Bioresource Technology 174 (2014) 243–255

Contents lists available at ScienceDirect

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

Performance optimization and validation of ADM1 simulations under

anaerobic thermophilic conditions
Nabil M. Atallah a, Mutasem El-Fadel a,⇑, Sophia Ghanimeh b, Pascal Saikaly c, Majdi Abou-Najm a
a
Department of Civil and Environmental Engineering, American University of Beirut, Lebanon
b
Department of Civil and Environmental Engineering, Notre Dame University – Louaize, Lebanon
c
Water Desalination and Reuse Center and Division of Biological and Environmental Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal
23955-6900, Saudi Arabia

h i g h l i g h t s

 ADM1 simulations of thermophilic anaerobic digesters treating food waste.

 Intermediary output influenced by different parameters depending on related processes.
 Methane-based calibration is less accurate in simulating intermediary by-products.
 Multiobjective optimization provided better overall results than methane optimization.
 Optimization results were validated upon their application on independent experiments.

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

Article history: In this study, two experimental sets of data each involving two thermophilic anaerobic digesters treating
Received 8 August 2014 food waste, were simulated using the Anaerobic Digestion Model No. 1 (ADM1). A sensitivity analysis was
Received in revised form 26 September conducted, using both data sets of one digester, for parameter optimization based on five measured per-
2014
formance indicators: methane generation, pH, acetate, total COD, ammonia, and an equally weighted
Accepted 29 September 2014
Available online 13 October 2014
combination of the five indicators. The simulation results revealed that while optimization with respect
to methane alone, a commonly adopted approach, succeeded in simulating methane experimental
results, it predicted other intermediary outputs less accurately. On the other hand, the multi-objective
Keywords:
Thermophilic anaerobic digestion
optimization has the advantage of providing better results than methane optimization despite not cap-
Food waste turing the intermediary output. The results from the parameter optimization were validated upon their
ADM1 independent application on the data sets of the second digester.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Anaerobic digestion (AD) is a biological treatment process that
involves a series of synergetic biochemical pathways that degrade
organic matter into a methane-rich gas that can be used as a source
of energy (Cesur, 2004). While it was initially applied in the treat-
ment of liquid wastes with low solids content, its application
evolved to targeting higher solid content wastes, such as food
waste (El Fadel et al., 2012) albeit the drawback of system instabil-
ity associated with the fast release of Volatile Fatty Acids (VFA) and
high ammonia levels (Ghanimeh et al., 2013; Banks et al., 2008;
⇑ Corresponding author at: American University of Beirut, Faculty of Engineering
and Architecture, Bliss Street, PO Box 11-0236, Beirut, Lebanon. Fax: +961 1 744
462.
E-mail address: mfadel@aub.edu.lb (M. El-Fadel).
Ward et al., 2008; Jeong et al., 2005). This problem is more pro-
nounced in thermophilic systems where the high temperature
(50–55 °C) increases degradation rates and speeds up the release
of VFAs. As a result, long-term operation of thermophilic digesters,
fed only with food waste, is often subject to instability and, in some
instances, irreversible accumulation of inhibiting metabolic
byproducts. In this context, the prediction of such disturbances
and reduction of their occurrences become critical to a successful
digester operation. For this purpose, the Anaerobic Digestion
Model (ADM) series were developed by the International Water
Association to test various biochemical reactions in the AD process
including disintegration, hydrolysis, substrate uptake and decay, as
well as physiochemical processes such as association/dissociation
and liquid–gas transfer (Esposito et al., 2011). ADM1 has report-
edly been successfully used in simulating AD of various types of
waste, including, but not limited to, municipal waste, sewage

http://dx.doi.org/10.1016/j.biortech.2014.09.143
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
244 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255
sludge, manure and black water, and showed high correlation with
experimental results (El Fadel et al., 2012; Kerroun et al., 2010;
Wichern et al., 2009; Lee et al., 2009; BouBaker and Ridha, 2007;
Jeong et al., 2005). Invariably, those applications rely on a set of
data pertaining to one application using the final output (methane)
to calibrate the model.
In this work, the ADM1 was applied for the first time to simu-
late the thermophilic AD of food waste using the performance data
of four lab scale digesters. The simulation involved, in conjunction
with a sensitivity analysis, parameter optimization and cross-
validation against independent experimental data sets both at
the intermediary by-products (pH, acetate, ammonia and Total
COD), and final experimental output (CH4-based results). To the
best of our knowledge, no similar work has been reported in the
literature.
2. Methods
2.1. Experimental program
Two anaerobic reactors (Bioflo 110, New Brunswick Scientific
Co.) of 14 L capacity (9 L working volume) were fed with food
waste collected from households and food markets, ground and
homogenized with a lab food grinder, and characterized. The raw
waste had a total solids content of 62–75 kg/m3 and a COD of
96–120 kg/m3.
Both reactors were operated at 55 °C and were continuously
mixed with an internal impeller at 80 rpm. The digesters were
fed with an equal batch of waste 3 times per week (Monday,
Wednesday and Friday) resulting in the lowest daily loading rate
over the weekend (Friday, Saturday and Sunday). Accordingly, a
harmonic behavior of daily methane generation was observed with
the lowest value being after Friday’s feeding (i.e., on Saturday, Sun-
day and Monday). Wasting occurred at a volume of 700 ml to
achieve a weekly average HRT of 30 days. The experiment lasted
for 700 days and two separate sets of experimental data, with sta-
ble average weekly feeding rate, were selected for model calibra-
tion and validation:
Set 1 – Digesters A and B were run at a stable organic loading
rate (OLR) of 2.4 gVS/L/d for 115 days (days 376–491) and
referred to as A1 and B1, respectively.
Set 2 – The digesters were run at a constant OLR of 2 gVS/L/d for
58 days (days 569–627) and the results are referred to as A2 and B2
for digesters A and B, respectively.
2.2. Experimental analysis
The temperature control was automated through a control unit
connected to a built-in temperature probe and a heating blanket.
The pH was continuously measured using a submerged pH probe
and controlled by manual addition of NaOH (5 M) solution – when
needed. Biogas measurements were taken once or twice daily,
using the water displacement method for total gas yield and a dual
wavelength infrared cell with reference channels (GEM-2000 mon-
itor, Keison Products, UK) for CH4 and CO2 concentrations (% by
volume). Biochemical analysis was conducted on a weekly basis
whereby a fraction of the wasted material was used to measure
total and volatile solids and total COD. Then, samples were centri-
fuged (4700 rpm, 10 min) and passed through filters with 1.2 lm
openings for analysis of soluble solids, soluble COD, ammonia,
and alkalinity. For VFAs, the filtrate was further passed through
0.2 lm syringe filter and acidified with phosphoric acid to pH of
2. The concentrations of acetate, propionate and butyrate inside
the digesters were measured using a gas chromatograph (Trace
GC Ultra, Thermo Electron corporation) equipped with a flame ion-
ization detector and a TR-FFAP capillary column with nitrogen car-
rier gas.
COD (total and soluble) was determined using the modified
5220D procedure of Standard Methods for the Analysis of Water
and Wastewater (APHA et al., 1998) by HACH high-range COD kit
(HACH Company, Loveland, Colorado). Solid content (total, sus-
pended, dissolved and volatile) was analyzed using Standard Meth-
ods (APHA et al., 1998) 2540B and 2540E procedures. Partial and
total alkalinities (PA and TA, respectively) were measured by titra-
tion with HCl (0.2 N) to pH of 5.75 and 4.3, respectively. Total
ammonia content was determined by spectrophotometry using
HACH high-range ammonia kit (HACH Company, Loveland,
Colorado).
Carbon and nitrogen content in the feed were determined using
an organic elemental analyzer (Flash-1112 series EA, Thermo Finn-
igan). Total organic carbon in the feed was measured by combus-
tion catalytic oxidation/NDIR technique using a dedicated TOC
analyzer (TOC-VCSH Total Organic Carbon Analyzer, Shimadzu Cor-
poration, Japan). Total Phosphorous in the feed was measured
using inductively coupled plasma mass spectrophotometry (Agi-
lent 7500ce, EPA 200.8-3050).
2.3. Simulation process
The Anaerobic Digestion Model (ADM), developed by the Inter-
national Water Association (IWA), was adopted in this study. The
model ensures mass balance amongst various bacterial communi-
ties interacting with a heterogeneous substrate (Eqs. (1) and (2)) to
represent transformation processes within the reactor boundaries.
X
dSliq;i Q  
¼ : Sin;i  Sliq;i þ qj ti:j ð1Þ
dt V liq
j¼119
where Sliq,i = reactor concentration of soluble state variable i;
Q = flow into and out of the reactor, m3/day; Vliq = liquid reactor vol-
ume, m3; Sin,i = input concentration of soluble state variable I;
Rqjmi,j = the sum of the specific kinetic rate (qj) of process j multi-
plied by the stoichiometric coefficients (vi,j).
dX liq;i Q   X
¼ : X in;i  X liq;i þ qj ti:j ð2Þ
dt V liq j¼119
where Xliq,i = reactor concentration of particulate state variable i;
Xin,i = input concentration of particulate state variable i.
In addition, acid-base equilibrium (Eq. (3)) is incorporated to
simulate pH temporal profile and associated potential inhibition:
Sac Spr Sbu Sva
SCatþ þ SNHþ þ SHþ  SHCO3      SOH  SAn ¼ 0
4 64 112 160 208
ð3Þ
where Sac , Spro , Sbu , Sva , SNH4 and SHCO3 are the concentrations of
ionized forms of buffer components.
Also, liquid–gas transfer processes are considered (Eq. (4)) to
determine biogas generation and composition:
dSgas;i qgas V liq
¼ Sgas;i þ q ð4Þ
dt V gas V gas T;i
where Sgas,i = gas phase concentration of gas component i; qgas = gas
flow outside the reactor; Vliq = reactor liquid volume; Vgas = reactor
gas volume (headspace volume); qT,i = specific mass transfer rate
of gas i.
The set of governing equations is solved simultaneously to sim-
ulate the dynamics and biological kinetics in the reactors. Details
about model governing equations, input parameters, and underly-
ing assumptions are described in Batstone et al. (2002).
 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255
The ADM1-based code using the MatlabÒ/SimulinkÒ platform
(Rosen and Jeppson, 2006) was modified to allow for varying daily
flow rates. A separate module was incorporated to generate the
ADM1 input from experimental feed parameters using a transfor-
mation matrix (Zaher et al., 2009). Initial conditions in the reactors
were assumed to be similar to those reported for the AD of food
waste (Bajzelj, 2009). The model’s biochemical, physical, and phys-
ico-chemical parameters were categorized through a sensitivity
analysis to select the most influential ones in subsequent optimiza-
tion. For this purpose, the model was extended with a loop that
calls for each parameter independently and assigns to it a range
of values, while keeping all other parameters constant. The
assigned values were stored separately in an Excel sheet and ran-
ged between 90% and 300% of benchmark values reported by
Rosen and Jeppson (2006). Five performance indicators were
adopted in the analysis of the simulation results namely, daily
methane generation rate (L/d), pH level, acetate (mg/L), ammonia
(mg/L), and total COD (mg/L). In addition, a sensitivity analysis
for an equally weighted combination (EWC) of the five indicators
was also conducted. The Sensitivity Index (SI) for the performance
indicators was calculated using Eq. (5a) (Souza et al., 2013) while
for the EWC Eq. (5b) was used:
8P
>
>
jSfixed ðtÞSnew ðtÞj
ðaÞ
>
< N
SI ¼ XNp P
jSfixed ðtÞSnew ðtÞj
>
> 1
X ðbÞ
> Np
: i¼1 Sfixed ðtÞ
where Sfixed(t) and Snew(t) are the results of using a benchmark
(fixed) value of a parameter and the new results of varying the same
parameter, respectively, calculated at time (t); N is the number of
days and Np is the number of performance indicators.
For the EWC, the SI was standardized because the five perfor-
mance indicators have different units and as such Eq. (5b) was
used. For example, the pH is dimensionless and ranges between
0 and 14 while the other indicators do not have an upper bound.
So, for an effective sensitivity analysis and later on optimization,
all indicators should lie on the same scale.
The parameters to which the simulation results exhibited most
sensitivity were then optimized with the experimental data by
minimizing the error between simulated and experimental output
using the least square error method (Eqs. (6a) and (6b)). The error
was calculated automatically by applying the fminsearch function
in MatlabÒ on the results of two experiments (A1 and A2).
8 N
>
> X
>
>
> ½Oi ðtÞ  Si ðtÞ2 ðaÞ
< i¼1
Least Square Error ¼ ( )
>
> XNp X N h i 2
>
> Oi ðtÞSi ðtÞ
ðbÞ
>
: Oi ðtÞ
j¼1 i¼1
where Oi is the observed or measured value at time t, Si is the ADM1
simulated value corresponding to Oi at time t, and N is the number
of points in the data set.
Eq. (6a) was adopted for the five performance indicators while
for the EWC; Eq. (6b) was used for the same already mentioned
reason.
Finally, after the sensitive parameters were optimized for the
various performance indicators (intermediary and final outputs)
on experiments A1 and A2, model validation was conducted using
those same parameters on intermediary outputs of experiments B1
and B2.
The daily methane generation rate was selected to validate the
model taking into consideration that the sensitivity of a parameter
and its influence on the model depend on the number of mecha-
nisms associated with it (Jeong et al., 2005). Knowing that methane
production is related to most processes, it is often used for
245
calibration and validation of AD models (Souza et al., 2013; Zhou
et al., 2012; Jeong et al., 2005).
3. Results and discussion
3.1. Experimental results
At first, the digesters were seeded with manure only and diges-
ter A was run at 100 rpm mixing speed whereas digester B was run
without mixing. The startup process lasted about 190 days during
which the Organic Loading Rate (OLR) was gradually increased to
2.4 gVS/L/d in digester A and 1.9 gVS/L/d in digester B, causing sys-
tem overload in both digesters. Details of the startup procedure
and results are presented in Ghanimeh et al., 2012.
After about 60 days of reduced feeding, both digesters were
reseeded. Digester A was inoculated with a control seed mix con-
sisting of wasted digestate, cattle manure, and activated sludge.
Digester B was inoculated with the control mix and additional
landfill leachate and municipal waste compost. The OLR was
slowly increased to 2.4 gVS/L/d, over 230 days, with continuous
mixing at 80 rpm. The digesters were run under steady loading
between day 376 and day 491. During this period, the specific
methane generation was relatively stable at an average of 330
ð5Þ and 370 L CH4/kg VS in digesters A and B, respectively. The total
concentration of VFAs was low (average = 510 and 220 mg Ac/L
in A and B, respectively) and average alkalinity was 4600 mg/L in
digester A and 5300 mg/L in digester B. The OLR was subsequently
reduced to about 2 gVS/L/d and maintained constant between day
569 and day 627. During this period, average specific methane gen-
eration was closely similar in both digesters with an average of
350 L CH4/kg VS. The VFAs level was 770 mg/L and 230 mg/L, on
average, in digesters A and B, respectively. Afterwards, the digest-
ers underwent an organic shock for one week, followed by inter-
rupted feeding and gradual incremental loading (Ghanimeh et al.,
2012).
3.2. Sensitivity analysis
The sensitivity analysis of reactors A1 and A2 yielded similar
patterns as B1 and B2, respectively, for all measured performance
indicators. Therefore, only the results of A1 and A2 are reported
in this paper. Results for B1 and B2 are provided in the accompany-
ing electronic appendix.
While some parameters are highly sensitive at one end of the
ð6Þ simulated range, they were less sensitive at the other end. Taking
the methane indicator for example, its results exhibited the great-
est sensitivity to the inhibitory free ammonia concentration for
acetate degraders (KI NH3 ) and the rate of uptake of propionate
(Km_pro) at the low KI NH3 and Km_pro values and a minor influence
at the high KI NH3 and Km_pro values within the range used
(Fig. 1a). In contrast, methane results are highly sensitive at the
high range of the decay rates for propionate (Kdec_Xpro) and hydro-
gen (Kdec Xh2 ) degraders and practically insensitive at the lower end
(Fig. 1b). If such parameters are considered for optimization, the
model might be biased towards the extreme at which the parame-
ter is most influential. As such, the other parameters are forced in a
direction to counterbalance the extreme deviation from bench-
mark values leading to a pseudo-optimum solution thus limiting
the flexibility of the system by restricting some parameters to
either side of benchmark values. Accordingly, the parameters
selected for further analysis and optimization are those showing
equally high sensitivity at both extremes of the range (Fig. 1c),
which secures flexibility and provides real optimization in either
direction of the benchmark value.
246 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255

Table 2
Sensitivity Index (SI) 3 Summary of combined sensitive parameters of Set 1 and 2.

2 Methane pH Acetate Ammonia TCOD EWC

1 f h2 su fac_su fpro_su fpro_su fbu_su f h2 su

fpro_su Km_su fac_su fac_su fpro_su fpro _su
0 fac_su Km_ac Km_aa Km_su fac_su fac_su
0 100 200 300 400 Km_ac Ks_ac Km_ac Km_aa Km_ac Km_ac
Fraction of benchmark value (%) Ks_ac Kdec_xsu Ks_ac Ks_aa Ks_ac Ks_ac
(a) KI_NH3 Km_pro
Kdec_xsu Kdec_xaa Kdec_xsu Km_ac Kdec_xsu Kdec_xsu
Y_su Y_su Kdec_xaa Kdec_xsu Y_su Y_su
Y_aa Y_aa Y_su Kdec_xaa Y_aa Y_aa
Y_ac Y_ac Y_aa Y_su Y_ac Y_ac
Sensitivity Index (SI)

0.5 Y h2 Y h2 Y_ac Y_aa Y h2 Y h2

0.4 Y h2 Y_ac
0.3 Y h2
0.2
0.1
0 A high similarity was observed in simulating A1 and A2 exper-
0 100 200 300 400 imental results. Thus, a combined set of sensitive parameters was
Fraction of benchmark value (%) developed (Table 2) and used for subsequent analyses and optimi-
(b) Kdec_Xh2 Kdec_Xpro zation. Consistent with the findings of Jeong et al. (2005), simula-
tions based on methane exhibited high sensitivity to the yield of
catabolism of hydrogen (f h2 su ), propionate (fpro_su) and acetate
Sensitivity Index (SI)

4 (fac_su) from sugars, in addition to some anabolism yields (Ysu,

3 Yaa, Yac, Yh2 ), the Monod maximum specific uptake rate from ace-
2 tate (Km_ac), and the half saturation constant for acetate (Ks_ac).
1 Similarly, the simulations exhibited sensitivity to the decay rate
0 of sugar degraders (Kdec_Xsu), which was one of the prominent fac-
0 100 200 300 400 tors in the thermophilic digester in Lee et al. (2009) rather than the
Fraction of benchmark value (%) mesophilic one (similar to our case). Note that Batstone et al.
(c) Km ac Ks ac (2002) reported low sensitivity to the yields of anabolism and
kinetic parameters. The simulation results using acetate-based
Fig. 1. Sensitivity index of selected parameters (taking methane as indicator): (a) analysis were equally sensitive to the same parameters defined
Inhibitory free ammonia concentration for acetate degraders (KI NH3 ) and rate of for the methane-based best fit with the exception of the yield of
uptake of propionate (Km_pro); (b) decay rates for propionate (Kdec_Xpro) and
hydrogen catabolism (f h2 su ), the Monod maximum uptake rate
hydrogen degraders (Kdec h2 ); (c) uptake rate for acetate (Km_ac) and half saturation
constant for acetate (Ks_ac). for amino acids (Km_aa), and the decay rate of amino acids degrad-
ers (Kdec-Xaa). The latter two parameters did not cause high sensi-
tivity in systems treating a mixed waste of flour and dog food
Therefore, sensitivity indices at both extremities of the simu- (Lee et al., 2009). When examining the sensitivity results of the
lated range (90% and +300% away of benchmark values) were cal- EWC, it is readily noticeable that they are the same as that of the
culated separately and the parameters were ranked according to methane optimization, hence it is expected that optimization using
their respective Sensitivity Index (rank 1 for highest SI and rank this approach will fine-tune the methane parameters to capture
52 for lowest SI) for both extremes of the range. Then, the param- the trend of other performance indicators as well. In short, the
eters were prioritized based on the average of their ranks at both results indicate that sensitive parameters differ depending on asso-
extremities and the parameters with an average SI less than or ciated processes (Table 2) which infers that using methane gener-
equal to 10 were selected (Table 1). ation in the optimization process may not produce the best fit
solution for all other performance indicators.

Table 1
Parameters of high sensitivity with respect to all performance indicators and EWC.

Sensitive parameters Average SIa ranking of sensitive parameters

Methane pH Acetate Ammonia COD (Total) EWC
A1 A2 A1 A2 A1 A2 A1 A2 A1 A2 A1 A2
fac_su 6 4 8 6.5 9 3 7 8 8.5 5 5.5 3
fpro_su 8 7 – – – 9.5 10 8 7.5 7.5 – 7
fbu_su – – – – – – – – 10 8.5 – –
f h2 su – 5 – – – – – – – – – 9.5
Km_su – – – 7 – – 6.5 6 – – – –
Km_aa – – – – 7.5 7 6 5.5 – – – –
Ks_aa – – – – – – 10 8.5 – – – –
Km_ac 2.5 3 2.5 3 3 2 8.5 7 2 2 3 2.5
Ks_ac 7 5.5 8.5 9.5 8.5 9 – – 6.5 5.5 6.5 6
Kdec_xsu 6.5 – 3.5 5.5 6 6.5 – 5.5 6.5 10 6 –
Kdec_xaa – – – 7.5 8 8.5 7.5 7 – – – –
Y_su 2.5 2 1 1 3 3 3 2 2 1 2 1.5
Y_aa 9 – 7 – 9 8.5 8.5 9.5 10 – 8 –
Y_ac 6 9 7.5 – 4.5 6 7 – 5.5 – 5 –
Y h2 7 7 8.5 – 8.5 7 9 – 6.5 6 7 7.5
a
Average of SI at 90% and +300% away from benchmark values (SI = sensitivity index).
 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255
3.3. Model calibration: optimization based on methane
The results of the optimization process for A1 and A2, based on
the methane generation best fit, are shown in Table 3 and com-
pared to the literature. The calibrated parameters of A1 are closely
similar to the base parameters reported by Rosen and Jeppson
(2006) with a deviation ranging between 0.7% and 30.0% in abso-
lute value while a larger offset is observed for digester A2 with a
deviation ranging between 6.2% and 98.5% in absolute value. A
similar high deviation (259%) from the values given in Rosen and
Jeppson (2006) was observed for Ks_ac in Jeong et al. (2005). The
results of both digesters showed that the yield of sugars Y_su is
the most sensitive parameter with the highest deviation of
98.5% (outside the sensitivity range of 90% to 300%) in A2.
Fig. 2 displays the plots of the 5 performance indicators of A1
based on methane optimization. The model predicts methane gas
generation adequately and follows closely the experimental pat-
tern throughout the experiment duration (Fig. 2a). Even though
the model under predicts the acetate level, it captures the general
trend and depicts the presence of a sudden jump, around day 95
(Fig. 2c), which is of major importance for system stability and con-
trol. Similarly, the pH was generally underestimated; yet the sim-
ulated plot follows the quasi-stable experimental behavior and
clearly captures the alarming decrease, on day 95 (Fig. 2b), coincid-
ing with the sudden increase in acetate. As to the ammonia level,
the simulated results started off the true values but converged,
after day 50, to coincide with experimental data (Fig. 2d). The pat-
tern of total COD, consisting of an increasing curve followed by a
stabilizing period, was captured but with a considerable offset
from real values (Fig. 2e).
Fig. 3 displays the plots of the 5 performance indicators of A2,
based on methane optimization. Similar to A1, the daily methane
generation was captured (Fig. 3a). Compared to A1, the pH results
were closer to real values with a minimal offset beyond day 20
(Fig. 3b). Similarly, the simulated acetate concentrations coincide
with real values, where provided, except for day 29 where the
model shows a steep peak (Fig. 3c). This can be either a false alarm-
ing output or a true acetate surge that was not captured by exper-
imental data, due to the low sampling frequency, and occurring
during a period (between days 25 and 35) of relatively low pH
(Fig. 3b). Similar to A1, the error in ammonia predictions was
decreasing with time (Fig. 3d) but did not reach convergence, most
probably because of the short experimental duration (50 days
compared to 114 days for A1). Unlike A1, the TCOD results of A2
showed good correlation with experimental data (Fig. 3e).
The simulated methane pattern for A1 is harmonic with a rela-
tively constant period and amplitude (Fig. 2a) which fairly agrees
with the feeding pattern mentioned in the materials and methods
section. While for A2, the simulated pattern (Fig. 3a) is inconsistent
with its feeding pattern indicating that steady-state conditions,
Table 3
Estimated parameters for digesters A1 and A2.
Parameter Initial values Rosen and Jeppson (A1) (% deviation from initial
(2006) value)
f h2 su 0.19 0.2 (5.26%)
fpro_su 0.27 0.269 (0.37%)
fac_su 0.41 0.381 (7.1%)
Km_ac 8 9.313 (16.4%)
Ks_ac 0.15 0.151 (0.67%)
Kdec_xsu 0.02 0.0226 (13%)
Ysu 0.1 0.07 (30%)
Yaa 0.08 0.085 (6.25%)
Yac 0.05 0.0497 (0.6%)
Y h2 0.06 0.058 (3.33%)
The percent deviation is shown in bold.
247
where ADM1 performs best, were not fully achieved thus causing
the A2 parameters to deviate more from the benchmark values.
This suggests that the initial values reported by Rosen and
Jeppson (2006) are ideal for conditions similar to that of A1 and
for methane-based optimization as will be demonstrated when
conducting optimization based on other performance indicators.
A comparison of the average absolute percent relative error
between the five component indicators as a result of methane opti-
mization is summarized in Table 4. Note that methane, acetate and
TCOD simulation results exhibited an error that is within similar
ranges reported in the literature (Jeong et al., 2005; Lee et al.,
2009; Wichern et al. 2008). However, the error in the simulated
pH was higher than that reported by Wichern et al. (2008) which
can be attributed to different experimental temperatures (thermo-
philic in this study vs mesophilic by Wichern et al. (2008)). It is
worth noting that the high absolute percent relative error in
ammonia for digester A1 is due to the huge difference between
the model and experimental results at the beginning of the simu-
lation, between day 0 and 40. If we discount these points, the
110% error on ammonia for A1 (Table 4) would be 29.67%. Also,
the high discrepancy in acetate results may be attributed to the
low number of experimental data points. For instance, the high
average error for A2 (54%, Table 4) is mainly due to an outlier on
day 29. If only this point is omitted, the average error drops to 14%.
3.4. Model calibration: optimization based on other performance
indicators
In an attempt to further improve the calibration results, the
optimization process was repeated for A1 and A2 using major per-
formance indicators other than methane, including pH, ammonia,
acetate, TCOD and finally an EWC of the five performance indica-
tors. The results showed a greater deviation from the initial values,
in comparison with methane-based optimization (Table 5). For
example, acetate-based optimization showed that the deviation
of the parameters ranged between 2.2–113.5% and 6.3–307.5%
(absolute value) for A1 and A2, respectively, compared to
0.4–30.0% and 12.2–98.5% for A1 and A2, respectively, in meth-
ane-based optimization, with TCOD and ammonia exhibiting the
widest deviation ranges. As for the EWC, the deviation was some-
where between that of methane and other parameters and ranged
between 0.5–77% for A1 and 11.3–132% for A2, reflecting the effect
of combining all performance indicators.
The simulated results (Figs. 4 and 5) showed that optimization
based on various performance indicators (with the exception of
ammonia) is able to capture the general experimental trend, but
with a higher error compared to methane-based optimization
curves (Table 6a). The second-best results were those of acetate-
based optimization. In contrast, ammonia-based optimization
yielded unrealistic results and wrong overall patterns.
(A2) (% deviation from initial Jeong et al. (2005) Lee et al. (2009)
value)
0.178 (6.23%) – –
0.033 (87.8%) 0.54 –
0.374 (8.86%) 0.202 –
14.41 (80%) – 14
0.1215 (19%) 259 0.6
0.0245 (22.6%) – 0.03
0.001 (98.5%) 0.05 –
0.1 (25.6%) – –
0.0434 (13.6%) 0.1 –
0.1 (68.1%) 0.0282 –
248 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255

Fig. 2. Simulated and experimental data for A1 digester based on methane optimization: (a) methane; (b) pH; (c) acetate; (d) ammonia; (e) TCOD.

On the other hand, optimizing on each performance indicator
improves its respective errors, as shown in Table 6 (a). For exam-
ple, pH-based optimization reduced the error in pH simulation
results from 9.4% to 1.2% for A1 and from 5.7% to 2.2% for A2. These
findings are further verified in Figs. 4 and 5, where optimization on
each performance indicator brings the simulated results closer to
the real pattern and values of that specific indicator, for both
digesters A1 and A2. Hence, optimizing for methane, even though
it yields realistic patterns, does not guarantee the optimum solu-
tion for all outputs and thus it is critical to define the desired
importance of each component prior to the optimization process.
Alternatively, the EWC can provide a unified solution with overall
improved average results compared to optimization based only on
methane. In fact, this approach exhibited major improvements for
A2, namely in ammonia (16.5%), acetate (11%) and TCOD
(10%), with a minor increase in error in methane (from 14% to
14.6%) and pH (from 5.7% to 6.6%). Also, all performance indicators
for A1 were moderately improved, with the exception of ammonia
(5% increase in error), with the highest improvements being in ace-
tate (7%) and TCOD (3%). The higher overall percentage of
improvement in A2 over A1 can be attributed to the higher devia-
tion of the parameters from the benchmark. Yet, the decrease in
the error, in both experiments, could not be reduced to levels close
to those determined separately for each performance indicator. In
 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255 249

Fig. 3. Simulated and experimental results of A2 digester based on methane optimization: (a) methane; (b) pH; (c) acetate; (d) ammonia; (e) TCOD.

Table 4
Average absolute percent relative error based on methane optimization (Standard deviation).

Methane pH Acetate Ammonia TCOD

A1 13.7% (10.94%) 9.4% (2.65%) 58.18% (27.45%) 110.2% (117.66%) 70.16% (43.42%)
A2 14% (15.67%) 5.74% (2.56%) 54.1% (98.21%) 310.63% (193.77%) 22.2% (15.8%)
Jeong et al. (2005)a 5–40% – 10–97% – –
Lee et al. (2009)a 5–35% – 5–200% – 5–90%
Wichern et al. (2008)b 5–25% 1–5% 5–200% – –

The percent deviation is shown in bold.

a
The relative percent error was not reported and thus approximated as a min–max range.
b
The error was reported but, for consistency, reported as a min–max range.
 250
Table 5
Optimized parameters based on five performance indicators and EWC for A1 and A2.

Optimized value based on least square error in different performance indicators for A1 and A2 (% deviation from initial value)
Parameter Initial Methane pH Ammonia Acetate TCOD EWC
value
A1 A2 A1 A2 A1 A2 A1 A2 A1 A2 A1 A2
fac_su 0.41 0.381 0.46 (12.2%) 1.0211 (149%) 1.068 0.00134 1.3 (217.1%) 0.326 0.384 (6.3%) 0.0473 0.023 0.496 (21%) 0.6513
(7.1%) (160.5%) (99.6%) (20.5%) (88.46%) (94.4%) (58.85%)

N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255

fbu_su 0.13 - - - - - - - - 0.02 0.0312 - -
(84.62%) (76%)
fpro_su 0.27 0.269 0.037 - - 0.087 0.1406 0.2307 0.024 0.0118 0.0561 0.17 0.04273
(0.37%) (86.3%) (67.77%) (47.93%) (14.56%) (91.11%) (95.63%) (79.2%) (37.03%) (84.17%)
f h2 su 0.19 0.2 (5.26%) 0.1 (47.37%) - - - - - - - - 0.189 0.00733
(0.53%) (96.14%)
Km_su 30 - - 76.157 31.34 (4.46%) 4.36 34.16 - - - - - -
(153.85%) (85.5%) (13.87%)
Km_ac 8 9.313 4.23 (47.13%) 50.266 33.7 (321.3%) 78.03 5.24 7.824 4.89 153.43 18.9 (136.3%) 10.224 3.97650.3%)
(16.4%) (528.33%) (875.4%) (34.5%) (2.2%) (38.88%) (1817.9%) (27.8%)
Km_aa 50 - - - - 12.44 4.47 13.52 46.52 - - - -
(75.12%) (91.1%) (72.96%) (6.96%)
Ks_aa 0.3 - - - - 0.0612 0.238 - - - - - -
(79.6%) (20.67%)
Ks_ac 0.15 0.151 0.23 (53.3%) 0.0401 0.1405 - - 0.204 (36%) 0.338 0.076 0.8 (433.3%) 0.187 0.167 (11.33%)
(0.67%) (73.3%) (6.33%) (125.33%) (49.3%) (24.67%)
Kdec_xsu 0.02 0.0226 0.036 (80%) 0.011 (45%) 0.0219 (9.5%) 0.0192 (4%) 0.0421 0.0287 0.0251 0.008 (60%) 0.0024 0.0174 0.0464 (132%)
(13%) (110.5%) (43.5%) (25.5%) (88%) (13%)
Kdec_xaa 0.02 - - 0.00133 0.0565 0.0207 (3.5%) 0.0247 0.0427 0.0815 - - - -
(93.35%) (182.5%) (23.5%) (113.5%) (307.5%)
Y_su 0.1 0.07 0.00148 0.00144 0.0011 0.17 (70%) 0.002 (98%) 0.0655 0.00108 0.00366 0.002 (98%) 0.0534 0.001824
(30%) (98.52%) (98.56%) (98.9%) (34.5%) (98.92%) (96.34%) (46.6%) (98.18%)
Y_aa 0.08 0.085 0.0314 0.00321 0.0426 0.0733 0.22 (175%) 0.0561 0.05 (37.5%) 0.001 0.00175 0.1415 0.0104 (87%)
(6.25%) (60.75%) (96%) (46.75%) (8.375%) (30%) (98.75%) (97.8%) (76.9%)
Y_ac 0.05 0.0497 0.0603 0.00584 0.0133 0.192 (284%) 0.167 (234%) 0.0359 0.06 (20%) 0.0042 0.0103 0.0281 0.104 (108%)
(0.6%) (20.6%) (88.32%) (73.4%) (28.2%) (91.6%) (79.4%) (43.8%)
Y h2 0.06 0.058 0.026 0.0094 0.193 0.0035 0.46 (666.7%) 0.0662 0.0288 (52%) 0.0075 0.0028 0.0667 0.024 (60%)
(3.33%) (56.67%) (84.3%) (221.7%) (94.17%) (10.33%) (87.5%) (95.3%) (11.16%)

The percent deviation is shown in bold.

 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255 251

Fig. 4. Model optimization results of A1 based on 5 performance indicators and EWC: (a) methane; (b) pH; (c) acetate; (d) ammonia; (e) TCOD.

A1, the equally weighted combination reduced the error on pH,
acetate and TCOD from 9.4%, 58.2% and 70.2% (from methane based
optimization) to 8.4%, 51.4% and 67.4% which are still higher than
the minimum values reached in calibration on separate indicators
(1.21%, 40.8%, 49.6%). Similarly for A2, EWC calibration dropped
the error on ammonia, acetate and TCOD from 310.6%, 54.1% and
38.8% (from methane based optimization) to 8.4%, 51.4% and
67.4% which are still higher than the minimum values reached in
calibration on separate indicators. However, the equally weighted
combination remains a reliable approach since it reduces the errors
on methane-based optimization and provides a unified set of pre-
dictors that equally account for all performance indicators.
Finally, the following general observations can be drawn:
- The overall pattern of daily methane generation can be cap-
tured with optimization on any of the indicators used in this
study, at the exception of ammonia. But accurate values are
obtained only with methane- or acetate-based optimization.
- The simulated results of ammonia start at a high level and con-
verge to real values with time.
- Ammonia-based optimization is not able to capture the pattern
of any indicator, other than ammonia, and results in high errors.
- Multi-objective minimization improves the methane-based cal-
ibration results and provides a unified set of parameters equally
accounting for each performance indicator.
3.5. Model optimization: limitations

- Methane- and acetate-based optimization yield very close Despite the improvements made on ammonia and TCOD, both
results for all indicators. graphs (Fig. 5d and e, respectively) do not capture the trend and
252 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255

Fig. 5. Model optimization results of A2 based on five performance indicators and EWC: (a) methane; (b) pH; (c) acetate; (d) ammonia; (e) TCOD.

tend to have the same shape irrespective of the indicator used for
optimization. One possible reason could be that a micro fraction of
the entire sample used for measuring acetate, ammonia and TCOD
concentrations is not representative of the entire digester.
In comparison, one potential reason that the pH optimization
resulted in a significant improvement of pH estimates, despite
the fact that measurements were also taken at a single location,
was the presence of numerous experimental points which trans-
formed the problem to a data-fitting one. In other words, the high
repetition rate of pH measurements at single point, coupled with
mixing provided the optimization problem with a more represen-
tative dataset to optimize with.
As for the case of acetate optimization, despite the low number
of data points (less than the number of parameters), the trend was
fine-tuned from that of methane optimization due to the fact that
methane is a direct derivative of acetate. In other words, the trend
generated from methane optimization more or less replicates the
actual acetate. Thus selecting the starting point in the acetate opti-
mization process to match the parameters from the methane-
based optimization will bypass the setback of having a low number
of data points and simplify optimization to fine tuning. For digester
A2, this has worked perfectly by reducing the error from 54% to
3.2%. However, for A1, the low number of data points and high pos-
sibility of the data points not being representative of the digester
and improved methane optimization from 58% to 40% only. In fact,
the non-steady, wave like patterns of measured points could have
made it difficult for the optimizer to capture the trend starting
with Batstone’s suggested values.
For the cases of ammonia and TCOD, setting the starting point
equal to methane-based optimization or any other indicator-based
optimization did not significantly improve the result since none of
the indicator-based optimizations (other than ammonia) was able
to capture the actual trend. Notice for the case of ammonia, that all
component-based optimization have huge offsets between day 0
Table 6
Average absolute percent relative error based on 5 performance indicators for: (a) optimization on digesters A1 and A2; (b) validation on digesters B1 (using A1 results) and B2 (using A2 results) and (c) validation on digesters B1 (using
A2 results) and B2 (using A1 results).

Absolute Average offset from experimental value (%) (Standard deviation)

Performance Methane pH Ammonia Acetate TCOD
indicator*
(a) Error for optimization on digesters A1 and A2
A1 A2 A1 A2 A1 A2 A1 A2 A1 A2
Methane 13.7% (10.94%) 14% (15.67%) 9.4% (2.65%) 5.74% (2.56%) 110.2% (117.66%) 310.63% 58.18% (27.7%) 54.1% (98.21%) 70.16% (43.4%) 38.83% (15.8%)
(193.8%)
pH 64.62% 113.3% (46%) 1.21% (1%) 2.23% (1.9%) 149.76% 292.75% (198%) 87.84% (9.16%) 85.1% (4.06%) 53.27% (38%) 23.58% (14.1%)
(30.71%) (113.34%)
Ammonia 89% (19.6%) 95.8% (13.3%) 34.6% (13.37%) 57.47% (18.5%) 100% (108%) 218.8% (195%) 1774.9% (1022.5%) 1059.9% (740.5%) 150% (100.8%) 134.28%
(63.84%)
Acetate 15.55% (9.53%) 14.8% (19.5%) 8.5% (2.32%) 5.54%2.53%) 118.17% (118.7%) 314.5% (196.1%) 40.85% (39.3%) 3.22% (3.92%) 66.38% (42.3%) 19.1% (14.32%)
TCOD 55.61% (7.92%) 40.6% (13.3%) 6.4% (1.48%) 5.76% (2.81%) 159.11% (112.8%) 329.75% (192%) 97.15% (1.5%) 100.52% (133.5%) 49.6% (37.1%) 12% (10.71%)
EWC 13.6% (11.5%) 14.6% (16.56%) 8.4% (2.4%) 6.62% (2.55%) 115.4% (118.11%) 294.31 (194.7%) 51.4% (26.33%) 43.02% (12.21%) 67.4% (42.55%) 29.34% (19.41%)

N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255

(b) Error for validation on digesters B1 (using A1) and B2 (using A2)
B1 B2 B1 B2 B1 B2 B1 B2 B1 B2
Methane 15.22% (15.4%) 21.8% (10.7%) 13.33% (2.1%) 12.5% (1.27%) 181.47% 434.3% (384.4%) 62.06% (16.93%) 67.23% (58.7%) 112.88% (47.3%) 47.5% (31.38%)
(196.16%)
pH 65.61% 72.9% (31%) 4.38% (1.3%) 7.26% (1.3%) 237.77% (196%) 410.84% 88.46% (5.5%) 78.36% (14%) 91.8% (41.66%) 48.1% (26.37%)
(33.08%) (379.4%)
Ammonia 88.86% (19.7%) 94.5% (18.6%) 37.71% 63% (15.76%) 172.18% 313.23% 2405.26% 1072.83% (922.1%) 205.33% (101.3%) 187% (95.76%)
(12.02%) (186.63%) (342.8%) (1901.3%)
Acetate 16.37% 27.5% (23.75%) 12.5% (1.84%) 13.86% (5.3%) 194.36% (197.3%) 440.5% (388.2%) 36.73% (17.37%) 448.6% (832.6%) 108.08% (46%) 47.48% (34.1%)
(14.22%)
TCOD 55.83% (9.4%) 52.14% (9.7%) 10.53% (1.26%) 12.42% (1.33%) 249.9% (197.07%) 459.6% (393.5%) 96.88% (2.3%) 202.67% (337.4%) 87.3% (40.58%) 32.32% (19.52%)
EWC 15.24% (15.8%) 44.82% 12.4% (1.9%) 20.69% (11.6%) 189.45% 420% (369%) 38.4% (24.17%) 950.3% (1415.5%) 109.49% (46.37%) 75.85% (68.82%)
(68.68%) (197.08%)
(c) Error for validation on digesters B1(using A2) and B2 (using A1)
B1 B2 B1 B2 B1 B2 B1 B2 B1 B2
Methane 44.42% 70.56% 9.97% (1.25%) 34.62% 229.91% 400.4% (356.9%) 35% (22.05%) 2747.4% (2958.7%) 147.52% (79.58%) 109.24% (91.2%)
(19.77%) (38.76%) (15.85%) (195.67%)
pH 37.57% (24%) 83.16% (37.4%) 5.84% (1.6%) 5.44% (1.47%) 209.82% 445% (388%) 79.48% (7.5%) 93.53% (2.58%) 136.07% (67.92%) 34.32% (18.74%)
(196.44%)
Ammonia 97.7% (9.82%) 87.22% (21.1%) 64.5% (16.87%) 38.1% (12.34%) 143.15% (171.2%) 359.83% 1802.4% (835%) 856.48% (639.22%) 317.25% 115.8% (85.5%)
(344.5%) (127.77%)
Acetate 42.04% (20%) 70% (39.17%) 9.96% (1.28%) 37.86% 232% (197.7%) 386.3% (389.8%) 28.52% (17.6%) 1714.1% (2032.4%) 139.5% (75.69%) 106.4% (93.57%)
(19.87%)
TCOD 54.3% (8.96%) 52.74% (9.58%) 11.08% (1.47%) 11.71% (1.41%) 249.28% 460.5% (394%) 205.3% (175.55%) 98.7% (0.83%) 89.1% (41.08%) 30.32% (92.26%)
(197.07%)
EWC 99.9% (0.34%) 70.61% 40.77% (1.48%) 34.07% 249.3% (197%) 410.28% 6619.71% 3261.47% 320.3% (120.66%) 107.88%
(38.84%) (15.95%) (361.3%) (2483.5%) (3544.5%) (92.26%)

The percent deviation is shown in bold.

*
The components highlighted in bold respectively indicate the basis upon which optimization and validation were conducted.

253
254 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255

and day 40 from the experimental data due to the decaying curve.
The situation is less severe for TCOD where all models seem to
some extent overestimate the experimental data throughout the
duration but capture the experimental trend, especially for diges-
ter A2. Hence, it is recommended to consistently take multiple
measurements of each indicator both spatially and temporally.
3.6. Model validation
To validate the models of digester A in Sets 1 and 2, the param-
eters optimized on the various performance indicators generated
for A1 and A2 were used as an input in digesters B1 and B2. A sam-
ple of curves for validation of B1 using performance indicators of
A1 is shown in Fig. 6 and a summary of the errors of each perfor-
mance indicator from applying the parameters of A1 on B1 and
A2 on B2 is shown in Table 6b.
Despite the general increase in error from Table 6a (calibration
results) to Table 6b (validation results), the optimum approach for
modeling each performance indicator remains the same. This pro-
vides a strong validation of the optimization results with the only
exception being the acetate-based validation on digester B2, where
it did not yield the lowest error. The reason could be attributed to
the possibility of over fitting when optimizing for the acetate
parameter on digester A2 making the parameters only valid for
that specific digester at those specific points, and not optimum
for any other case.
In addition to validating the results of A1 and A2 on B1 and B2
respectively (Table 6b), the optimized parameters from A1 and A2
were applied to B2 and B1 respectively for further validation
(Table 6c). By comparing the ranking of the optimum approaches
between Table 6b and Table 6c, it is evident that the two are not
similar. This can be attributed to the fact that experiment set #1

Fig. 6. Model validation results of B1 using A1’s performance indicators and EWC parameters: (a) methane; (b) pH; (c) acetate; (d) ammonia; (e) TCOD.
 N.M. Atallah et al. / Bioresource Technology 174 (2014) 243–255
(A1 and B1) and experiment set #2 (A2 and B2) were started with
different inocula, resulting in different microbial compositions and
leading to major differences in key reaction rates and factors.
Because the EWC approach equally involves all of the indicators,
it is the most sensitive approach and thus displayed the highest
change. At the same time, EWC of A2 displayed higher change than
EWC of A1 since it had higher improvement on the methane-based
approach and displayed a greater deviation in the parameters.
4. Conclusion
ADM 1 was used to simulate two separate experimental setups
each involving two digesters (A and B) treating SS-OFMSW. The
sensitivity analysis on methane, pH, acetate, ammonia, TCOD and
equally weighted combination revealed that each component had
different influencing parameters depending on the processes
linked to it. It was found that methane optimization, a commonly
adopted approach, does not adequately predict other intermediary
outputs. However, the equally weighted multi-objective optimiza-
tion improved the results from that of methane-based optimiza-
tion. Validation certified the results obtained from the
optimization process with the exception of acetate based optimiza-
tion on A2 due to over-fitting.
Acknowledgements
This work was supported by the National Council for Scientific
Research, Lebanon. Special thanks are extended to the United
States Agency for International Development for its support in
acquiring the equipment used in the experimental program.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2014.
09.143.
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