Chemosphere 78 (2010) 1085–1092

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Estimation of greenhouse gas generation in wastewater treatment

plants – Model development and application
M. Bani Shahabadi, L. Yerushalmi, F. Haghighat *
Department of Building Civil and Environmental Engineering, Concordia University, 1455 de Maissonnuve Blvd. West Montreal, QC, Canada H3G 1M8

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

Article history: A comprehensive mathematical model has been developed to estimate greenhouse gas (GHG) emissions
Received 10 June 2009 by wastewater treatment plants (WWTP) resulting from on-site and off-site activities. The contribution of
Received in revised form 17 December 2009 individual processes to the production of GHGs in a typical hybrid treatment system for food processing
Accepted 18 December 2009
wastewaters has been determined. The results show that the recovery of biogas and its reuse as fuel have
a remarkable impact on GHG emissions and reduce the overall emissions by 1023 kg CO2e d1 from a
total of 7640 kg CO2e d1 when treating a wastewater at 2000 kg BOD d1. Furthermore, the recovery
Keywords:
of biogas and its combustion may be used to cover the entire energy needs of the treatment plant for aer-
Greenhouse gas
Wastewater treatment
ation, heating and electricity generation while creating emissions credit equal to 34 kg CO2e d1. The off-
Food processing site GHG emissions resulting from the manufacturing of material for on-site usage were identified as the
On-site and off-site emissions major source of GHG generation in hybrid treatment systems. These emissions account for the generation
Hybrid process of 4138 kg CO2e d1, or 62% of the overall GHG emissions when biogas recovery is carried out. The inclu-
sion of GHG emissions from nutrient removal as well as off-site processes in the overall GHG emissions of
WWTPs increased the accuracy and completeness of this estimation, lending support to the novelty of the
present study.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction transportation of fuels and materials for on-site consumption.

During the last two centuries, human activities such as the pro-
duction and consumption of fossil fuels, as well as agricultural and
industrial activities have caused an increase in the atmospheric
concentration of harmful greenhouse gases (GHG), particularly
CO2, CH4, and N2O (El-Fadel and Massoud, 2001). The increase in
atmospheric GHG concentration has led to climate change and glo-
bal warming effect, motivating international efforts such as the
Kyoto Protocol to reduce GHG emissions. The contribution of a
greenhouse gas to global warming is commonly expressed by its
global warming potential (GWP) which enables the comparison
of global warming impact of the gas and that of a reference gas,
typically carbon dioxide. On a 100-year basis, the GWP of carbon
dioxide, methane and nitrous oxide are 1, 23 and 296, respectively
(IPCC, 2001). Wastewater treatment plants (WWTPs) are recog-
nized as one of the larger minor sources of GHG emissions
(Sahely et al., 2006). WWTPs produce CO2, CH4, and N2O during
the treatment processes and CO2 from the energy demand of the
plant. Off-site GHG emissions result from several activities that in-
clude the production of electricity as well as the production and
* Corresponding author. Tel.: +1 514 848 2424x3192; fax: +1 514 848 7965.
E-mail addresses: m_banish@encs.concordia.ca (M. Bani Shahabadi), laleh@encs.
concordia.ca (L. Yerushalmi), haghi@bcee.concordia.ca (F. Haghighat).
These emissions are traditionally assigned to the energy sector in-
stead of the end-user which is the WWTP. Besides, under the IPCC
protocols, CO2 production from biogenic sources should not be
considered as GHG emissions. This assumption is true if biomass
or renewable fuels are produced without fossil fuel input, which
is rarely met in reality. These assumptions, along with the use of
the IPCC emission factors, result in under-estimation of GHG emis-
sions from WWTPs. In addition, most attempts to estimate GHG
emissions by WWTPs have focused on the contribution of carbona-
ceous biochemical oxygen demand (CBOD) to GHG emissions with-
out considering the impact of nutrient removal (El-Fadel and
Massoud, 2001; Keller and Hartley, 2003; Cakir and Stenstrom,
2005; Monteith et al., 2005; Sahely et al., 2006; Wei et al., 2008).
The implementation of abatement strategies to reduce GHG
emissions by WWTPs will further enhance their role in the protec-
tion of our environment while preventing the imposition of carbon
taxes on these industrial facilities. In order to achieve this objec-
tive, a comprehensive mathematical model has been developed
to provide a thorough estimation of GHG emissions resulting from
on-site and off-site activities of WWTPs. The inclusion of off-site
GHG emissions along with the impact of nutrient removal activi-
ties provides a more accurate assessment of these harmful emis-
sions. The application of the developed model was demonstrated
in the estimation of GHG emissions from a hybrid treatment

0045-6535/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2009.12.044
1086 M. Bani Shahabadi et al. / Chemosphere 78 (2010) 1085–1092
Nomenclature
A cross sectional area of heat escape from reactor (m2)
Aerobic aerobic reactor
An anaerobic reactor
BODu ultimate biochemical oxygen concentration (kg m3)
D digester
Ds.Methane dissolved CH4 in reactor effluent (kg CH4 d1)
Ebiogas recovery energy saving due to biogas recovery (kJ d1)
EFAlkalinity GHG emission factor for alkalinity production and
transportation (kg CO2e kg1 CaCO3)
EFi,Elect GHG emission factor of fuel i, used for electricity gener-
ation (kg CO2e kW h1)
Effaeration aeration efficiency
Eff electrical-conversion electrical conversion efficiency
Eff heat-conversion heat conversion efficiency
ElecAeration electricity required for aeration (kW h d1)
Electotal total electricity required (kW h d1)
kd endogenous decay coefficient for heterotrophic biomass
(d1)
kdn endogenous decay factor for nitrifying microorganisms
(d1)
K H;CH4 Henry’s Law constant of CH4 (kg m3 atm1)
MCH4 ;BOD mass of CH4 production because of BOD utilization
(kg CH4 d1)
MCH4 ;gaseous mass of available CH4 for recovery (kg CH4 d1)
MCH4 ;recovered mass of CH4 recovered (kg CH4 d1)
MCH4 ;vented mass of CH4 vented (kg CH4 d1)
MCH4 !CO2 ;flared mass of CO2 production by CH4 combustion during
biogas flaring (kg CO2 d1)
MCH4 !CO2 ;recovered mass of CO2 production by CH4 combustion
during biogas recovery (kg CO2 d1)
MCO2 CO2 production in reactor (kg CO2 d1)
MCO2 ;CBOD CO2 production during the carbonaceous BOD removal
(kg CO2 d1)
MCO2 ;denitrification;methanol CO2 production during denitrification by
methanol (kg CO2 d1)
system that treats food processing wastewaters. This design was
chosen in order to evaluate the potential reductions in GHG emis-
sions by placing an anaerobic process before the aerobic process
for concentrated wastewaters. The developed model identifies pro-
cesses that make the highest contribution to the generation of
GHGs and facilitates the implementation of abatement strategies
without compromising the quality of effluent. The application of
the model in the estimation of GHG emissions by alternative treat-
ment systems was investigated and the results were compared
with those obtained for hybrid treatment systems (Bani Shahabadi
et al., 2009).
2. Mathematical model development
This study concentrated on the on-site and off-site emissions of
CO2 and CH4, but did not examine N2O emissions due to the lack of
accurate data during full-scale and pilot-scale operations (Barton
and Atwater, 2002). N2O emissions occur during both nitrification
and denitrification processes and its generation can be prevented
by proper control and implementation of complete nitrification
and denitrification (Monteith et al., 2005). On-site GHG emissions
are due to liquid and solid treatment processes as well as biogas
and fossil fuel combustion for energy generation. Off-site GHG
emissions are related to the production of electricity for plant, pro-
duction and transportation of fuel and chemicals for on-site use,
degradation of remaining constituents in the WWTP’s effluent to
the aquatic recipients, as well as transportation and disposal of sol-
MCO2 ;denitrification;ww CO2 production during denitrification by
wastewater BOD (kg CO2 d1)
MU—CO2 ;electricity Upstream GHG production due to electricity con-
sumption (kg CO2e d1)
Mx;degraded
amount of biomass decayed indigenously inside reac-
tor (kg VSS d1)
MX,denitrification biomass production during denitrification
(kg VSS d1)
NOx concentration of NH4–N in the influent that is nitrified
(kg N m3)
PX,bio biomass production because of BOD utilization
(kg VSS d1)
PX,CBOD biomass production from carbonaceous BOD utilization
(kg VSS d1)
peri,Elect percentage contribution of fuel i to generate electricity
PPCH4 partial pressure of CH4 in reactor (kPa)
qheat loss heat loss through reactor sides, bottom and top (kJ d1)
Q effluent wastewater flow rate (m3 d1)
Qi influent wastewater flow rate (m3 d1)
rAerobic
oxygen;total total oxygen needs in aerobic reactor (kg O2 d )
1
Removed CBODdenit removed carbonaceous BOD because of deni-
trification (kg BOD m3)
S BOD concentration in the effluent (kg BOD m3)
Si influent BOD (kg BOD m3)
SRT solids retention time (d)
Tincoming,ww temperature of the incoming wastewater (°C)
Treactor temperature of reactor (°C)
U coefficient of heat transfer for walls, floor and roof of the
reactor (kJ m2 s1 °C1)
Y yield coefficient (kg VSS kg1 BOD)
Yn Biosynthesis yield coefficient for nitrifying bacteria
(g VSS g1 BOD)
s hydraulic retention time (d)
ids. In this study GHG emissions have been estimated only for the
biological treatment processes and the GHG emissions from sludge
conditioning and dewatering unit are not considered here. Also, the
off-site GHG emissions because of chemical manufacturing for dis-
infection of wastewater are not considered in this study. The sys-
tem boundary for the estimation of GHG generation, as well as
the flow diagram of a typical hybrid treatment system for indus-
trial wastewaters and the fate of produced biogas during anaerobic
processes is illustrated in Fig. 1. On-site GHG generating processes
are identified on the figure by a darker color. The modeling ap-
proach used liquid flow and mass balances for biomass and sub-
strate around the treatment system. In this study, the term BOD
represents the BODu measurement. Table 1 presents the major
operating and process parameters used in this work.
2.1. Estimation of on-site GHG emissions
2.1.1. Primary clarifier
The mass of solids and BOD removed by the primary clarifier are
estimated by the equations reported by Monteith et al. (2005).
2.1.2. Anaerobic reactor and anaerobic digester
Anaerobic contact process was considered for the anaerobic
treatment. The BOD of wastewater is either incorporated into
new biomass or it is converted to CO2 and CH4 under anaerobic
condition. A fraction of biomass is further converted to CO2 and
CH4 via endogenous respiration. The soluble substrate and biomass
 M. Bani Shahabadi et al. / Chemosphere 78 (2010) 1085–1092 1087

a c CO2 CH4
CO2
Leakage

Flare
CO2

Biogas Combustion
Recovery

Biogas

Biogas CO2
b
Anaerobic Anoxic/Aerobic
Reactor Reactor
Primary
Clarifier Clarifier Clarifier Effluent
Influent

Sludge Recycle Sludge Recycle

Sludge Sludge

Digester Effluent

Digested Sludge

Anaerobic
Digester

Biogas

Fig. 1. (a) Analysis boundary for estimating GHG emissions by a wastewater treatment plant, (b) flow diagram of a typical hybrid treatment system examined in this study,
(c) the fate of produced biogas. Dashed lines indicate the energy or chemical flow and solid lines indicate the mass flow.

are represented by the formula C10H19O3N and C5H7O2N, respec- The total CH4 production in the anaerobic reactor is the sum of
tively (Rittmann and McCarty, 2001). Although these formulas CH4 production due to BOD oxidation and the endogenous decay of
are commonly used to represent municipal wastewaters, they are biomass, as expressed in Eq. (4). During BOD utilization (Eq. (1))
employed in this study to represent wastewaters of food process- and biomass decay (Eq. (2)), CO2 is also produced in addition to
ing industry in order to simplify the equations. The equations for CH4. The overall CO2 production in the anaerobic reactor is esti-
carbonaceous substrate utilization and biomass decay in anaerobic mated by the following equation:
environment are presented by the following Eqs. (1) and (2).
MAn
CO2 ¼ 0:27 g CO2 g
1
BOD r An
BOD
0:02C10 H19 O3 N þ 0:094H2 O ! 0:004C5 H7 O2 N þ 0:049CO2
þ 0:58 g CO2 g1 VSS M An
x;degraded ð5Þ
þ 0:115CH4 þ 0:016HCO3
þ 0:016NHþ4 ð1Þ A fraction of CH4 dissolves in liquid and escapes the anaerobic
reactor with the effluent (Eq. (6)), contributing to GHG generation
in anaerobic WWTPs (Cakir and Stenstrom, 2005). The total
0:05C5 H7 O2 N þ 0:2H2 O ! 0:075CO2 þ 0:125CH4 þ 0:05NHþ4
amount of methane in biogas can be estimated accordingly:
þ 0:05HCO3 ð2Þ
DS:MethaneAn effluent ¼ Q An An An
i K H;CH4 PPCH4 ð6Þ
The influent and effluent BOD concentrations and the rate of
biomass production in the anaerobic reactor are calculated using
mass balance equations (Metcalf and Eddy, 2003). The CH4 produc-
MAn An
CH4 ;gaseous ¼ M CH4 ;total  DS:MethaneAn effluent ð7Þ
tion rate due to BOD oxidation and the total CH4 production in the The CH4 in biogas is either recovered for use as fuel, flared, or
anaerobic reactor are estimated from the following equations: directly vented into the atmosphere. The CO2 production resulting
h
from methane combustion is equal to:
M An
CH4 ;BOD ¼ 0:25 g CH4 g
1
BOD Q An An An
i ðSi  S Þ
i MAn 1
CH4 MAn
CH4 !CO2 ¼ 2:75 g CO2 g ð8Þ
 1:42 g BOD g1 VSS PAn
X;bio ð3Þ CH4

The fraction of CH4 that escapes the treatment process or is

M An An 1
VSS MAn vented into the atmosphere should be multiplied by the GWP fac-
CH4 ;total ¼ M CH4 ;BOD þ 0:35 g CH4 g x;degraded ð4Þ
tor of CH4, which is 23, in order to yield its CO2 equivalent. Thus,
1088 M. Bani Shahabadi et al. / Chemosphere 78 (2010) 1085–1092

Table 1
Major operating and process parameters of the wastewater treatment plant of food processing industry.

Parameter Value Reference

Influent
Flow rate (Qi) 1000 m3 d1 Xu and Nakhla (2006)
BOD (Si) 1700–2500 g BOD m3 Xu and Nakhla (2006)
Nitrogen (TKNi) 80–140 g N m3 Xu and Nakhla (2006)
VSS (Xi) 1000 g VSS m3 Xu and Nakhla (2006)
Temperature (T incoming ww ) 25 °C Xu and Nakhla (2006)

Primary clarifier
VSS removal fraction (PerPC
SS )
20% Monteith et al. (2005)
BOD removal fraction (PerPC 30% Monteith et al. (2005)
BOD )
Underflow rate (QPC) 30 m3 d1 Monteith et al. (2005)
Anaerobic reactor
Temperature (T An 25 °C Metcalf and Eddy (2003)
reactor )
Heterotrophic Yield (YAn) 0.08 g VSS g1 BOD Metcalf and Eddy (2003)
Decay rate (kd )
An 0.01 g g1 d1 Metcalf and Eddy (2003)
Solids retention time (SRTAn) 15 d Metcalf and Eddy (2003)
Sludge wasting ratio (Q An An 0.01 Metcalf and Eddy (2003)
w =Q i )

Aerobic reactor
Temperature(T Aerobic 20 °C Metcalf and Eddy (2003)
reactor )
Nitrifying Yield (Y Aerobic ) 0.12 g VSS g1 N Metcalf and Eddy (2003)
n
Heterotrophic Yield (YAerobic) 0.4 g VSS g1 BOD Metcalf and Eddy (2003)
Nitrifying decay rate (kdn
Aerobic
) 0.08 g g1 d1 Metcalf and Eddy (2003)
Heterotrophic decay rate (kd
Aerobic
) 0.12 g g1 d1 Metcalf and Eddy (2003)
Solids retention time (SRTAerobic) 5d Metcalf and Eddy (2003)
Sludge wasting ratio (Q Aerobic =Q Aerobic ) 0.01 Metcalf and Eddy (2003)
w i

Anaerobic digester
Temperature (T D
reactor )
35 °C Metcalf and Eddy (2003)
Heterotrophic Yield (YD) 0.08 g VSS g1 BOD Metcalf and Eddy (2003)
Decay rate (kd )
D 0.03 g g1 d1 Metcalf and Eddy (2003)
Solids retention time (SRTD) 30 d Metcalf and Eddy (2003)
Energy
1
Aeration efficiency (Effaeration) 7.2 g O2 kJ Cakir and Stenstrom (2005)
Heat conversion efficiency (Eff heat-conversion ) 0.83 Cakir and Stenstrom (2005)
Electricity conversion efficiency (Eff electrical-conv ersion ) 0.5 Cakir and Stenstrom (2005)
Material
Emission factor for alkalinity production and transmission (EFAlkalinity) 1.74 g CO2 g1 Alk Energy Efficiency Opportunity Guide in the Lime Industry (2001)
Emission factor for methanol production and transmission (EFmethanol) 1.54 g CO2 g1 methanol Dong and Steinberg (1997)

the total GHG production in the anaerobic reactor can be estimated
as:
M An An An
TotalCO2 ;biogas ¼ M CH4 !CO2 ;recovered þ M CH4 !CO2 ;flared
þ 23M An An
CH4 ;vented þ M CO2
The estimation of GHG emissions from the anaerobic digester is
similar to the procedure discussed for the anaerobic reactor. How-
ever, the main source of biogas production in the anaerobic reactor
is the oxidation of soluble BOD while anaerobic solids digestion
deals with the disintegration of solids (sludge). It is assumed that
70% of the available biomass in the digester is degraded (Metcalf
and Eddy, 2003) and the rest flows out the digester and degrades
downstream.
2.1.3. Anoxic/aerobic reactor
In the aerobic reactor, a fraction of the carbonaceous BOD is oxi-
dized to CO2 by the aerobic biomass and the rest is incorporated
into new biomass. A fraction of the produced biomass is further
converted to CO2 via endogenous respiration. In addition to carbon
removal, GHGs are also generated during the removal of nutrients,
particularly during the nitrogen removal process which is assumed
to be carried out by the nitrification–denitrification process. The
pre-anoxic process is considered to exist in this study for the re-
moval of carbonaceous and nitrogenous BOD in a single tank. In
the examined pre-anoxic process (Fig. 1), the aeration tank in the
complete mix process is divided into two zones of anoxic and aer-
obic. The influent wastewater is fed to the anoxic zone which is fol-
lowed by the aerobic zone. Nitrate is produced in the aerobic zone
and is returned to the anoxic zone via a recycle stream for the deni-
trification process. Carbonaceous BOD removal is carried out in
ð9Þ both aerobic and anoxic zones. The fraction of BOD consumed for
denitrification in the anoxic zone is referred to as Removed
CBODdenit.
The stoichiometric relationships for the utilization of carbona-
ceous BOD and biomass decay in the aerobic environment as well
as the equations for complete nitrification and denitrification are
presented below:
0:02C10 H19 O3 N þ 0:01NHþ4 þ 0:01HCO3 þ 0:1O2
! 0:03C5 H7 O2 N þ 0:11H2 O þ 0:06CO2 ð10Þ
0:05C5 H7 O2 N þ 0:25O2 ! 0:2CO2 þ 0:05NHþ4 þ 0:05HCO3
þ 0:05H2 O ð11Þ
0:127NHþ4 þ 0:24O2 þ 0:01CO2 þ 0:0025HCO3
! 0:0025C5 H7 O2 N þ 0:125NO3 þ 0:25Hþ þ 0:1175H2 O ð12Þ
0:02C10 H19 O3 N þ 0:193NO3 þ 0:19Hþ
! 0:001C5 H7 O2 N þ 0:02NHþ4 þ 0:096N2 þ 0:232H2 O
þ 0:173CO2 þ 0:02HCO3 ð13Þ
 M. Bani Shahabadi et al. / Chemosphere 78 (2010) 1085–1092
The effluent BOD concentration of the aerobic zone, and the to-
tal production of biosolids can be calculated by mass balance equa-
tions (Metcalf and Eddy, 2003). A nitrogen mass balance around
the aerobic reactor has been formed to estimate the concentration
of nitrified nitrogen (Metcalf and Eddy, 2003).
The CO2 production due to carbonaceous BOD removal pro-
cesses and the total CO2 production in the aerobic reactor are cal-
culated from the following equations:
h   i
Aerobic
M Aerobic
CO2 ;CBOD ¼ 0:33 Q i SAerobic
i  SAerobic  1:42 g BOD g1 VSS PAerobic
X;CBOD
ð14Þ
M Aerobic Aerobic
CO2 ;total ¼ M CO2 ;CBOD þ 1:56 g CO2 g
1
VSS M Aerobic
x;degraded ð15Þ
According to Eq. (13), the removal of CBOD and the generation
of VSS and CO2 during the denitrification process are calculated as
follows:
Removed CBODdenit ¼ 2:97 g BOD g1 N-Nitrate NOx Q Aerobic
i
ð16aÞ
MX;denitrification ¼ 0:042 g VSS g1 N-Nitrate NOx Q Aerobic
i ð16bÞ
M CO2 ;denitrification;ww ¼ 2:81 g CO2 g1 N-Nitrate NOx Q Aerobic ð16cÞ
i
In the present study, two scenarios were examined for the deni-
trification process: first, the remaining CBOD in the effluent of
anaerobic reactor is sufficient to support the denitrification process
in the anoxic zone and therefore there is no need for an external
carbon source; second, the remaining CBOD in the effluent of
anaerobic reactor is not enough and an external carbon source,
e.g. methanol is added to the system to supplement the internal
CBOD during the denitrification process. The second scenario is
common and it is considered in this study. The stoichiometric reac-
tion for the denitrification process using methanol (Crites and
Tchobanoglous, 1998) and the corresponding CO2 emissions are
estimated as follows:
5CH3 OH þ 6NO3 ! 3N2 þ 5CO2 þ 7H2 O þ 6OH ð17Þ
M CO2 ;denitrification;methanol ¼ 2:62 g CO2 g1 N-Nitrate NOx Q Aerobic
i
ð18Þ
The use of organic carbon in wastewater to supply the carbon
needs of denitrification process offers two advantages. First, a frac-
tion of BOD in wastewater is removed by anoxic processes, thus
lowering oxygen requirements of BOD removal and the associated
aeration energy demands and upstream GHG generation. Second,
the use of external carbon sources will be avoided, eliminating up-
stream GHG emissions due to the manufacturing and transporta-
tion of chemicals.
2.2. Estimation of off-site GHG emissions
The off-site GHG emissions resulting from electricity generation
are calculated according to the following equation:
X  hand, fossil fuel burning and electric heaters generate extra GHG
M U—CO2 ;electricity ¼ Electotal peri;Elect EFi;Elect ð19Þ
In this study, the electricity generation mix of Canada is considered
and the values for peri,Elect and EFi,Elect were extracted from Sahely
et al. (2006). The electricity consumption rate of 0.3 kW h m3
wastewater for hybrid treatment systems was used. Sahely et al.
(2006) assumed this value for the aerobic WWTPs treating munici-
pal wastewaters. Considering that the electricity requirement of
anaerobic reactors is in general much less than those of aerobic
1089
treatment systems, one can conclude that electricity consumption
rate in hybrid treatment systems is close to and slightly higher than
that for aerobic treatment systems. This electricity consumption
rate is only related to the mixing of liquid in the reactors, illumina-
tion of plants and operation of electrical devices such as pumps.
These values do not take into consideration the heating of wastewa-
ter and aeration requirements which were calculated indepen-
dently from the total electricity needs of the plant in order to
identify the contribution of aeration energy and heating energy de-
mands to the total GHG emissions.
The production and transportation of chemicals for on-site use
are also responsible for off-site GHG emissions. Material usage
mainly includes alkalinity to control liquid pH in the reactors,
and methanol to provide a carbon source for the denitrification
process. The amount of chemicals used during the treatment pro-
cess was calculated from the relevant stoichiometric equations,
and the corresponding off-site GHG emissions were estimated by
using the emission factors presented in Table 1.
Natural gas (NG) is considered to be imported to the plant to
satisfy the energy needs. The upstream GHG emissions because
of production and transportation of NG are calculated by using
the emission factors reported by Sahely et al. (2006).
2.2.1. Energy saving and off-site GHG emissions related to the
anaerobic reactor
If the biogas generated in the anaerobic reactor is recovered and
used for electricity generation, then the savings in energy con-
sumption of the WWTP can be estimated as follows:
Ebiogas recovery ¼ 50:1  103 kJ kg
1
CH4 M An
CH4 ;recovered Eff electrical-conversion
ð20Þ
If the recovered CH4 is converted to heating energy in boilers for
warming up the wastewater, the energy savings is calculated by
Eq. (18), except Effelectrical-conversion is replace by Effheat-conversion.
Temperatures between 25 and 35 °C are usually used in order to
support high rates of anaerobic biological reactions and to provide
a stable treatment operation. Heating is needed to elevate the tem-
perature of influent wastewater to the reactor (Eq. (19)) and to
compensate for the heating losses through the walls, floor and roof
of the reactor (Eq. (20)):
 
HAn An
T An An 1  1
WW ¼ Q i reactor  T incoming ww 4200 kJ kg C ð21Þ
h    
qAn An An An An An An An An
heat loss ¼ Awall U wall T reactor  T wall þ Aroof U roof T reactor  T roof
 i
1
þ AAn An An An
floor U floor T reactor  T floor 86400 s d ð22Þ
The heating energy is provided by biogas usage, on-site fossil fuel
burning, or electric heaters. The reuse of biogas for heating yields
no additional GHG emissions compared to what was presented so
far; GHG emissions from the burning of biogas produced by the
anaerobic reactor were estimated by Eq. (9) (M An
Total CO2 ;biogas ) and by
the corresponding equation for the anaerobic digester. On the other
emissions.
2.2.2. Off-site GHG emissions related to the aerobic reactor
The energy needs of the aerobic reactor and the resulting GHG
emissions are mainly due to aeration which supplies oxygen for
aerobic processes. Total oxygen consumed in the aerobic reactor
and the corresponding electricity requirements are calculated as
follows:
1090 M. Bani Shahabadi et al. / Chemosphere 78 (2010) 1085–1092

h   i
r Aerobic Aerobic
SAerobic  SAerobic  1:42 g BOD g1 VSS PAerobic
oxygen;total ¼ Q i i X;CBOD
þ 4:33 g O2 g1 N Q Aerobic
i ðNOx Þ
ð23Þ
r Aerobic
oxygen;total
ElecAeration ¼ ð24Þ
Eff aeration
Off-site GHG emissions result from the degradation of the
remaining constituents in the effluent of the aerobic reactor. This
term is calculated based on the effluent BOD concentration of this
reactor and the corresponding CO2 generations due to its aerobic
biodegradation (Eq. (10)).
2.2.3. Energy saving and off-site GHG emissions related to the
anaerobic digester
The savings in GHG emissions due to the recovery of digester
biogas can be calculated from Eq. (18), by replacing the term
MAn D
CH4 ;recovered by M CH4 ;recovered .
The off-site GHG emissions due to the degradation of remaining
biosolids in the digester effluent are also important and were esti-
mated by using Eq. (2).
The total heating energy needs of the digester is estimated from
Eqs. (19) and (20). It is assumed that only 20% of the heat loss cal-
culated by Eq. (20) relates to the heating needs of anaerobic diges-
ter after insulation. The transportation and disposal of solids
emerging from the digester are also responsible for off-site GHG
emissions. In this study, it is assumed that the generated solids
are transported to landfills for final disposal. It is also assumed that
the remaining biodegradable solids undergo anaerobic degradation
in the landfill and the landfill biogas is recovered for use in energy-
generating processes. In this case, the off-site GHG emissions from
the handling and transportation of solids to landfills were esti-
mated by multiplying the total mass of solids produced during
the treatment process by the corresponding emission factor of
food processing industry by hybrid treatment systems. Four differ-
ent influent BOD and nitrogen concentrations were considered and
the resulting GHG emissions by individual processes under the
examined conditions are presented in Table 2. The results show
that the increase of organic loading rate (OLR) (cases 1–4) in-
creases the overall GHG emissions. This is mainly due to the rise
in GHG emissions by on-site biological processes despite higher
GHG emission savings due to biogas recovery at higher OLRs. The
increase of influent nitrogen concentration (Table 2, cases 2–1 to
2–4) enhances total GHG emissions, mostly because of higher
chemical consumption that results in higher off-site GHG emis-
sions due to more material usage. The GHG savings due to biogas
recovery decrease as a result of higher energy demands when the
influent nitrogen concentration increases. Some intermediate re-
sults of the estimated amounts of chemicals used in the four differ-
ent examined cases are presented in Table 3. It is seen that as the
influent BOD concentration increases, the alkalinity and methanol
requirements decrease. These intermediate results are very helpful
to interpret the GHG emissions results.
According to model predictions for case 2–2, the influent and
effluent BOD concentrations to the biological reactors are 1400
and 805 g BOD m3 for anaerobic reactor, 811 and 2 g BOD m3
for aerobic reactor, and 12 292 and 35 g BOD m3 for the anaerobic
digester, respectively. The analysis of results indicated that
108 kg methanol d1 is needed to support the denitrification pro-
cess in the anoxic reactor, with a contribution of 167 kg CO2 d1
to the off-site GHG emissions. The high influent BOD concentration
in the digester feed of 12 292 g BOD m3 results from the primary
clarifier’s underflow which feeds the digester. The results show
that the manufacturing and transport of materials, mainly alkalin-
ity and methanol, for on-site use are the major sources of GHG gen-
Table 3
Intermediate results of the estimated amounts of chemicals used for different cases.a

24 kg CO2e t1 waste for long distance trips for Canadian sources Anaerobic digester Methanol Alkalinity
(Torrie, 2003). The GHG emissions produced from the landfill were effluent BOD requirement to requirement
estimated from Eq. (2) based on the remaining biodegradable car- (g BOD m3) support denitrification (g Alk d1)
(g methanol d1)
bon in the digester sludge.
Case (1) 35 109 2304
Case (2–2) 35 108 2282
3. Results and discussion Case (3) 35 107 2267
Case (4) 35 106 2245
The developed model was employed for the estimation of GHG a
See Table 2 for the explanation of cases.
emissions during the treatment of wastewaters originating from

Table 2
Estimated GHG emissions by individual processes in the examined hybrid treatment system treating wastewaters having various influents BOD and nitrogen concentrations.

GHG emissions (kg CO2 d1) Normalized GHG emissions by

influent BOD
Examined On-site Off-site Material Energy Extra Saving Solids Total GHG
(kg CO2 kg1 BOD) (WBR)
cases biological carbon used demand due disposal emissions
processes degradation to biogas
NBRa WBRb NBR WBR
recovery
(1) 1689 456 4178 989 52 0 3 7315 6379 3.75
(2–1) 1993 478 3971 979 0 44 4 7425 6402 3.2
(2–2) 2035 475 4138 988 0 34 4 7640 6617 3.31
(2–3) 2057 474 4221 993 0 30 4 7748 6725 3.36
(2–4) 2120 470 4471 1006 0 16 4 8070 7048 3.52
(3) 2266 488 4111 988 0 92 4 7857 6776 3.08
(4) 2613 507 4070 988 0 179 4 8182 7015 2.81

Case (1): OLR = 1000(Q)1700(BOD) influent nitrogen concentration = 100 g N m3.

Case (2–1): OLR = 1000(Q)2000(BOD) – influent nitrogen concentration = 80 g N m3.
Case (2–2): OLR = 1000(Q)2000(BOD) – influent nitrogen concentration = 100 g N m3.
Case (2–3): OLR = 1000(Q)2000(BOD) – influent nitrogen concentration = 110 g N m3.
Case (2–4): OLR = 1000(Q)2000(BOD) – influent nitrogen concentration = 140 g N m3.
Case (3): OLR = 1000(Q)2200(BOD) – influent nitrogen concentration = 100 g N m3.
Case (4): OLR = 1000(Q)2500(BOD) – influent nitrogen concentration = 100 g N m3.
a
NBR = no biogas recovery.
b
WBR = with biogas recovery.
 M. Bani Shahabadi et al. / Chemosphere 78 (2010) 1085–1092
eration and produce 4138 kg CO2 d1 or 54% of the overall on-site
and off-site emissions of the plant. This is due to the high GHG
emission factor for the production of these materials and their rel-
atively high demand during the treatment process. Biological pro-
cesses are the second major source of GHG emissions with
2035 kg CO2 d1 or 27% of the total GHG emissions. In case 2–2
(Table 2), 15 kg CH4 d1 escapes in the anaerobic reactor effluent
that is equivalent to the emissions of 345 kg CO2 d1 if not oxidized
in the aerobic reactor. The energy demands of the plant in the ab-
sence of biogas recovery is responsible for 13% of GHG emissions,
while the emissions due to solids disposal are very small and
amount to 3.6 kg CO2 d1 or 0.05% of the overall emissions. The re-
sults also show that biogas recovery and reuse as fuel covers the
total energy needs of the hybrid treatment plant for aeration, heat-
ing and electricity (988 kg CO2 d1), and considerably reduce GHG
emissions of the treatment plant. The recovery and reuse of biogas
eliminate the need to import fossil fuels for on-site energy gener-
ation and the excess energy from the produced biogas may be used
for the generation of electricity and sold to the power grid. This ac-
tion reduces the total GHG emissions attributed to the wastewater
treatment plant by 34 kg CO2 d1, while reducing the dependence
of power generation system on other energy resources that gener-
ate excessive GHGs. Accordingly, the biogas recovery and reuse re-
duce the total GHG emissions by 1023 kg CO2 d1, considering the
GHG emission savings due to the elimination of energy demand
and the additional GHG emission savings by electricity generation
from the remaining biogas. With the incorporation of biogas recov-
ery, on-site biological processes as well as off-site degradation of
carbon and off-site GHG emissions related to on-site material
usage are accountable for 31, 7, and 62% of total GHG emissions
attributed to the hybrid treatment system, respectively. In the hy-
brid treatment system examined in this study, GHG reduction
strategies must focus on reducing material usage in the plant or
using materials with less off-site GHG emissions. Off-site degrada-
tion of the remaining carbonaceous material in the effluent and
sludge makes a considerable contribution to the overall GHG emis-
sions of the plant (Table 2). Therefore, an increase in the efficiency
of treatment will reduce the degradable constituents in the effluent
and sludge while producing biogas which can serve as a source of
energy for the plant, further reducing the overall GHG emissions.
The overall on-site and off-site GHG emissions from case 2–2
are shown in Fig. 2. This figure shows that the overall off-site
GHG emissions are substantially higher than the on-site GHG emis-
sions that are related to the treatment processes and on-site en-
ergy generation. In fact, the off-site GHG emissions increase the
overall emissions of the treatment plant by 214% in the absence
of biogas recovery, and by 225% with biogas recovery compared
Fig. 2. Comparison of the overall on-site and off-site GHG emissions by the hybrid
treatment system illustrated in case 2–2 (see Tables 2 and 3). NBR = no biogas
recovery, WBR = with biogas recovery.
1091
Table 4
Comparison of the results of our model with previous studies.
Type of treatment Monteith Our Keller and Our
et al. (2005) model Hartley (2003) model
Aerobic treatment 0.228–0.245 0.20 0.438 0.44
kg CO2 m3 WW
Hybrid treatment – – 0.35 0.39
kg CO2 m3 WW
to on-site emissions. Biogas recovery and reuse as fuel removes
623 kg CO2 d1 emissions resulting from the preparation and han-
dling of NG and its transportation for on-site use.
The energy needs of various processes and energy generation
due to biogas recovery are also calculated in this study. Energy in
the form of biogas is produced by the anaerobic reactor and the
anaerobic digester in the amount of 4098 and 6216 MJ d1, respec-
tively for case 2–2. Anaerobic digestion produces the highest
amount of energy equal to 60% of the total produced energy. The
energy consuming processes are anaerobic reactor’s heating, aera-
tion, digester heating, and electricity needs of the rest of plant that
amount to 1473, 924, 4569 and 1080 MJ d1, respectively (the
influent wastewater and the anaerobic reactor are both at 25 °C
and no heating is required to elevate the wastewater’s tempera-
ture. However, because of heat loss from the anaerobic reactor,
heating is required to maintain a constant temperature). The high-
est energy consuming process is the digester heating that accounts
for 57% of the total energy needs of the plant in the examined hy-
brid treatment system. This implies that efficient digesters with
less heating needs and a higher degree of VSS stabilization will re-
duce the energy needs of the treatment plant and increase biogas
production, leading to an overall GHG reduction of the WWTP.
The validity of the developed model was verified through com-
parison with previous studies using the same process parameters
and assumptions, as presented in Table 4. The results show that
the predictions of the model developed in the present study con-
form well to the previous studies.
Keller and Hartley (2003) and Greenfield and Batstone (2005) re-
ported the production of 1.04 and 1.06 kg CO2 kg1 COD removed
from anaerobic/aerobic municipal wastewater treatment plants,
respectively. These values are lower than the values obtained in
the present study. Based on the IPCC guidelines (IPCC, 2001), the
COD of municipal wastewaters is 2.4 times greater than the corre-
sponding BOD. Therefore, the estimated GHG emissions of the
WWTPs according to Keller and Hartley (2003) are equal to
2.5 kg CO2 kg1 BOD and those obtained by Greenfield and Batstone
(2005) are equal to 2.54 kg CO2 kg1 BOD. The present study esti-
mated that the GHG emissions from the examined hybrid industrial
wastewater treatment plant (case 2–2) are equal to 3.31 kg CO2 kg1
BOD (Table 2). This value is 32% higher than the value reported by
Keller and Hartley (2003) and 30% higher than that reported by
Greenfield and Batstone (2005). The observed difference is due to
the incorporation of off-site GHG emissions in the present study
which was not completely considered in the aforementioned stud-
ies. In addition, the reference studies had concentrated on municipal
wastewaters, contrary to the present study which is based on indus-
trial wastewaters and contains higher concentrations of soluble BOD
and VSS compared to municipal wastewaters.
4. Conclusions and recommendations
A comprehensive mathematical model was developed that en-
abled the estimation of GHG generation by a typical hybrid waste-
water treatment system and determined the contribution of
individual processes to on-site and off-site GHG emissions. Based
on the results of this study, the following strategies are recom-
mended to reduce GHG emissions in a wastewater treatment
1092 M. Bani Shahabadi et al. / Chemosphere 78 (2010) 1085–1092
plant: (1) recovery and reuse of biogas for energy generation to re-
place fossil fuel combustion and to satisfy the heating require-
ments of treatment plant, (2) increased energy efficiency of
WWTPs to reduce electricity needs of the plant, (3) increased effi-
ciency of anaerobic digester to produce more biogas, (4) operation
of anaerobic reactor and digester at lower temperatures, thus low-
ering the heating energy needs of the WWTP, (5) manufacturing of
material destined for on-site consumption (such as methanol and
carbonate) by alternative methods that produce lower amounts
of GHGs.
GHG emissions will likely develop into a major factor that will
influence the choice of treatment processes and the overall design
of wastewater treatment plants in response to regulatory measures
and international treaties such as the Kyoto Protocol.
Acknowledgements
The authors would like to express their gratitude to the Natural
Sciences and Engineering Research Council of Canada (NSERC) and
Concordia University for their financial support. The authors grate-
fully acknowledge the constructive comments of the anonymous
reviewers which improved the quality of this paper.
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