a characteristic sediments.
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accessibility to microorganisms. Indeed, without any biologiques aerobies au cours de la phase d’exploitation d’un
consideration of oxygenation limit, the same material casier d’un centre d’enfouissement technique. Ph.D. Thesis, Genie
des procedes, Institut National des Sciences Appliquees de
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