Abstract: An anaerobic continuously stirred tank reactor (CSTR) integrated with an external tubular nanofiltration membrane module was

operated for 466 days. Studies were conducted to compare the efficiencies in flux and operational permeability recovery of two different
chemical cleaning processes. Chemically enhanced backwashes (CEBs) were applied for approximately 176 days of the study and their
influence on chemical cleaning performance and membrane fouling rate following chemical cleanings were also investigated. The anaerobic
nanofiltration membrane bioreactor used in the study was fed a high-strength, potato starch–based synthetic wastewater (average chemical
oxygen demand of 83.4 g=L and average total suspended solids of 5.8 g=L). Important findings were that a static, one-phase cleaning process
using caustic cleaning chemicals outperformed a dynamic, three-phase cleaning process that also incorporated acidic cleaning chemicals; the
acidic phase of the three-phase cleaning had a detrimental effect on the overall cleaning procedure’s performance; CEBs enhanced the per-
formance of cleaning processes; and, finally, caustic cleaning solutions provided benefits to both membrane cleaning effectiveness and rate of
fouling in the short term but may lead to an increased rate of membrane fouling in the long term. DOI: 10.1061/(ASCE)EE.1943-
7870.0001524. © 2019 American Society of Civil Engineers.
Author keywords: Anaerobic membrane bioreactor; Chemical cleaning; Chemically enhanced backwash; Membrane fouling;
Nanofiltration membrane.

Introduction anaerobic systems such as high concentration of biomass retention

With an ever-growing population, sustainable water and waste-
water treatment technologies will become essential in solving water
scarcity problems prone to develop in upcoming years. Anaerobic
membrane bioreactors (AnMBRs) offer a promising means of
sustainable and value-added wastewater treatment, coalescing the
benefits of anaerobic digestion for the treatment of municipal and
industrial wastewaters with the almost 100% solid–liquid separa-
tion potential of membrane integrated wastewater treatment tech-
nologies. Anaerobic digestion for wastewater treatment provides
certain benefits over more commonly used conventional aerobic
technologies, such as high-rate suspended-growth systems, very
high removal efficiencies of biochemical oxygen demand (BOD)
and chemical oxygen demand (COD), resource recovery (value-
added products such as methane in its biogas and the possible
recovery of select biochemicals such as volatile fatty acids in its
mixed-liquor and effluent), lower sludge yield, and low carbon
footprint (Kinnunen et al. 2015; Meng et al. 2009; Ozgun et al.
2013; Pilli et al. 2016; Skouteris et al. 2012). Through the integra-
tion of membrane separation technologies within anaerobic di-
gestion, further benefits are provided over non-membrane-based
1
Graduate Student, Dept. of Civil Engineering, Univ. of New
Brunswick, 17 Dineen Dr., Fredericton, NB, Canada E3B 5A3 (corre-
sponding author). Email: h557d@unb.ca
2
Professor, Dept. of Civil Engineering, Univ. of New Brunswick, 17
Dineen Dr., Fredericton, NB, Canada E3B 5A3. Email: singhk@unb.ca
3
Process Engineer, ADI Systems, Inc., 370 Wilsey Rd., Fredericton,
NB, Canada E3B 6E9. Email: gustavo.zanatta@evoqua.com
Note. This manuscript was submitted on July 18, 2018; approved on
October 26, 2018; published online on March 6, 2019. Discussion period
open until August 6, 2019; separate discussions must be submitted
for individual papers. This paper is part of the Journal of Environmental
Engineering, © ASCE, ISSN 0733-9372.
(as the effectiveness of biomass retention becomes independent of
sludge settleability due to membranes’ near-complete solid–liquid
separation capabilities), compact design, and, most importantly, the
ability to produce a superior quality effluent for possible recycle
or high-quality discharge to meet stringent wastewater disposal
regulations (Skouteris et al. 2012).
What continues to remain the most significant factor limiting the
cost effectiveness of membranes in wastewater treatment applica-
tions (both municipal and industrial) is membrane fouling (Ramos
et al. 2014). Membrane fouling may be defined as the combination
of processes leading to flux deterioration and transmembrane pres-
sure (TMP) increase due to surface or internal pore blockage of the
membrane (Lousada-Ferreira et al. 2014). Surface or internal pore
blockage is generated through the contact and deposition of sus-
pended particles, colloids, and solutes present in the mixed liquor
on the membrane surface or in its pores, henceforth referred to as
foulants (Iorhemen et al. 2016). Membrane fouling increases TMP
and decreases flux, while the control of foulant deposition increases
manpower and energy requirements, demands costly chemical
cleaning (that further requires waste handling), and may also
result in increased deterioration of the membrane material, affecting
its lifespan (Ramos et al. 2014). Foulant mitigation for a membrane
module is a two-pronged approach: first, the membrane-fouling
rate should be minimized, and second, technologies to restore the
flux of a fouled membrane must be implemented (Liao et al. 2006).
Physical cleaning processes (e.g., gas scouring, backwashing,
relaxation) have only proven to be effective at removing some pore-
clogging and cake-layer membrane foulants (Liao et al. 2006).
Chemical cleanings, using low- to moderate-strength corrosive or
caustic solutions, are highly effective at removing both the gel layer
and cake layer developed through solids deposition on the mem-
brane surface and pore-blocking foulants, making them typically
more efficient at recovering membrane flux. These chemical

© ASCE 04019018-1 J. Environ. Eng.

J. Environ. Eng., 2019, 145(5): 04019018

Table 2. Membrane resistance coefficients calculated following each
chemical membrane cleaning process (unit: 10−12 × m−1 )
Cleaning process KM KR K IR
1 0.62 4.66 0.73
2 9.33 2.00
3 17.3 2.60
4 18.7 1.45
5 6.27 1.32
6 6.34 3.72
first placed inline. Reversible membrane fouling occurred rapidly
when the membrane module was first placed inline, resulting in a
quick drop in membrane flux (a loss of 35% in MLF over 5 days),
which merited the first chemical cleaning. The membrane resis-
tance coefficients were calculated (Table 2) to further support this
observation. Following Cleaning Process 1, K R was found to be
much greater than K IR (values of 4.66 × 10−12 m−1 and 0.73 ×
10−12 m−1 , respectively), indicating that the majority of foulant
removed was reversible membrane fouling. Since this was the first
chemical cleaning applied to the membrane module, K IR was also
at its lowest value throughout the study. As the majority of mem-
brane fouling was contributed from reversible foulants, which are
removed effectively through chemical cleaning processes, and there
was little contribution from irreversible membrane foulants relative
to other cleaning methods, Cleaning Process 1 appeared much more
effective. With this consideration in mind, it is difficult to distin-
guish whether Cleaning Process 1 was superior in terms of clean
water flux recovery over all other cleaning processes due to its
cleaning conditions or whether its enhanced performance was sim-
ply due to occurring so soon after the membrane was first placed
inline. Wang et al. (2017) did find that the maximum amount
of organics in their chemical cleanings was desorbed through the
use of an alkaline and acidic cleaning process when treating MBR
effluent. Cleaning Process 1 results agree with this observation, as
the cleaning conditions provided both alkaline and acidic chemicals
and it had the largest clean water flux recovery, indicating more
foulant removal.
Cleaning Processes 4 and 5 outperformed Cleaning Processes 2
and 3 in terms of clean water flux recovery. This result was not
initially anticipated because, due to the accumulation of irreversible
membrane fouling over the course of membrane operation, succes-
sively applying the same cleaning conditions typically results in
a decrease in flux and OP recoveries with each successive clean
(Sun et al. 2016). Since all four of these cleaning processes were
identical in conditions, it was expected that irreversible membrane
foulants would accumulate, making each successive membrane
cleaning process less efficient than the one preceding it. A differ-
ence that was present leading into Cleaning Processes 4 and 5 was
that there were CEBs present 60% (73 days) and 100% (77 days) of
the time, respectively, leading into each of these chemical cleaning
processes. Cleaning Process 5 had more CEBs prior to it and out-
performed Cleaning Process 4. Similarly, Cleaning Process 4 had
more CEBs prior to it compared to Cleaning Processes 2 and 3 (as
there were no CEBs in place leading into Cleans 2 and 3) and out-
performed them. From this observation, it would appear that regu-
lar CEBs synergize with chemical cleaning processes and enhance
their performance in terms of clean water flux recovery. Regular
contact between a low-strength caustic chemical cleaning solution
known for its efficiency in removing organic membrane foulants
and a wastewater/mixed liquor composed almost entirely of organic
matter as a source of membrane foulants (with average volatilities
for the wastewater and mixed liquor of 99% and 94%, respectively)
© ASCE 04019018-6
J. Environ. Eng., 2019, 145(5): 04019018
would allow the CEBs to be quite efficient in both removing
built-up membrane foulants and preventing their rate of accu-
mulation while operating. Zhang et al. (2007) found that, when
operating a tubular polyethersulfone side stream AnMBR for the
treatment of swine manure, long-term operation without chemical
cleaning processes resulted in residual membrane fouling that was
difficult to remove with the chemicals used in their study (nitric
acid and ethylenediaminetetraacetic acid). By using a constant
chemical cleaning process, the build-up of residual membrane
foulants might have been prevented. In this study, the prevention
of the build-up of difficult-to-remove membrane foulants was ob-
served, and a constant source of chemical cleaning was supplied
through CEBs, resulting in more effective fouling mitigation. It was
found that K R increased by 85% over 106 days between Cleaning
Process 2 and Cleaning Process 3, whereas K R increased by only
8% over 121 days between Cleaning Process 3 and Cleaning
Process 4, indicating a decrease in the rate of K R accumulation.
With the cleaning conditions of Cleaning Processes 2 and 3 being
identical, and operating conditions being fairly consistent in the
periods following these cleaning processes, the primary reason for
the decline in reversible foulant accumulation may be attributed to
CEBs being in place 60% of the days following Cleaning Process 3.
K R was 6.27 × 10−12 m−1 following Cleaning Process 5. A de-
crease in this value from Cleaning Process 4 to 5 indicates that the
rate of reversible foulant build-up was greatly reduced during
this period of operation, which may again be attributed to regular
CEBs being in place.
The irreversible fouling resistance coefficient typically increases
over the duration of membrane filtration and would not be antici-
pated to decrease unless operational or cleaning conditions could
be enhanced significantly. Considering that K IR decreased from
Cleaning Process 3 to 4, and again from Cleaning Process 4 to 5,
while all of these cleaning processes operated under the same
conditions, indicates that the presence of CEBs might also en-
hance regular cleaning protocols in such a way that irreversible
foulants (that could not be removed without CEBs in place) could
then be removed. Zhang et al. (2007) concluded that weekly mem-
brane cleanings provided no significant benefits in membrane per-
formance compared to monthly membrane cleanings, attributing
the lack of benefits to the fact that irreversible fouling accumulated
more rapidly than the frequency of either cleaning. Perhaps the
daily CEBs in this study occurred frequently enough that irre-
versible foulants were unable to accumulate effectively between
membrane cleanings. From Cleaning Process 5 to 6 the K R value
remained quite steady between cleans, whereas K IR increased by a
factor of 2.8 with CEBs regularly in place for 26 days of operation.
This indicates that Cleaning Process 5 may have been superior to
Cleaning Process 6 since K IR increased once again between cleans.
Similar to the results for clean water flux recovery, Cleaning
Processes 1, 5, and 4 offered the largest clean water OP recoveries
with values of 49%, 31%, and 30%, respectively. Since the recov-
eries in clean water operational permeability are near identical to
the recoveries in clean water flux, this indicates that the chemical
cleanings had similar recoveries in TMP. One reason why Clean 1
outperformed all of the others by a large margin may again be
attributed to its early application and lack of irreversible foulant
accumulation.
In terms of MLF and MLOP recoveries, all cleaning processes
exhibited good performance, with the lowest MLF recovery being
Cleaning Process 3 (with a value of 67%) and the lowest MLOP
recovery being Cleaning Process 2 (62%). Compared to the largest
clean water flux and OP recoveries of 53% and 49%, respectively,
this indicates that the chemical cleanings were much more effective
at recovering inline mixed-liquor flux rather than clean water flux.
J. Environ. Eng.
sludge wastage rate increasing the foulant contribution from solu-
ble microbial products (SMPs) known to block membrane pores
and too low of a sludge wastage rate promoting the development
and growth of extracellular polymeric substances (EPSs), again
contributing to membrane fouling (Iorhemen et al. 2016; Ibeid
et al. 2016; Jarusutthirak and Amy 2006; Le-Clech et al. 2006).
Studies have found that an optimum SRT range for both the min-
imization of SMP and EPS is around 25–30 days (Barker and
Stuckey 1998). Since the SRT for both of these periods of operation
was well above this value and within 25% of one another, SRT most
likely did not substantially contribute to their observed differences
in the rate of decline in operational permeability. Additionally, the
average backwash flow rate was greater during the period of oper-
ation following Cleaning Process 1, which would have contributed
towards a slower rate of operational permeability decline. Despite
the operating conditions being on average quite similar, no CEBs
being in place, and post–Chemical Cleaning Process 1 conditions
having more favorable physical cleaning processes in place, the
operating period following Cleaning Process 2 showed a much
lower rate of OP decline. The lower rate of OP decline may have
been primarily due to the nature of the chemical cleaning itself,
again supporting earlier conclusions that Cleaning Processes 2–5
were superior to Cleaning Processes 1 and 6.
Chemically enhanced backwashes were first applied to the
membrane module 40% of the way through the period of operation
following Cleaning Process 3. The average operating conditions
following Cleaning Processes 2 and 3 were relatively constant.
The largest discrepancies between these periods of operation were
the average backwash flow rate, which decreased by 11.3 L=h, and
the average SRT, which increased by 137 days from the period of
operation following Cleaning Process 2 to the period of operation
following Cleaning Process 3. Increasing the SRT would be ex-
pected to promote SMP foulant development, which would lead
to increased pore blockage. This in turn would result in less effi-
cient backwashes and, paired with a decreased backwash flow rate,
should have resulted in an increased rate of operational permeabil-
ity decline. The rate of operational permeability decline did in-
crease; however, the increase was very minimal, with a rate of
decline of 0.03 L=m2 =h=bar=day. The presence of CEBs for
60% of the operational period following Cleaning Process 3 likely
assisted in preventing the build-up of pore-blocking irreversible and
reversible foulants, resulting in this minimal increase in the rate of
operational permeability decline. Additionally, following Cleaning
Process 3 was the longest period of operation and the longest stand-
ardized period of operation. Zhou et al. (2014) found that the use of
sodium hydroxide backwashes retarded the rates of total foulant
and irreversible foulant accumulation, attributing their increased
performance to the combined hydraulic and chemical mechanisms
enhancing the detachment of biopolymers. It appears that CEBs are
beneficial, initially, in terms of reducing the rate of operational per-
meability decline and extending the duration of operation between
membrane cleanings. Ramos et al. (2014) were able to delay the
requirement for recovery cleaning by 3 years by incorporating
CEBs. This study fell short of a 3-year extension, likely due to dif-
ferences in membrane modules, and mixed-liquor/feed wastewater
characteristics, yet an extension over conditions without CEBs in
place was possible.
The period of operation following Cleaning Process 4, with
CEBs in place 100% of the time, saw the rate of decline in opera-
tional permeability increase by only 0.01 L=m2 =h=bar=day over
the period of operation following Cleaning Process 3. The reason
for this minimal increase in the rate of operational permeability de-
cline, and the second highest standardized duration of operation, is
most likely, once again, the presence of CEBs. Following Cleaning
© ASCE 04019018-8
J. Environ. Eng., 2019, 145(5): 04019018
Process 5, with CEBs in place 100% of the time, the rate of decline
in operational permeability increased to 0.12 L=m2 =h=bar=day, a
threefold increase over the rate following Cleaning Process 4. The
duration of operation and the standardized duration of operation
both reached their lowest values of 26 and 75 days, respectively,
during this period of operation as well. Zhou et al. (2014) found
that the average pore size of their PVDF membranes increased
after 1 week of operation with 1% sodium hypochlorite cleaning.
This resulted in a decrease in both their fouling resistance coeffi-
cients and operating periods between cleans. Wang et al. (2018)
noticed both their clean water flux and rate of hydraulic resistance
accumulation increased with an increased soak time in a sodium
hypochlorite cleaning solution, attributing the increase to an
enlargement in the pore size of the membrane module. Constant
contact between caustic cleaning solutions and the membrane sur-
face may provide initial benefits; however, over time it may lead to
an increased rate of fouling due to pore size enlargement.
Recent studies have also noted an increasing trend between the
quantity of dissolved organic matter and dose of sodium hypochlo-
rite the biomass is exposed to (Cai et al. 2016; Cai and Liu 2016).
Cai and Liu (2016) noted that increasing the concentration of dis-
solved organic matter in the mixed liquor resulted in an increased
membrane-fouling rate, although they found that following an
exposure of 55 mg-NaOCl=g-MLVSS the soluble COD concentra-
tion increased by only 180 mg=L, and under the operating condi-
tions provided in this study the dose would have been in the range
of 6–7 mg-NaOCl=g-MLVSS, meaning the impact in this case
would have been very minimal. Nonetheless, it is important to con-
sider that increased exposure to sodium hypochlorite may have
increased the generation of SMPs, which would have contributed
to the increased rate of decline in operational permeability as well.
Initially, the CEBs may be beneficial in retarding the rate of irre-
versible foulant accumulation on the membrane module and in its
pores, but over time the constant contact between the chemical sol-
ution and the membrane surface could be damaging. The pore size
of the membrane module used for this study was unable to be in-
vestigated prior to and following exposure to CEBs because this
would have required destroying the module, and it was decided that
the membrane would be stored for reuse following the conclusion
of the study. If the average pore size of the membrane did increase,
there was no impact on its TSS removal efficiency: it remained
above 99.9% throughout the duration of the entire study.
Conclusions
Two different chemical cleaning conditions were applied to a tubu-
lar, nanofiltration membrane module a total of six times, and each
chemical cleaning process’s individual performance was evaluated
and compared to that of the others. The membrane module was
operated as part of an AnMBR system for 466 days of continuous
operation. Over its course of operation, CEBs were eventually in-
corporated as a means of enhanced physical cleaning, and their
influence on membrane fouling mitigation and the chemical clean-
ings applied were also investigated. Overall, the following conclu-
sion may be drawn from this study:
• The static, one-solution chemical cleaning processes offered
higher recoveries in clean water flux, clean water operational
permeability, mixed-liquor flux, and mixed-liquor operational
permeability, on average, than the three-solution chemical
cleaning processes if the performance of Cleaning Process 1
can be attributed to its having taken place so early in the mem-
brane’s operational period, making the one-solution chemical
cleaning process the highest performing alternative.
J. Environ. Eng.
Wat. Sci. Tech. Vol. 28. No.2. pp. 165-176. 1993. 0273-1223/93 $6'00 0'00
Printed in Great Britain. All rights reserved. Copyright © 1993 IAWQ

ANAEROBIC-AEROBIC TREATMENT OF
POTATO-STARCH WASTEWATER

U. Abeling and C. F. Seyfried

Institut for Siedlungswasserwirtscha/t und Abfalltechnik (Water Supply and Treatment of

Solid Wastes). University of Hannover. Welfengarten I. D-3000 Hannover I. Germany

ABSTRACT

Production of potato starch produces wastewaters witb high concentrations of COD, nitrogen and
phosphorus. The best known and most economical solution for tbe nearly full elimination of tbese substances
is tbe two-stage anaerobic-aerobic treatment. The anaerobic pretreatment must only go so far as to maintain
enougb COD for biological nitrogen and phosphorus elimination in tbe aerobic stage. To optimize tbis
process, several tests have been carried out on nitrification/denitrification by means of tbe intermediate
product nitrite. The carbon consumption amounts to only 60% in comparison witb denitrification via nitrate.
The essential parameter for regulating tbe process is tbe concentration of free ammonia in tbe reactor.
Concentrations of I to 5mg NH31l inhibit tbe nitratation but not tbe nitritation. A separation of botb partial
steps is possible. The content of ammonia was controlled by means of continuous NH4 and pH measuring.

The process is suitable for many wastewaters witb low CODrrKN ratios and higb nitrogen concentrations. If
tbere are undesired nitrite peaks in an aerobic treatment plant caused by bigh pH values and temperatures,
specific nitrogen elimination by means of nitrite is a reliable treatment system.

KEYWORDS

Potato-starch wastewater; anaerobic-aerobic treatment; high-strength ammonium wastewater;

nitrification/denitrification via nitrite; nitritation; nitratation; industrial wastewater; nitrogen removal.

INTRODUCTION

In Europe, about 4.7 Mio. t starch and starch decay products are produced each year. The main raw materials
used are com (60% of the production) and potatoes and wheat (nearly 20% each). The largest product group
is the true starches with nearly 30%, followed by glucose (23%), isoglucose (13%) and modified starch
(12%). Most starch is employed in the food industry (for example sweets, drinks, fruit manufacturing - total
57%), the paper and paperboard industry (25%), as well as the chemical and pharmaceutical industry (10%).
Whereas a short time ago most of the attention was directed to production processes and commercializing,
nowadays wastewater avoidance and wastewater treatment are becoming more and more important. The cost
share of advanced wastewater treatment in the total production costs amounts to nearly 15%.

The starch wastewaters have high nitrogen and phosphorus concentrations. In Germany both nutrients must
be largely eliminated, and this will soon apply to the whole of the European Community as far as the
harmonization of environmental protection is concerned.

For purification of industrial wastewaters, especially for starch factories, more and more two-stage
anaerobic-aerobic processes have been used during the last few years. This is useful - for energetic reasons
- when highly concentrated wastewaters are to be treated, as a substantial part of the organic load can be

1 65
Abstract: An anaerobic continuously stirred tank reactor (CSTR) integrated with an external tubular nanofiltration membrane module was
operated for 466 days. Studies were conducted to compare the efficiencies in flux and operational permeability recovery of two different
chemical cleaning processes. Chemically enhanced backwashes (CEBs) were applied for approximately 176 days of the study and their
influence on chemical cleaning performance and membrane fouling rate following chemical cleanings were also investigated. The anaerobic
nanofiltration membrane bioreactor used in the study was fed a high-strength, potato starch–based synthetic wastewater (average chemical
oxygen demand of 83.4 g=L and average total suspended solids of 5.8 g=L). Important findings were that a static, one-phase cleaning process
using caustic cleaning chemicals outperformed a dynamic, three-phase cleaning process that also incorporated acidic cleaning chemicals; the
acidic phase of the three-phase cleaning had a detrimental effect on the overall cleaning procedure’s performance; CEBs enhanced the per-
formance of cleaning processes; and, finally, caustic cleaning solutions provided benefits to both membrane cleaning effectiveness and rate of
fouling in the short term but may lead to an increased rate of membrane fouling in the long term. DOI: 10.1061/(ASCE)EE.1943-
7870.0001524. © 2019 American Society of Civil Engineers.
Author keywords: Anaerobic membrane bioreactor; Chemical cleaning; Chemically enhanced backwash; Membrane fouling;
Nanofiltration membrane.

Introduction anaerobic systems such as high concentration of biomass retention

With an ever-growing population, sustainable water and waste-
water treatment technologies will become essential in solving water
scarcity problems prone to develop in upcoming years. Anaerobic
membrane bioreactors (AnMBRs) offer a promising means of
sustainable and value-added wastewater treatment, coalescing the
benefits of anaerobic digestion for the treatment of municipal and
industrial wastewaters with the almost 100% solid–liquid separa-
tion potential of membrane integrated wastewater treatment tech-
nologies. Anaerobic digestion for wastewater treatment provides
certain benefits over more commonly used conventional aerobic
technologies, such as high-rate suspended-growth systems, very
high removal efficiencies of biochemical oxygen demand (BOD)
and chemical oxygen demand (COD), resource recovery (value-
added products such as methane in its biogas and the possible
recovery of select biochemicals such as volatile fatty acids in its
mixed-liquor and effluent), lower sludge yield, and low carbon
footprint (Kinnunen et al. 2015; Meng et al. 2009; Ozgun et al.
2013; Pilli et al. 2016; Skouteris et al. 2012). Through the integra-
tion of membrane separation technologies within anaerobic di-
gestion, further benefits are provided over non-membrane-based
1
Graduate Student, Dept. of Civil Engineering, Univ. of New
Brunswick, 17 Dineen Dr., Fredericton, NB, Canada E3B 5A3 (corre-
sponding author). Email: h557d@unb.ca
2
Professor, Dept. of Civil Engineering, Univ. of New Brunswick, 17
Dineen Dr., Fredericton, NB, Canada E3B 5A3. Email: singhk@unb.ca
3
Process Engineer, ADI Systems, Inc., 370 Wilsey Rd., Fredericton,
NB, Canada E3B 6E9. Email: gustavo.zanatta@evoqua.com
Note. This manuscript was submitted on July 18, 2018; approved on
October 26, 2018; published online on March 6, 2019. Discussion period
open until August 6, 2019; separate discussions must be submitted
for individual papers. This paper is part of the Journal of Environmental
Engineering, © ASCE, ISSN 0733-9372.
(as the effectiveness of biomass retention becomes independent of
sludge settleability due to membranes’ near-complete solid–liquid
separation capabilities), compact design, and, most importantly, the
ability to produce a superior quality effluent for possible recycle
or high-quality discharge to meet stringent wastewater disposal
regulations (Skouteris et al. 2012).
What continues to remain the most significant factor limiting the
cost effectiveness of membranes in wastewater treatment applica-
tions (both municipal and industrial) is membrane fouling (Ramos
et al. 2014). Membrane fouling may be defined as the combination
of processes leading to flux deterioration and transmembrane pres-
sure (TMP) increase due to surface or internal pore blockage of the
membrane (Lousada-Ferreira et al. 2014). Surface or internal pore
blockage is generated through the contact and deposition of sus-
pended particles, colloids, and solutes present in the mixed liquor
on the membrane surface or in its pores, henceforth referred to as
foulants (Iorhemen et al. 2016). Membrane fouling increases TMP
and decreases flux, while the control of foulant deposition increases
manpower and energy requirements, demands costly chemical
cleaning (that further requires waste handling), and may also
result in increased deterioration of the membrane material, affecting
its lifespan (Ramos et al. 2014). Foulant mitigation for a membrane
module is a two-pronged approach: first, the membrane-fouling
rate should be minimized, and second, technologies to restore the
flux of a fouled membrane must be implemented (Liao et al. 2006).
Physical cleaning processes (e.g., gas scouring, backwashing,
relaxation) have only proven to be effective at removing some pore-
clogging and cake-layer membrane foulants (Liao et al. 2006).
Chemical cleanings, using low- to moderate-strength corrosive or
caustic solutions, are highly effective at removing both the gel layer
and cake layer developed through solids deposition on the mem-
brane surface and pore-blocking foulants, making them typically
more efficient at recovering membrane flux. These chemical

© ASCE 04019018-1 J. Environ. Eng.

J. Environ. Eng., 2019, 145(5): 04019018

cleanings can be performed either as a preventive maintenance op-
eration to maintain permeate flux [through incorporating chemical
cleanings into regular physical cleaning processes, for example
chemically enhanced backwashes (CEBs)], or as a recovery oper-
ation to recover membrane flux from a severely fouled membrane
module (Ramos et al. 2014). Chemically enhanced backwashes
combine conventional physical backwashing with chemical clean-
ing in one process, which could be of high importance for the
design and operation of membrane bioreactor (MBR) systems
for wastewater treatment. Recent studies using CEBs have typically
been performed at long intervals (weekly or monthly cleaning proc-
esses) (Zhou et al. 2014). There have been few comparative studies
on different cleaning methods and conditions, and scant informa-
tion exists on CEBs, in general, in the literature (Ramos et al. 2014;
Zhou et al. 2014). Snowdon et al. (2018) observed that one 60 s
CEB every 24 h resulted in increased permeate flux, operational
permeability, and net flux, demonstrating CEBs’ effectiveness as
a preventive maintenance operation.
This research project compared the efficiency of two different
chemical cleaning processes applied to one membrane module
integrated within a continuously operated pilot-scale AnMBR sys-
tem. The two chemical cleaning processes were applied to the
membrane module only once it was severely fouled, acting as a
recovery operation. As a secondary objective, the project investi-
gated the impact of daily CEBs on the effectiveness of each
chemical cleaning process. The novel pilot-scale AnMBR system
consisted of a 1,000 L anaerobic continuously stirred tank reactor
(CSTR) integrated with an external nanofiltration tubular mem-
brane module. The reactor and membrane configuration provided
benefits over conventional cleaning processes in that the membrane
module did not need to be removed for chemical cleanings (since it
could be isolated from the CSTR through a recirculation loop). This
resulted in minimal downtime and maintenance work required for
chemical cleaning processes. With few direct comparative studies
on different chemical cleanings applied to the same membrane
module, and little information in the literature on CEBs, there
Fig. 1. Simplified PFD of experimental setup.
© ASCE 04019018-2
J. Environ. Eng., 2019, 145(5): 04019018
are, to the authors’ best knowledge, no studies investigating the
impact of daily CEBs on the effectiveness of chemical cleaning
processes.
Materials and Methods
Reactor Configuration
A 1,000 L stainless steel anaerobic CSTR was equipped with an
external nanofiltration tubular membrane module and operated in
cross-flow mode. A simplified process flow diagram (PFD) of the
configuration may be viewed in Fig. 1. The anaerobic CSTR was
equipped with a heat wrap, which maintained the reactor temper-
ature at an average value of 36.2°C (
0.5°C) throughout the dura-
tion of the study. The operational temperature of approximately
36°C was selected since it is the upper limit of mesophilic anaerobic
digestion (25°C–35°C) and maximized biogas generation, which
was desired (Metcalf & Eddy, Inc. 1991).
Reactor-mixed liquor was continuously recirculated from the
CSTR to the membrane module and back into the CSTR by a pro-
gressive cavity pump (Nemo, New Brunswick, Canada). This pump
maintained a mixed-liquor flow rate of 6,000 L=h, which resulted
in the targeted membrane surface cross-flow velocity of 2.5 m=s
and a complete recirculation of reactor contents every 10 min.
A cross-flow velocity of 2.5 m=s was selected since it is deemed
to be the minimum operational cross-flow velocity that must be
maintained for the membrane module based on manufacturer rec-
ommendations. It was desired to operate at the lower spectrum of
the operational cross-flow velocity to minimize energy demands.
The membrane module was cylindrical in shape, composed of poly-
vinylidene fluoride (PVDF), with an outer diameter of 50 mm and
a total length of 1.436 m. The module contained 13 tubular mem-
brane channels, each 8 mm in diameter, which resulted in a total
membrane area of 0.42 m2 . The membrane surfaces had a mean
pore size of 30 nm.
J. Environ. Eng.
Table 1. Chemical cleaning conditions
Cleaning Recirculation Soak time Number of backwashes and
process Cycle time (min) (min) duration (number and min) Chemical used
1 1 30 N/A 2 and 2 min 1% sodium hydroxide
2 N/A 20 N/A
3 30 N/A 2 and 2 min
4 30 N/A 2 and 2 min 1% citric acid
5 N/A 20 N/A
6 30 N/A 2 and 2 min
7 30 N/A 2 and 2 min 1% sodium hydroxide and sodium hypochlorite
8 N/A 20 N/A
9 30 N/A 2 and 2 min
2 1 30 N/A N/A 1% sodium hydroxide and sodium hypochlorite
2 N/A 60 N/A
3 30 N/A N/A
3 1 30 N/A N/A 1% sodium hydroxide and sodium hypochlorite
2 N/A 60 N/A
3 30 N/A N/A
4 1 30 N/A N/A 1% sodium hydroxide and sodium hypochlorite
2 N/A 60 N/A
3 30 N/A N/A
5 1 30 N/A N/A 1% sodium hydroxide and sodium hypochlorite
2 N/A 60 N/A
3 30 N/A N/A
6 1 30 N/A 2 and 2 min 1% sodium hydroxide
2 N/A 20 N/A
3 30 N/A 2 and 2 min
4 30 N/A 2 and 2 min 1% citric acid
5 N/A 20 N/A
6 30 N/A 2 and 2 min
7 30 N/A 2 and 2 min 1% sodium hydroxide and sodium hypochlorite
8 N/A 20 N/A
9 30 N/A 2 and 2 min

chemical cleaning process. Finally, the chemicals used outline the
exact concentration of chemical cleaning solutions applied to the
membrane module during each cleaning condition.
Clean water flux was measured by isolating the CSTR recircu-
lation line from the CSTR itself, allowing a 50-L tank to be filled
with clean water (maintained at around 30°C) and filtered through
the membrane module. Each clean water test recirculated the clean
water at five flow rates in increasing order (790, 1,580, 2,360,
3,150, and 3,940 L=h), and the resultant membrane fluxes and
TMPs were measured. Five different increasing flow rates were se-
lected to provide incremental increases in flux and TMP, reaching
the maximum flow rate of the recirculation loop at approximately
3,940 L=h. Operational permeability is defined as membrane flux
divided by instantaneous operational TMP, in other words pressure-
averaged flux, and may be defined by Eq. (1) (Hamden de Andrade
et al. 2013):
Ji
OPi ¼ ð1Þ
ΔPi
In Eq. (1), OPi is the instantaneous operational permeability
(L=m2 =h=bar), J i is the instantaneous membrane flux (L=m2 =h),
and ΔPi is the instantaneous transmembrane pressure (bar). Opera-
tional permeability was considered so that TMP could be factored
into the flux recovery analysis. Clean water recoveries were calcu-
lated by dividing the post–chemical cleaning clean water flux or
post–chemical cleaning clean water OP by the initial clean water
flux or initial OP values measured on Day 1 of operation, and then
multiplying by 100. Once the membrane module was placed back
inline for mixed-liquor recirculation, and after 24 h of recirculation
at a flow rate of 6,000 L=h, the flux and TMP of the membrane
module were also measured. These values allowed the MLF
and MLOP to be calculated. The mixed-liquor recoveries were
calculated by dividing the post–chemical cleaning MLF or post–
chemical cleaning MLOP values by the initial MLF or initial
MLOP values measured on Day 2 of operation, and then multiply-
ing by 100. Equations used to calculate clean water and mixed-
liquor recoveries are displayed in Eqs. (2) and (3), respectively:
J; OPPC
CW J;OP ð%Þ ¼ × 100 ð2Þ
J; OPo
J; OPPC
MLJ;OP ð%Þ ¼ × 100 ð3Þ
J; OPo
In Eq. (2), CW J;OP is the clean water flux or operational per-
meability recovery (%), J; OPPC is the post–membrane cleaning
clean water membrane flux or clean water operational permeability
(L=m2 =h, L=m2 =h=bar), and J, OPo is the initial clean water mem-
brane flux or clean water operational permeability (L=m2 =h,
L=m2 =h=bar). In Eq. (3), MLJ;OP is the mixed-liquor flux or opera-
tional permeability recovery (%), J; OPPC is the post–membrane
cleaning mixed-liquor membrane flux or mixed-liquor operational
permeability (L=m2 =h, L=m2 =h=bar), and J; OPo is the initial
mixed-liquor membrane flux or mixed-liquor operational per-
meability (L=m2 =h, L=m2 =h=bar).
Membrane resistance coefficients were calculated using the
resistance-in-series model [Eq. (4)]. This equation was adopted and
developed from other studies (Ruigomez et al. 2017):

© ASCE 04019018-4 J. Environ. Eng.

J. Environ. Eng., 2019, 145(5): 04019018

cleanings can be performed either as a preventive maintenance op-
eration to maintain permeate flux [through incorporating chemical
cleanings into regular physical cleaning processes, for example
chemically enhanced backwashes (CEBs)], or as a recovery oper-
ation to recover membrane flux from a severely fouled membrane
module (Ramos et al. 2014). Chemically enhanced backwashes
combine conventional physical backwashing with chemical clean-
ing in one process, which could be of high importance for the
design and operation of membrane bioreactor (MBR) systems
for wastewater treatment. Recent studies using CEBs have typically
been performed at long intervals (weekly or monthly cleaning proc-
esses) (Zhou et al. 2014). There have been few comparative studies
on different cleaning methods and conditions, and scant informa-
tion exists on CEBs, in general, in the literature (Ramos et al. 2014;
Zhou et al. 2014). Snowdon et al. (2018) observed that one 60 s
CEB every 24 h resulted in increased permeate flux, operational
permeability, and net flux, demonstrating CEBs’ effectiveness as
a preventive maintenance operation.
This research project compared the efficiency of two different
chemical cleaning processes applied to one membrane module
integrated within a continuously operated pilot-scale AnMBR sys-
tem. The two chemical cleaning processes were applied to the
membrane module only once it was severely fouled, acting as a
recovery operation. As a secondary objective, the project investi-
gated the impact of daily CEBs on the effectiveness of each
chemical cleaning process. The novel pilot-scale AnMBR system
consisted of a 1,000 L anaerobic continuously stirred tank reactor
(CSTR) integrated with an external nanofiltration tubular mem-
brane module. The reactor and membrane configuration provided
benefits over conventional cleaning processes in that the membrane
module did not need to be removed for chemical cleanings (since it
could be isolated from the CSTR through a recirculation loop). This
resulted in minimal downtime and maintenance work required for
chemical cleaning processes. With few direct comparative studies
on different chemical cleanings applied to the same membrane
module, and little information in the literature on CEBs, there
Fig. 1. Simplified PFD of experimental setup.
© ASCE 04019018-2
J. Environ. Eng., 2019, 145(5): 04019018
are, to the authors’ best knowledge, no studies investigating the
impact of daily CEBs on the effectiveness of chemical cleaning
processes.
Materials and Methods
Reactor Configuration
A 1,000 L stainless steel anaerobic CSTR was equipped with an
external nanofiltration tubular membrane module and operated in
cross-flow mode. A simplified process flow diagram (PFD) of the
configuration may be viewed in Fig. 1. The anaerobic CSTR was
equipped with a heat wrap, which maintained the reactor temper-
ature at an average value of 36.2°C (
0.5°C) throughout the dura-
tion of the study. The operational temperature of approximately
36°C was selected since it is the upper limit of mesophilic anaerobic
digestion (25°C–35°C) and maximized biogas generation, which
was desired (Metcalf & Eddy, Inc. 1991).
Reactor-mixed liquor was continuously recirculated from the
CSTR to the membrane module and back into the CSTR by a pro-
gressive cavity pump (Nemo, New Brunswick, Canada). This pump
maintained a mixed-liquor flow rate of 6,000 L=h, which resulted
in the targeted membrane surface cross-flow velocity of 2.5 m=s
and a complete recirculation of reactor contents every 10 min.
A cross-flow velocity of 2.5 m=s was selected since it is deemed
to be the minimum operational cross-flow velocity that must be
maintained for the membrane module based on manufacturer rec-
ommendations. It was desired to operate at the lower spectrum of
the operational cross-flow velocity to minimize energy demands.
The membrane module was cylindrical in shape, composed of poly-
vinylidene fluoride (PVDF), with an outer diameter of 50 mm and
a total length of 1.436 m. The module contained 13 tubular mem-
brane channels, each 8 mm in diameter, which resulted in a total
membrane area of 0.42 m2 . The membrane surfaces had a mean
pore size of 30 nm.
J. Environ. Eng.
Wat. Sci. Tech. Vol. 28. No.2. pp. 165-176. 1993. 0273-1223/93 $6'00 0'00
Printed in Great Britain. All rights reserved. Copyright © 1993 IAWQ

ANAEROBIC-AEROBIC TREATMENT OF
POTATO-STARCH WASTEWATER

U. Abeling and C. F. Seyfried

Institut for Siedlungswasserwirtscha/t und Abfalltechnik (Water Supply and Treatment of

Solid Wastes). University of Hannover. Welfengarten I. D-3000 Hannover I. Germany

ABSTRACT

Production of potato starch produces wastewaters witb high concentrations of COD, nitrogen and
phosphorus. The best known and most economical solution for tbe nearly full elimination of tbese substances
is tbe two-stage anaerobic-aerobic treatment. The anaerobic pretreatment must only go so far as to maintain
enougb COD for biological nitrogen and phosphorus elimination in tbe aerobic stage. To optimize tbis
process, several tests have been carried out on nitrification/denitrification by means of tbe intermediate
product nitrite. The carbon consumption amounts to only 60% in comparison witb denitrification via nitrate.
The essential parameter for regulating tbe process is tbe concentration of free ammonia in tbe reactor.
Concentrations of I to 5mg NH31l inhibit tbe nitratation but not tbe nitritation. A separation of botb partial
steps is possible. The content of ammonia was controlled by means of continuous NH4 and pH measuring.

The process is suitable for many wastewaters witb low CODrrKN ratios and higb nitrogen concentrations. If
tbere are undesired nitrite peaks in an aerobic treatment plant caused by bigh pH values and temperatures,
specific nitrogen elimination by means of nitrite is a reliable treatment system.

KEYWORDS

Potato-starch wastewater; anaerobic-aerobic treatment; high-strength ammonium wastewater;

nitrification/denitrification via nitrite; nitritation; nitratation; industrial wastewater; nitrogen removal.

INTRODUCTION

In Europe, about 4.7 Mio. t starch and starch decay products are produced each year. The main raw materials
used are com (60% of the production) and potatoes and wheat (nearly 20% each). The largest product group
is the true starches with nearly 30%, followed by glucose (23%), isoglucose (13%) and modified starch
(12%). Most starch is employed in the food industry (for example sweets, drinks, fruit manufacturing - total
57%), the paper and paperboard industry (25%), as well as the chemical and pharmaceutical industry (10%).
Whereas a short time ago most of the attention was directed to production processes and commercializing,
nowadays wastewater avoidance and wastewater treatment are becoming more and more important. The cost
share of advanced wastewater treatment in the total production costs amounts to nearly 15%.

The starch wastewaters have high nitrogen and phosphorus concentrations. In Germany both nutrients must
be largely eliminated, and this will soon apply to the whole of the European Community as far as the
harmonization of environmental protection is concerned.

For purification of industrial wastewaters, especially for starch factories, more and more two-stage
anaerobic-aerobic processes have been used during the last few years. This is useful - for energetic reasons
- when highly concentrated wastewaters are to be treated, as a substantial part of the organic load can be

1 65
 Potato-starch wastewater 167

t:----I:;;.;;;,;::;;;;�)_---__1 transport and

'---.--./ washing water

starch/potato - protein -coagulation )..-----l potato juice

juice seperation

S��t-----1 process water

Figure I. Flow diagram of potatO staJeh production

TABLE 1. Potato-Starch Production - Wastewater Characteristics and Specific volumes

washing water process water potato juice

(after protein-coagulation)

pH-Value 6 - 7 6 - 7 5 - 6
COD [mg/l] 2,000 - 4,000 4,000 - 8,000 50,000 - 60,000 (25,000 - 30,000)
TKN [mg/l] 150 - 30 150 - 600 3,600 - 4,400 (1,800 - 2,200)
tot. P [mg/l] 20 - 40 20 - 40 800 - 1,000 (400 - 500)

m3/t potatoes 0. 3 - 1.0 0.6 - 1.3 0.8 - 1.0

The washing water resulting from potato washing is recycled. The solid matter (earth, plant parts etc.) is
eliminated in a sedimentation tank, and any lost part of the water is substituted by fresh water continuously.
The longer the campaign lasts, COD and TKN concentration increases, because the potato quality decreases
for the reason of storage. The process water (starch washing water) contains the contamination component
fme starch, which cannot be gained. The main component of the high strength potato juice is protein. It goes
into a protein extraction, where about 50% of the protein is coagulated, separated, dried and packed for sale.
A still highly contaminated wastewater with 25-30g CODn remains.

Modern manufacturers use circular movement of the water during washing and starch extraction to reduce
the specific wastewater quantities to keep the values preferably in the low regions of the range in Table 1.
The application of an effective technique for starch extraction also reduces the concentrations. Anyway, in
the field of potato juice the technical limits are reached by reducing the concentration by 50% by means of
protein extraction. The wastewater percentage is also layed down by the water content of the potatoes and
changes only slightly. Table 2 shows the specific wastewater quantities and concentrations of a potato starch
factory which was opened in 1987 in Germany (Liichow). The treatment capacity amounts to 300 000
t1campaign (end August until mid March).
 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308 3299

Nomenclature

SNH NHþ 4 þ NH3 nitrogen (g N m )

3
SS readily biodegradable organic matter (g O2 m3)
SND soluble biodegradable organic nitrogen XS slowly biodegradable organic matter (g O2 m3)
(g N m3) SI soluble inert organic matter (g O2 m3)
XND particulate biodegradable organic nitrogen XI particulate inert organic matter (g O2 m3)
(g N m3) XBH active heterotrophic biomass (g O2 m3)
XNI particulate inert organic nitrogen (g N m3) XBAI active NHþ 3
4 oxidisers biomass (g O2 m )
SNOI NO 3
2 nitrogen (g N m ) XBAA 
active NO2 oxidisers biomass (g O2 m ) 3

SNOA NO3 nitrogen (g N m3) XP particulate inert organic matter from biomass
SO oxygen (g O2 m3) decay (g O2 m3)

wastewater, a model allows to quickly screen many poten- chemical oxygen demand (COD) hydrolysis could signifi-
tial design and management alternatives. cantly affect the denitrification.
For the evaluation and the optimization of the treat- The objective of this work was to develop and to cali-
ment of urban wastewaters, various models have been brate a mathematical model for the simulation of the mod-
developed and edited by the IWA task group (Henze ified SBR, treating piggery wastewaters. First, an analysis
et al., 1987), such as the activated sludge models (ASM). of the processes involved in nitrogen removal was carried
These models are largely used for domestic sewage but out based on the experimental results. Then, a mathemati-
the modelling is overlooked in the treatment of livestock cal model was built and calibrated using the experimental
wastes and industrial effluents (Orhon, 1998). The available data.
activated sludge models were specifically designed and cal-
ibrated for urban wastewater treatment, and therefore, the
extension of such models to more concentrated influents
such as piggery wastewaters, appears particularly interest-
ing but requires specific experiments and research.
In contrast to the domestic sewage, a very limited
amount of data on the kinetic and stoichiometric processes
and on the influent fractionation are available for piggery
wastewaters (Andreottola et al., 1997). The ASM models
describe the processes of nitrification and denitrification
as one-step processes. However, nitrogen removal for con-
centrated wastewaters, as the piggery wastewaters, might
result in the inhibition of nitrification by free ammonia
and nitrous acid (Anthonisen et al., 1976), and nitrification
might be limited by the dissolved oxygen (DO) concentra-
tion (Wiesmann, 1994). Therefore, the simplified assump-
tion, used in the ASM models, is no longer applicable
for the description of nitrogen removal processes in this
case. In fact, the free ammonia inhibition and/or the
nitrous acid inhibition and/or the dissolved oxygen limita-
tion frequently lead to nitrite accumulation. High temper-
atures can also lead to nitrite accumulation (Hellinga
et al., 1998). Consequently, more sophisticated model
assumptions are required for an adequate description of
the system efficiency. In this case, each process must
be described as a two-step process including nitrite as
intermediate (Andreottola et al., 1997). Moreover, some
authors studied and compared the heterotrophic yields
under aerobic and anoxic conditions (Gujer et al., 1999;
Orhon et al., 1996; Boursier et al., 2004). The observed
lower anoxic heterotrophic yield leads to a lower COD to
NO 3  N ratio for the denitrification. That is more partic-
ularly important for the wastewaters with high N concen-
tration where the kinetics and the stoichiometry of the
3300 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308

known amount of piggery wastewater was added in the
reactor through a buffer tank where the quantity added
was weighed and recorded. The reactor was equipped with
a foam breaker working during the aerobic phases and a
fine bubbles diffuser fed with a compressor (2–5 m3 h1).
For the mixing, a centrifugal pump (30 m3 h1) circulated
the activated sludge, during the anoxic phases from the
bottom to the top of the reactor. Water was continuously
added in the reactor (65 l per day) to compensate for the
evaporation caused by the high temperature and the aera-
tion. At the end of each cycle, an amount of the activated
sludge equal to the piggery wastewater added at the begin-
ning of the cycle was withdrawn from the reactor. The bio-
logical reactor was equipped with on-line measurements of
DO (WTW Oxi197 oxygen meter), temperature (Ponselle
PONAPF-TTRANS), oxidation–reduction potential (Pon-
selle PONAPF-EHTRANS) and pH (Ponselle PONAPF-
PHTRANS) allowing measurements at 10 min. intervals.
The system operated without sludge recirculation nor
decantation in the reactor, leading to a solids retention
time equal to the hydraulic retention time. For each exper-
iment, each whole-cycle of the modified SBR was scheduled
as follows:
• a feeding phase,
• an anoxic phase,
• an aerobic phase,
• a withdrawal phase.
2.2. Experimental
the reactor reached steady-state conditions (after more
than three hydraulic residence times), the characterisation
of the effluent was done (COD, soluble COD and total
nitrogen) and was followed by a study of the evolution
of NHþ  
4 , NO2 and NO3 in the reactor, during one
cycle.
Immediately after run 1, a second study of the evolution
 
of NHþ 4 , NO2 and NO3 , during one cycle, was performed
(run 2). At the beginning of this cycle, 1 l of ammonium
carbonate solution (13.5 kg N m3) was added in the reac-
tor during the feeding phase, together with the piggery
wastewater (PW1). For this experiment, the other experi-
mental conditions were similar to run 1.
For run 3, as for run 1, the reactor was initially filled
with 50 l of activated sludge coming from the same farm
and 50 l of tap water. About 600 l of raw piggery waste-
water was collected in an experimental farm near Rennes
(France) and was mechanically sieved (1 mm) using a
rotary screen. The liquid fraction called piggery wastewater
2 (PW2) was stored at 4 C and was used for run 3. For this
run, the duration of a cycle was equal to 12 h, consisting of
7 h of anoxic conditions and 5 h of aerobic conditions. At
the beginning of each cycle, 4.4 l of PW2 was added in the
reactor, leading to a working volume of 104.4 l and a HRT
equal to 11.9 days. At the end of each cycle, the same
amount of activated sludge was withdrawn. A characterisa-
tion of the effluent (COD, soluble COD and total nitrogen)
 
and a study of the evolution of NHþ 4 , NO2 and NO3 dur-
ing a cycle, were performed when more than 3 hydraulic
residence times had passed.
The main characteristics of each piggery wastewater
used in this study are presented in Table 2.

Runs PW HRT (days) P1 (h) P2 (h) P3 (h) P4 (h) Observations

1 1 11.0 0.1 3.9 19.9 0.1 Effluent characterisation and study of a cycle
2 1 11.0 0.1 3.9 19.9 0.1 Study of a cycle (ammonium carbonate was added)
3 2 11.9 0.1 6.9 4.9 0.1 Effluent characterisation and study of a cycle
PW: piggery wastewater, P1: feeding phase, P2: anoxic phase, P3: aerobic phase, P4: withdrawal phase.
3302 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308

threshold of inhibition. On the contrary, the free ammonia Table 4

concentrations observed during the treatment of piggery Nitrogen mass balance during run 1 and 3
wastewaters, were higher than the threshold of inhibition Runs Influent (g N) Effluent (g N) N2 (g N) Mass balance (%)
(0.1–10 mg N l1) found in the literature (Anthonisen 1 46.0 18.0 25.0 93.5
et al., 1976). Temperature, used in the SHARON process, 3 18.9 4.5 14.5 100.5
could also influence nitrite accumulation (Hellinga et al.,
1998). Indeed, above 20 C, the NO 2 oxidisers growth rate was equal to 100.5%. According to these nitrogen mass bal-
is faster than the NHþ 4 oxidisers growth rate. This differ- ances, the nitrogen not taken into account was close to the
ence could partially explain the accumulation of NO 2 experimental errors (67%). These results indicate clearly
experimentally observed. DO could also limit significantly that the nitrification during the aerobic phase followed by
1
the NO 2 oxidisers below 0.5–1.0 mg O2 l (Wiesmann, the denitrification during the anoxic phase were the domi-

½NHþ   10pH able fraction was replaced by a simplified first-order

½NH3  ¼  4  ð1Þ
6344 hydrolysis process (Boursier et al., 2004),
exp þ 10pH
273 þ T • the distinction between the anoxic heterotrophic yield
and the aerobic heterotrophic yield (Gujer et al., 1999;
In addition to the study of the evolution of nitrogen in the Orhon et al., 1996; Boursier et al., 2004),
þN 2
reactor, a nitrogen mass balance (defined as N Effluent  • the limitation by NHþ
N Influent 4 of the growth of heterotrophic
100Þ was calculated for run 1 and 3 (Table 4). The N2, pro- and autotrophic biomass.
duced by denitrification during each cycle, was estimated as
the difference between the NO 
2 plus NO3 at the beginning The model distinguishes 15 components and 11 biol-
and at the end of the anoxic phase. For run 1, the feeding ogical processes for the oxidation of organic matter, the
provided 46 g of nitrogen in the reactor while 18 g were nitrification and the denitrification (Appendix A.1). The stoi-
withdrawn at the end of the cycle. Considering the calcu- chiometry of these processes is shown in Appendix A.2.
lated N2 produced by denitrification, the nitrogen mass For the heterotrophic biomass, the kinetic and stoichi-
balance was equal to 93.5%. For run 3, the mass balance ometric values are identical to the ASM1 (Henze et al.,
2000), except the aerobic and anoxic heterotrophic yield
Table 3 and the maximum specific hydrolysis rate (Boursier et al.,
Comparison between the average NO2 oxidation rate (r1), NH3 and 2004). Concerning the autotrophic biomass, the kinetic
DO concentrations during the first part of the aerobic phase (0.2
and stoichiometric values suggested by Hao et al.
days 6 Time 6 0.6 days)
(2002a,b) were used. All values are reported in Appendix
Runs r1 (mg N l1 h1) NH3 (mg N l1) DO (mg O2 l1)
A.3. Several kinetic parameters depend on the temperature.
1 7.5 35.6 0.14 The basic Arrhenius kinetic equation for the dependency
2 16.8 53.4 0.28
on temperature, implemented in the model, is as follows:
3304 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308

Fig. 5. Experimental and simulated nitrogen concentrations during the cycles of run 1, 2 and 3.

anoxic heterotrophic yield of 0.53 was used instead of aero-
bic heterotrophic yield of 0.6, leading to a lower need of
COD for denitrification. Even if this difference seems low,
it is not negligible and particularly important with nitrogen
concentrated effluent and sequential batch reactors. More-
over, the difference of oxygen half-saturation constant for
ammonium and nitrite oxidisers previously observed (Wies-
mann, 1994) was confirmed during this work.
However, some model limitations were observed during
this work and would require more research. During this
study, the simulations were performed using a constant
temperature while the temperature varied in the experimen-
tal reactor. The variation of temperature, mainly during run
forms of nitrogen (NO 
2 and NO3 ) was not correctly simu-
lated during the anoxic phase of run 3 (Fig. 5). For a better
modelling result, a distinction between the heterotrophic
biomass reducing NO 
3 to NO2 and the heterotrophic

biomass reducing NO2 to N2 would probably be necessary
(Huang and Hao, 1996). The influence of organic matter
limitation on nitrite accumulation during denitrification (Oh
and Silverstein, 1999) could also be considered in order to
improve the simulations. Finally, during this work, the
developed model was calibrated and validated using only
two piggery wastewaters with different compositions. Addi-
tional works using others piggery wastewaters and longer
HRT would allow to improve the model.
 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308 3305

4. Conclusions waters. It could be used also for other concentrated waste-

In this study, a mathematical model was developed and
was calibrated for the simulation of the modified SBR,
treating piggery wastewaters. This model based on
ASM1, allowed to simulate nitrite as intermediate of nitri-
fication and also of denitrification. The results obtained
during this study identified the DO concentration, rather
than NH3, as the main factor influencing the NO 2 oxida-
tion rate, and leading to accumulation of NO 2 during
nitrification. The experimental data coming from three
runs carried out with two different piggery wastewaters
were used for the calibration and the validation of the
model. Finally, a set of model parameters was determined,
and allowed to describe the behaviour of the nitrogen
during the biological treatment of piggery wastewaters.
However, the results seem to indicate a variation between
piggery wastewaters of the maximum specific hydro-
lysis rate, which ranged between 6 and 25 g COD
(g COD day)1.
This model could be used for improving the design and
operation of the biological treatment of piggery waste-
waters after calibration. Taking into account nitrite as
intermediate of the nitrification and the denitrificiation
could be an interesting tool allowing the determination of

conditions for partial nitrification of NHþ4 to NO2 directly
followed by denitrification. For this, more research is
needed to include and model all effects that can potentially
influence NO 2 accumulation.
5. Web references
ASModel1.0: http:/scilabsoft.inria.fr/contribution/display-
Category.php?category=SCICOS or http://beline. homeli-
nux.net/fabrice/rubrique.php3?id_rubrique=15
Acknowledgements
This study was financially supported by the French
national program ‘‘Porcherie Verte’’. We thank professor
P. Lessard (University Laval, Québec) and Dr. A. Tré-
mier (Cemagref) for the help and the comments on this
paper.

Appendix A

A.1. Process kinetics for organic matter oxidation, nitrification and denitrification

j Process rate Definition

   
SS SO S NH Aerobic growth of heterotrophs
q1 lH X BH
SS þ K S S O þ K OH S NH þ K NH
     
SS K OH S NH S NOI S NOI
q2 lH gG X BH Aerobic growth of heterotrophs
SS þ K S S O þ K OH S NH þ K NH S NOI þ K NOI S NOI þ S NOA
with SNOI
     
SS K OH S NH S NOA S NOA
q3 lH gG X BH Aerobic growth of heterotrophs
SS þ K S S O þ K OH S NH þ K NH S NOA þ K NOA S NOI þ S NOA
with SNOA
   
S NH SO S NH
q4 lAI X BAI Aerobic growth of NHþ
4
S NH þ K NAI S O þ K OAI S NH þ K NH
oxidisers
   
S NOI SO S NH
q5 lAA X BAA Aerobic growth of NO
2
S NOI þ K NAA S O þ K OAA S NH þ K NH
oxidisers

q6 bH Æ XBH Decay of heterotrophs

q7 bAI Æ XBAI Decay of NHþ 4 oxidisers
q8 bAA Æ XBAA Decay of NO 2 oxidisers
q9 KA Æ SND Æ XBH Ammonification of soluble
      organic nitrogen
SO K OH S NOI S NOI
q10 K H þ gH Hydrolysis of entrapped
S O þ K OH S O þ K OH S NOI þ K NOI S NOI þ S NOA
   i organics
K OH S NOA S NOA
þ gH XS
S O þ K OH S NOA þ K NOA S NOI þ S NOA
 
X ND
q11 q10 Hydrolysis of entrapped
Xs
organic nitrogen
3306 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308

A.2. Process stoichiometry for organic matter oxidation, nitrification and denitrification

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
SI SS XI XS XBHI XBAI XBAA XP SO SNOI SNOA SNH SND XND XNI
1 ð1Y H Þ
q1 YH 1 YH  iBN

1 1Y HD
q2 Y HD 1  1:71Y HD
 iBN

1 1Y HD 1Y HD
q3 Y HD 1  1:14Y HD
 1:14Y HD
iBN

q4 1  3:43Y
Y AI
AI 1
Y AI iBN  Y1AI

q5 1  1:14Y
Y AA
AA
 Y 1AA 1
Y AA iBN
q6 1  fP 1 fP iBN  fP fP Æ iBN
Æ iBN
q7 1  fP 1 fP iBN  fP fP Æ iBN
Æ iBN
q8 1  fP 1 fP iBN  fP fP Æ iBN
Æ iBN
q9 1 1
q10 1 1
q11 1 1

A.3. Default values at 20 C for the model and parameters used for simulating run 1, 2 and 3 (-: default value was used)

Symbol Definition Default Run 1 Run 2 Run 3 Ref.

value
YH Aerobic yield heterotrophic 0.6 – – – Boursier et al. (2004)
biomass (g COD g COD1)
YHD Anoxic yield heterotrophic 0.53 – – – Boursier et al. (2004)
biomass (g COD g COD1)
lH Maximum specific growth rate for 6 – – – Henze et al. (2000)
heterotrophic biomass (day1)
bH Decay coefficient for heterotrophic 0.62 – – – Henze et al. (2000)
biomass (day1)
KS SS half-saturation coefficient for 20 – – – Henze et al. (2000)
heterotrophic biomass (g COD m3)
KOH SO half-saturation coefficient for XBH 0.2 0.05 0.05 0.05 Henze et al. (2000)
(g COD m3)
KNH SNH half-saturation coefficient 0.05 – – – Henze et al. (2000)
for biomass (g N m3)
KNOI SNOI half-saturation coefficient for XBH 0.5 – – – Henze et al. (2000)
under anoxic conditions (g N m3)
KNOA SNOA half-saturation coefficient for 0.5 – – – Henze et al. (2000)
under anoxic conditions (g N m3)
gG Correction factor for lH under anoxic 0.8 – – – Henze et al. (2000)
condition (dimensionless)
gH Correction factor for hydrolysis under 0.4 – – – Henze et al. (2000)
anoxic condition (dimensionless)
KH Maximum specific hydrolysis rate 3 25 25 6 Boursier et al. (2004)
(g COD (g COD day)1)
KA Ammonification rate 0.08 – – – Henze et al. (2000)
(m3 COD (g day)1)
(continued on next page)
3308 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308
treatment using sequencing batch reactors. Water Res. 38, 3340–
3348.
Lee, S.M., Jung, J.Y., Chung, Y.C., 2000. Measurement of ammonia
inhibition of microbial activity in biological wastewater treatment
process using dehydrogenase assay. Biotechnol. Lett. 22, 991–994.
Nielsen, P.H., 1996. Adsorption of ammonium to activated sludge. Water
Res. 30 (3), 762–764.
Oh, J., Silverstein, J., 1999. Acetate limitation and nitrite accumulation
during denitrification. J. Environ. Eng. ASCE 125 (3), 234–242.
Orhon, D., 1998. Evaluation of industrial biological treatment design on
the basis of process modelling. Water Sci. Technol. 38 (4–5), 1–8.
Orhon, D., Okutman, D., 2003. Respirometric assessment of residual organic
matter for domestic sewage. Enzyme Microb. Tech. 32 (5), 560–566.
Orhon, D., Sozen, S., Artan, N., 1996. The effect of heterotrophic yield on
the assessment of the correction factor for anoxic growth. Water Sci.
Technol. 34 (5–6), 67–74.
Peu, P., Béline, F., Martinez, J., 2004. Volatile fatty acids analysis from
pig slurry using high performance liquid chromatography. Int. J.
Environ. An. Ch. 84 (13), 1017–1022.
Sollfrank, U., Gujer, W., 1991. Characterisation of domestic wastewater
for mathematical modelling of the activated sludge process. Water Sci.
Technol. 23, 1057–1066.
Villaverde, S., Fdz-Polanco, F., Garcia, P.A., 2000. Nitrifying biofilm
acclimatation to free ammonia in submerged biofilters: start-up
influence. Water Res. 34, 602–610.
Wiesmann, U., 1994. Biological nitrogen removal from wastewater.
Adv. Biochem. Eng. Biot. 51, 113–154.
Wilderer, P.A., Jones, W.L., Dau, U., 1987. Competition in denitrification
systems affecting reduction rate and accumulation of nitrite. Water
Res. 21, 239–245.
sludge wastage rate increasing the foulant contribution from solu-
ble microbial products (SMPs) known to block membrane pores
and too low of a sludge wastage rate promoting the development
and growth of extracellular polymeric substances (EPSs), again
contributing to membrane fouling (Iorhemen et al. 2016; Ibeid
et al. 2016; Jarusutthirak and Amy 2006; Le-Clech et al. 2006).
Studies have found that an optimum SRT range for both the min-
imization of SMP and EPS is around 25–30 days (Barker and
Stuckey 1998). Since the SRT for both of these periods of operation
was well above this value and within 25% of one another, SRT most
likely did not substantially contribute to their observed differences
in the rate of decline in operational permeability. Additionally, the
average backwash flow rate was greater during the period of oper-
ation following Cleaning Process 1, which would have contributed
towards a slower rate of operational permeability decline. Despite
the operating conditions being on average quite similar, no CEBs
being in place, and post–Chemical Cleaning Process 1 conditions
having more favorable physical cleaning processes in place, the
operating period following Cleaning Process 2 showed a much
lower rate of OP decline. The lower rate of OP decline may have
been primarily due to the nature of the chemical cleaning itself,
again supporting earlier conclusions that Cleaning Processes 2–5
were superior to Cleaning Processes 1 and 6.
Chemically enhanced backwashes were first applied to the
membrane module 40% of the way through the period of operation
following Cleaning Process 3. The average operating conditions
following Cleaning Processes 2 and 3 were relatively constant.
The largest discrepancies between these periods of operation were
the average backwash flow rate, which decreased by 11.3 L=h, and
the average SRT, which increased by 137 days from the period of
operation following Cleaning Process 2 to the period of operation
following Cleaning Process 3. Increasing the SRT would be ex-
pected to promote SMP foulant development, which would lead
to increased pore blockage. This in turn would result in less effi-
cient backwashes and, paired with a decreased backwash flow rate,
should have resulted in an increased rate of operational permeabil-
ity decline. The rate of operational permeability decline did in-
crease; however, the increase was very minimal, with a rate of
decline of 0.03 L=m2 =h=bar=day. The presence of CEBs for
60% of the operational period following Cleaning Process 3 likely
assisted in preventing the build-up of pore-blocking irreversible and
reversible foulants, resulting in this minimal increase in the rate of
operational permeability decline. Additionally, following Cleaning
Process 3 was the longest period of operation and the longest stand-
ardized period of operation. Zhou et al. (2014) found that the use of
sodium hydroxide backwashes retarded the rates of total foulant
and irreversible foulant accumulation, attributing their increased
performance to the combined hydraulic and chemical mechanisms
enhancing the detachment of biopolymers. It appears that CEBs are
beneficial, initially, in terms of reducing the rate of operational per-
meability decline and extending the duration of operation between
membrane cleanings. Ramos et al. (2014) were able to delay the
requirement for recovery cleaning by 3 years by incorporating
CEBs. This study fell short of a 3-year extension, likely due to dif-
ferences in membrane modules, and mixed-liquor/feed wastewater
characteristics, yet an extension over conditions without CEBs in
place was possible.
The period of operation following Cleaning Process 4, with
CEBs in place 100% of the time, saw the rate of decline in opera-
tional permeability increase by only 0.01 L=m2 =h=bar=day over
the period of operation following Cleaning Process 3. The reason
for this minimal increase in the rate of operational permeability de-
cline, and the second highest standardized duration of operation, is
most likely, once again, the presence of CEBs. Following Cleaning
© ASCE 04019018-8
J. Environ. Eng., 2019, 145(5): 04019018
Process 5, with CEBs in place 100% of the time, the rate of decline
in operational permeability increased to 0.12 L=m2 =h=bar=day, a
threefold increase over the rate following Cleaning Process 4. The
duration of operation and the standardized duration of operation
both reached their lowest values of 26 and 75 days, respectively,
during this period of operation as well. Zhou et al. (2014) found
that the average pore size of their PVDF membranes increased
after 1 week of operation with 1% sodium hypochlorite cleaning.
This resulted in a decrease in both their fouling resistance coeffi-
cients and operating periods between cleans. Wang et al. (2018)
noticed both their clean water flux and rate of hydraulic resistance
accumulation increased with an increased soak time in a sodium
hypochlorite cleaning solution, attributing the increase to an
enlargement in the pore size of the membrane module. Constant
contact between caustic cleaning solutions and the membrane sur-
face may provide initial benefits; however, over time it may lead to
an increased rate of fouling due to pore size enlargement.
Recent studies have also noted an increasing trend between the
quantity of dissolved organic matter and dose of sodium hypochlo-
rite the biomass is exposed to (Cai et al. 2016; Cai and Liu 2016).
Cai and Liu (2016) noted that increasing the concentration of dis-
solved organic matter in the mixed liquor resulted in an increased
membrane-fouling rate, although they found that following an
exposure of 55 mg-NaOCl=g-MLVSS the soluble COD concentra-
tion increased by only 180 mg=L, and under the operating condi-
tions provided in this study the dose would have been in the range
of 6–7 mg-NaOCl=g-MLVSS, meaning the impact in this case
would have been very minimal. Nonetheless, it is important to con-
sider that increased exposure to sodium hypochlorite may have
increased the generation of SMPs, which would have contributed
to the increased rate of decline in operational permeability as well.
Initially, the CEBs may be beneficial in retarding the rate of irre-
versible foulant accumulation on the membrane module and in its
pores, but over time the constant contact between the chemical sol-
ution and the membrane surface could be damaging. The pore size
of the membrane module used for this study was unable to be in-
vestigated prior to and following exposure to CEBs because this
would have required destroying the module, and it was decided that
the membrane would be stored for reuse following the conclusion
of the study. If the average pore size of the membrane did increase,
there was no impact on its TSS removal efficiency: it remained
above 99.9% throughout the duration of the entire study.
Conclusions
Two different chemical cleaning conditions were applied to a tubu-
lar, nanofiltration membrane module a total of six times, and each
chemical cleaning process’s individual performance was evaluated
and compared to that of the others. The membrane module was
operated as part of an AnMBR system for 466 days of continuous
operation. Over its course of operation, CEBs were eventually in-
corporated as a means of enhanced physical cleaning, and their
influence on membrane fouling mitigation and the chemical clean-
ings applied were also investigated. Overall, the following conclu-
sion may be drawn from this study:
• The static, one-solution chemical cleaning processes offered
higher recoveries in clean water flux, clean water operational
permeability, mixed-liquor flux, and mixed-liquor operational
permeability, on average, than the three-solution chemical
cleaning processes if the performance of Cleaning Process 1
can be attributed to its having taken place so early in the mem-
brane’s operational period, making the one-solution chemical
cleaning process the highest performing alternative.
J. Environ. Eng.
• No cleaning processes were able to recover clean water flux
and operational permeability very efficiently (with the highest
clean water flux recovery being 53%). However, all cleaning
processes were able to recover mixed-liquor flux and opera-
tional permeability effectively (with a lowest mixed-liquor flux
recovery of 67%).
• The citric acid portion of Cleaning Process 6 had a detrimental
effect on its overall foulant removal effectiveness.
• Daily CEBs enhanced the foulant removal of successive chemi-
cal cleaning processes applying the same cleaning conditions.
• Daily CEBs decreased the rate of foulant accumulation.
• Considering these results and those of Snowdon et al. (2018),
daily low-strength CEBs were observed to be an effective strat-
egy for both membrane fouling preventive maintenance and as
assistance in chemical cleaning recovery operations.
Acknowledgments
The authors would like to acknowledge and thank the following
funding agencies and industrial collaboration: the Natural Science
and Engineering Research Council (NSERC), the New Brunswick
Innovation Foundation (NBIF), and ADI Systems Inc. They would
also like to thank Jonathan Dargavel and Dr. Dennis Connor for
their help and contributions with data collection and testing
throughout the duration of the study.
References
APHA (American Public Health Association). 2005. Standard methods for
the examination of water and wastewater. Washington, DC: APHA.
Barker, D. J., and D. C. Stuckey. 1998. “A review of soluble microbial
products (SMP) in wastewater treatment systems.” Water Res. 33 (14):
3062–3082. https://doi.org/10.1016/S0043-1354(99)00022-6.
Cai, W., J. Liu, X. Zhang, W. J. Ng, and Y. Liu. 2016. “Generation of
dissolved organic matter and byproducts from activated sludge during
contact with sodium hypochlorite and its implications to on-line chemi-
cal cleaning in MBR.” Water Res. 104: 44–52. https://doi.org/10.1016/j
.watres.2016.07.065.
Cai, W., and Y. Liu. 2016. “Enhanced membrane biofouling potential
by on-line chemical cleaning in membrane bioreactor.” J. Membr. Sci.
511: 84–91. https://doi.org/10.1016/j.memsci.2016.03.039.
Hach Company. 2002. Water analysis handbook. Loveland, CO: Hach
Company.
Hamden de Andrade, L., F. D. dos Santos Mendes, J. Cawettiere Espindola,
and M. C. Santos Amaral. 2013. “Internal versus external submerged
membrane bioreactor configurations for dairy wastewater treatment.”
Desalin. Water Treat. 52 (16–18): 2920–2932. https://doi.org/10
.1080/19443994.2013.799048.
Ibeid, S., M. Elektorowicz, and J. A. Oleszkiewicz. 2016. “Impact of elec-
trocoagulation of soluble microbial products on membrane fouling at
different volatile suspended solids concentrations.” Environ. Technol.
38 (4): 385–393. https://doi.org/10.1080/09593330.2016.1195879.
Iorhemen, O. T., R. A. Hamza, and J. H. Tay. 2016. “Membrane bioreac-
tor (MBR) technology for wastewater treatment and reclamation:
Membrane fouling.” Membranes 6 (2): 33. https://doi.org/10.3390
/membranes6020033.
Jarusutthirak, C., and G. Amy. 2006. “Role of soluble microbial products
(SMP) in membrane fouling and flux decline.” Environ. Sci. Technol.
40 (3): 969–974. https://doi.org/10.1021/es050987a.
Kinnunen, V., A. Yla-Outinen, and J. Rintala. 2015. “Mesophilic anaerobic
digestion of pulp and paper industry biosludge-long-term reactor per-
formance and effects of thermal pretreatment.” Water Res. 87: 105–111.
https://doi.org/10.1016/j.watres.2015.08.053.
Le-Clech, P., V. Chen, and T. A. G. Fane. 2006. “Fouling in membrane
bioreactors used in wastewater treatment.” J. Membr. Sci. 284 (1–2):
17–53. https://doi.org/10.1016/j.memsci.2006.08.019.
© ASCE 04019018-9
J. Environ. Eng., 2019, 145(5): 04019018
Leedy, P., and J. Ormrod. 2005. Practical research: Planning and design.
New York: Pearson.
Liao, B. Q., J. T. Kramer, and D. M. Bagley. 2006. “Anaerobic membrane
bioreactors: Applications and research directions.” Crit. Rev. Environ.
Sci. Technol. 36 (6): 489–530. https://doi.org/10.1080/1064338060
0678146.
Lousada-Ferreira, M., J. B. van Lier, and J. H. J. M. van der Graaf. 2014.
“Impact of suspended solids concentration on sludge filterability in full-
scale membrane bioreactors.” J. Membr. Sci. 476: 69–75. https://doi.org
/10.1016/j.memsci.2014.11.012.
Meng, F., S. R. Chae, A. Drews, M. Kraume, H. S. Shin, and F. Yang. 2009.
“Recent advances in membrane bioreactors (MBRs): Membrane fouling
and membrane material.” Water Res. 43 (6): 1489–1512. https://doi.org
/10.1016/j.watres.2008.12.044.
Metcalf & Eddy, Inc.. 1991. Chap. 10 in Wastewater engineering treat-
ment, disposal, and reuse, 987–988. New York: McGraw-Hill.
Ozgun, H., R. Kaan Dereli, M. Evren Ersahin, C. Kinaci, H. Spanjers, and
J. B. van Lier. 2013. “A review of anaerobic membrane bioreactors for
municipal wastewater treatment: Integration options, limitations, and
expectations.” Sep. Purif. Technol. 118: 89–104. https://doi.org/10
.1016/j.seppur.2013.06.036.
Pilli, S., T. T. More, S. Yan, R. D. Tyagi, and R. Y. Surampalli. 2016.
“Fenton pre-treatment of secondary sludge to enhance anaerobic diges-
tion: Energy balance and greenhouse gas emissions.” Chem. Eng. J.
283: 285–292. https://doi.org/10.1016/j.cej.2015.07.056.
Ramos, C., F. Zecchino, D. Ezquerra, and V. Diez. 2014. “Chemical clean-
ing of membranes for an anaerobic membrane bioreactor treating food
industry wastewater.” J. Membr. Sci. 458: 179–188. https://doi.org/10
.1016/j.memsci.2014.01.067.
Ruigomez, I., E. Gonzalez, S. Guerra, L. E. Rodriguez-Gomez, and L. Vera.
2017. “Evaluation of a novel physical cleaning strategy based on HF
membrane rotation during the backwashing/relaxation phases for
anaerobic submerged MBR.” J. Membr. Sci. 526: 181–190. https://doi
.org/10.1016/j.memsci.2016.12.042.
Skouteris, G., D. Hermosilla, P. Lopez, C. Negro, and A. Blanco. 2012.
“Anaerobic membrane bioreactors for wastewater treatment: A review.”
Chem. Eng. J. 198–199: 138–148. https://doi.org/10.1016/j.cej.2012.05
.070.
Snowdon, J., K. S. Singh, and G. Zanatta. 2018. “Optimization of an
external nanofiltration anaerobic membrane bioreactor treating a high-
strength starch-based wastewater.” J. Environ. Eng. 144 (6): 04018032.
https://doi.org/10.1061/(ASCE)EE.1943-7870.0001376.
Sun, Y., Y. Fang, P. Liang, and X. Huang. 2016. “Effects of online chemical
cleaning on removing biofouling and resilient microbes in a pilot mem-
brane bioreactor.” Int. Biodeterior. Biodegrad. 112: 119–127. https://
doi.org/10.1016/j.ibiod.2016.05.010.
Wang, J., K. Li, D. Yu, J. Zhang, and Y. Wei. 2017. “Fouling characteristics
and cleaning strategies of NF membranes for the advanced treatment of
antibiotic production wastewater.” Environ. Sci. Pollut. Res. 24 (10):
8967–8977. https://doi.org/10.1007/s11356-015-5408-4.
Wang, Q., H. Zeng, Z. Wu, and J. Cao. 2018. “Impact of sodium hypochlo-
rite cleaning on the surface properties and performance of PVDF mem-
branes.” Appl. Surf. Sci. 428: 289–295. https://doi.org/10.1016/j.apsusc
.2017.09.056.
Young, J., and R. Cowan. 2004. Respirometry for environmental science
and engineering. Springdale, AR: SJ Enterprises.
Zhang, J., H. C. Chua, J. Zhou, and A. G. Fane. 2006. “Factors affecting
the membrane performance in submerged membrane bioreactors.”
J. Membr. Sci. 284 (1–2): 54–66. https://doi.org/10.1016/j.memsci
.2006.06.022.
Zhang, J., S. I. Padmasiri, M. Fitch, B. Norddahl, L. Raskin, and E.
Morgenroth. 2007. “Influence of cleaning frequency and membrane his-
tory on fouling in an anaerobic membrane bioreactor.” Desalination
207 (1–3): 153–166. https://doi.org/10.1016/j.desal.2006.07.009.
Zhou, Z., F. Meng, H. Lu, Y. Li, X. Jia, and X. He. 2014. “Simultaneous
alkali supplementation and fouling mitigation in membrane bioreactors
by on-line NaOH backwashing.” J. Membr. Sci. 457: 120–127. https://
doi.org/10.1016/j.memsci.2014.01.008.
J. Environ. Eng.
 o 1
Potato-s1arCb wastewater
00 2P ..---""T'I'-r----,.---.,..---, 98
171

10 I;?, 7" 9o

III 80
I.S +---��,..-_+---+_---;
20
NH.
I I 70

II 1/-lS·C
_UJ
30·C J I _S·C 60

60
/I HNo,-N
III
O.S+---+-�r\t---+_---;
70

I Vi NHJ
20

90
1/ /" 10
�V OP�,--��--�6-���---��
8
o
6 7 8 9 10 11 12 13
pH pH

+ -
17 NH -N . 10PH 46 N0 -N
4 2
(mg/I) HN0 -- (mg/l)
2
= • ---

14 YKw + 10pll 14 K · 10pll

.

"t, .. ioniz.tion constant of the _i. equilibrhlD equation K

•
• •(-2,300/(273 + ·C»

•
lew Ionization constant of water ANTHONISEN ET AL. (1976)

•(6,344/273+·C)
Figure 4 . Dissociation balances NlLt+/NH3 and N02IHN02 (Nybuis, 1985).
/K
"t, w ..

The inhibition of Nitrosomonas and Nitrobacter by ammonia has been proved in much fundamental research
(Anthonisen, 1974; Bergeron, 1978; Neufeld et al., 1980; Nyhuis, 1985; Dombrowski, 1991; Balmelle et al.,
1992). Recently, there have appeared several speculations that - especially concerning Nitrobacter - the
inhibition is not caused by NH3' but by the intermediate product hydroxylamine (NH20H) (Yang and
Alleman, 1992). Here also the non-dissociated form is supposed to be responsible. Further tests referring to
this remain to be reported.

If nitrification should be reduced to the fIrSt partial step (nitritation), the activity of the Nitrobacter must be
largely reduced and the Nitrosomonas must correspondingly gain growth advantages. In several tests with
continuously operated laboratories Nyhuis (1985) could prove that Nitrosomonas (NH4 � NOV and
Nitrobacter (N02 � N03 ) show different reactions on ammonia and nitric acid. The sensibility of
Nitrobacter vis-a.-vis ammonia is much bigger than the substrate inhibition of Nitrosomonas. Nyhuis found
for Nitrobacter an inhibition even from 1 mg/l NH3 onwards; over 10 mg/l there was no more growth.
Nitrosomonas was inhibited only at concentrations of 40 mg/l onwards. Theoretically, at an ammonia
concentration of 10 mg NHyt in the aerobic tank the nitratation should be completely inhibited, while the
nitritation happens at maximal rate. The tests described hereafter were carried out to fix the inhibition limits
in continuous operation, and above all to find out whether both processes can be completely decoupled.

EJij!!<rlmental units

Two plants had been operated in parallel each with one anoxic and one aerobic reactor. In the first plant a
complete nitrification/denitrification with nitrate had been carried out. The arrangement of the second plant
is shown in Figure 5. In the aerobic reactor the pH value was controlled by means of a NaOH dosage and
regulated to pH 8.2-8.4. Furthermore the content of ammonium was controlled by means of regulation of the
oxygen supply. The nitrification tanks in unit 2 were filled with plastic media (Fa. NSW AG) with a specific
surface of 150m2 /m3 . As residual concentrations of ammonium and nitrite occur due to this kind of system,
 172 U. ABELING and C. F. SEYFRIED

a secondary treatment reactor was unstalled for residual nitrification and nitratation. The pH value was
regulated here to pH 7.0-7.5. The dimensions of the plants and the operation parameters are listed in Table 4.

TABLE 4. Design and Operation Parameters

plant 1 p1 ant 2
nitrific. denitrific. nitritation
denitritation

volume [1] 300 224 380 340

Vdeni/Vtot [-] 0.43 0.47
flow [l/d] 96 120
recycle [%] 1,070 1,210
max. eff. of denio [%] 91.5 92.4
pH 7.4 7.6 8.3 8.5
temperature [DC] 20 20
sludge loading (oeni) 0.10 0.11
[kg BODS/kg MLSS·d ]

Denitrification Nitritation intermediate Nitratation

N02 .. N2. fixed film reactor settling tank fixed film reactor
NH4" N02 N02" N03

return sludge
�
r------------�--l
I Recycle
I
I I
I

,.-1-,
influent I \ effluent
t---+
effluent

\......_�I
=

Anaerobic
reactor

f-;L,,,!
, .
. --------------_ .
•

�t:::: :::
...
...

PC
-

Figure 5. Flow diagram of the pilot plant for nitritationlnitratation

Characterization of the wastewater

The anaerobic pilot plants were fed with pretreated wastewater from the potato starch production. The
anaerobic pretreatment was carried out so that extensively there was a lack of organic carbon for the
denitratation as well as for the denitritation. The average values of the concentrations in the inlet to as well
as in the outlet from the anaerobic pretreatment can be taken from Table 5.
 Potato-starch wastewater 173

TABLE 5. Chemical Characterization of Potato Starch Wastewater

COD BDD
S
organic TKN NH -N
4
N�-N Tot P SS BDD ITKN
S
CDD/TKN
acids
[mslll [-l [-l

ra.. wastewater 17,000 10,000 870 150 190 11.5 19.5

anaerobic effl. 1,600 700 500 820 730 10 180 1,000 0.85 1.95

CQntrol 2f the DitritaUIlD

Both plants were started with nitrifying sludge from the aerobic stage of the large-scale. The inhibition of
the nitritation was planned to be achieved in the second plant by increasing the pH value. According to the
basic research work by Anthonisen (1974), each of the non-ionized forms of the ammonium and of the
nitrite have - as ammonia (NH3) and as nitrous acid (HNOz) - an inhibition effect on the Nitrosomonas and
the Nitrobacter. The Nitrobacter react more sensitively so that the concentrations in the range O. I to 1.0 mg
NH� are sufficient for starting an inhibition. The dissociation balance for ammonium-ammonia is
dependent on the temperature and on the pH value (Fig. 4.). At the pH value of 8.3 and a temperature of
20DC, 7.3% of the ammonium are present as ammonia. A concentration of 20 mg/l NH4-NIl in the reactor
thus produces an ammonia concentration of 1.8 mg NH31l.

The adjustment of the pH value was effected by means of a computer controlled dosage of soda solution
(NaOH). The fluctuation range amounted to ± O. I pH. As the content of ammonia at a constant pH value is
dependent on the altitude of the ammonia concentration in the reactor, and as this fluctuated, a pH control
alone is not sufficient. At a total nitrification the ammonia concentration is equal to zero, anyhow, due to
lack of ammonium in the reactor. This is the reason why also the content of ammonium had been adjusted
by computer-controlled aeration in order to achieve a constant concentration of ammonia. The measurement
was carried out with the help of a continuous NH4 analyzer (Bran & Liibbe). The temperature remained
constant during the measurement phases, which is important because the inhibiting effect of decreasing
temperatures is greater for Nitrobacter than for Nitrosomonas (Randall and Buth, 1984). Hence, nitrite
accumulation is possible due to lack of temperature control.

Nitrification

Inboth plants a complete nitrification respectively, and nitritation at space loadings of 0.3 kg NH4-N/m 3.d
could be reached. Thus, nitrification by means of nitrite with equal COD value in the influent has no
advantages as far as the required nitrification volume is concerned, because the necessary sludge age is the
same in both cases. Anyway, there is need of only 75% of the oxygen for complete nitrification.

As ammonia in higher concentrations also has an inhibiting influence on Nitrosomonas, several tests were
carried out to fmd out the influence of ammonia concentration on nitritation rate. Figure 6 shows the results.
Contrary to other authors, who analyzed much higher inhibition limits, a reduction was stated of the
nitritation rate from 7 mg/l NH3 onwards (Hyhuis, 1985: 40-200 mg NH� Anthonisen, 1974: 10-150 mg
NH�). Neufeld (1980) also found the start of inhibition to be from 10 mg NH� onwards.
The curve of nitritation rate follows an enlarged Haldane function (Eq.1), which - in addition - considers
the HNOrconcentration as non-competitive inhibition.
 Potato-slarch wastewater 175

Nitrogen removal

Both pilot plants were operated under substrate limited conditions in order to guarantee a direct
comparability of denitrification results over nitrite and nitrate. Furthermore, the maximum possible
denitrification was limited to 92% by the recycle water quantity. To reach low nitrate effluent concentrations
at high influent concentrations, a simultaneous/intermitting denitrification process should be chosen.
Otherwise, a very high recycle rate is required.

In Table 6, the average results of nitrogen elimination over nitrite and nitrate are shown. It shows that by
means of nitrite a considerably higher elimination rate can be achieved. It must be take into account that
both processes were substrate-limited. With sufficient substrate supply, with plant 2 there can be achieved
effluent rates from about 60 mg N03-Nn (maximum possible value depending on recycle water quantity);
meanwhile in plant I at equal substrate supply the effluent concentration would be come up to 330 mg
N03-Nn.

TABLE 6. Results - Nitro!:en Remoyal - Ayera" values <April-June 1991)

influent effluent
plant plant 2
nitritation nitratation

COO [mg/l] 1,600 80.0 90.0 70.0

TKN [mg/l] 820 3.0 23.6 3.2
NH4-N [mg/l] 750 1.0 20.0 1.2
N0 2-N [mg/l] 0.5 21.6 0.6
r
NO N [mg/l] 10 348.0 63.4 102.3
ef ect of
N-elimination [%] 57.1 86.8 87.1
effect of
denitrification [%] 59.6 95.9
COOt NOx-N [-] 3.63 2.28
- 63 % of plant 1

As already mentioned, according to the results of the batch test, a complete decoupling of nitritation is not
possible (Figure 4). Anyway, the COD consumption in the process over nitrite compared to over nitrate
came to only 63% in the semi-technical tests, which means only a little margin to the 60% which is possible
by way of calculation (refer to Table 3). Therefore, a large separation may be supposed.

It was important to find out whether the improved elimination results of plant 2 were possibly due to strip­
effects in the activation; hence a balance-sheet of the basins was established. Independent of the pH value,
wrong amounts of ± 7% resulted from this (Abeling and Seyfried, 1992). Thus, considerable nitrogen
elimination by means of stripping of ammonia can be excluded.

CONCLUSIONS

The example of potato starch wastewater was showed that wastewaters with high nitrogen concentrations
and an unfavourable CODIN ratio < 3.5 can be completely cleaned and made operational with the
nitrification/denitrification process. 37% of the carbon can be saved, compared to the conventional nitrogen
elimination over nitrite. With the help of anaerobic pretreatment, this carbon can be transferred to methane,
which contributes to optimization of the anaerobic-aerobic process from an economical point of view. The
operating costs are reduced by about 20%, and in total there are lower investment costs (tank volumes,
sludge treatment, aeration).

In order to achieve low nitrate effluent concentrations at high nitrogen concentrations, a simultaneous
denitrificatiuon process is recommended. The process must be two-staged because oxidation of the
176 U. ABELINO and C. F. SEYFRIED

remaining nitrite and ammonia concentrations is required. The process is controlled by continuous pH value
and ammonium measurements.

As the pH value must be increased to 8-8.5, the process is suitable above all for wastewaters which are
located in this pH value range. On the one hand, often undesired nitrite upgradings appear which cause
considerable operation break-downs, but with a specific decoupling of nitritation from nitratation, this can
be avoided.

RFERENCES
Abeling, U. and Seyfried, C. F. (1992) Anaerobic-areobic treatment of high-strength ammonium wastewater - nitrogen removal
via nitrite. Wilt. Sci. Techn., 26, No. 5-6, 1007-1015
Anthonisen, A. C. (1974) The effects of the free ammonia and free nitrous acid on the nitrification process. Ph.D. Thesis, Cornell
University, Engineering, agriCUltural
Anthonisen, A. C., Loehr, R C., Prakasam, T. B. S. and Srinatu, E. O. (1976) Inhibition of nitrification by ammonia and nitrous
acid. J. Wat. Poilu!. Control. Fed., 48, 835-852
Austermann-Haun, U. (1990) Stiltkefabriken. Vortrag beim Lebrgang .. Abwasserbebandlung in der Erui1hrungs- und
Getrllnkeindustrie", Technische Akademie Esslingen, Ostfildern, 11JI2.10.1990
Beccari, M., Passino, R, Ramadori, R and Tandoi, V. (1983) Kinetics of dissimilatory nitrate and nitrite reduction in suspended
growth culture. J. Wat. Poilu!. Control Fed., 55, 58-64
Balmelle, B., Nguyen, K. M., Capdeville, B., Cornier, J. C. and Degiun, A. (1992) Study of factors controlling nitrite build-up in
biological processes for water nitrification. Wat. Sci. Techn., 26, No. 5-6, 1017-1025
Bergeron, P. (1978) Untersuchungen zur Kinetik der Nitriflkation. Karlsruher Berichte zur Ingenieurbiologie, Heft 12
Chen, S. K., Juaw, C. K. and Cheng, S. S. (1991) Nitrification and denitrification of high-strength ammonium and nitrite
wastewater with biofilm reactors. Wat. Sci. Tech., 23, No. 1-3, 1417-1425
Dombrowski, T. (1991) Kinetik der Nitrif1kation und Reaktionstecbnik der Stickstoffeliminierung aus hochbeIasteten Abwllssern.
Forschungsberichte VD!, Reihe 15, Nr. 87, VOl-Verlag Diisseldorf
Nanninga, H. J. and Gottschal, J. C. (1986) Anaerobic purification of wastewater from a potato-starch producing factory. Water
Res., 20, 97-103
Neufeld, R. D., Hill, A. J. and Adekoya, D. O. (1980) Phenol and free ammonia inhibition to Nitrosomonas avtivity. Wat. Res., 14,
1695-1703
Nyhnis, O. (1985) Beitrag zu den MOglichkeiten der Abwasserbehandlung bei Abwllssem mit erMhten Stickstoffkonzentrationen.
Verliffentlichungen des Institutes /fir Siedlungswasserwirtschaft und Abfalltechnik, University Hannover, FRG, 61,
Randall, C. W. and Buth, D. (1984) Nitrite build-up in activated sludge resulting from temperature effects. J. Wat. Pollut. Control
Fed., 56, 1039-1044
Seyfried, C. F. and Austermann-Haun, U. (1990) Large scale anaerobic/aerobic treatment plants for wastewaters from a molasses
distillery, pectin-factory and waste of starch factories. Wat. Sci. Techn., 22, No. In, 353-360
Tunmermans, P. and Van Haute, A. (1983) Denitrification with methanol. Hyphomicrobrium sp. Wat. Res., 17, 1249-1255
Van Versefeld, H. W., Meijer, E. M. and Stouthamer, A. H. (1977) Energy conservation during nitrate respiration in Paracoccus
denitrificans. Arch Microbiol., 112, 17-23
Yang, L. and Alleman, J. E. (1992) Investigation of batchwise nitrite build-up by enriched nitrification culture. Wat. Sci. Techn.
26, No. 5-6, 997-1005
Reproduced with permission of copyright
owner. Further reproduction prohibited
without permission.
3300 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308

known amount of piggery wastewater was added in the
reactor through a buffer tank where the quantity added
was weighed and recorded. The reactor was equipped with
a foam breaker working during the aerobic phases and a
fine bubbles diffuser fed with a compressor (2–5 m3 h1).
For the mixing, a centrifugal pump (30 m3 h1) circulated
the reactor reached steady-state conditions (after more
than three hydraulic residence times), the characterisation
of the effluent was done (COD, soluble COD and total
nitrogen) and was followed by a study of the evolution
of NHþ  
4 , NO2 and NO3 in the reactor, during one
cycle.

at 4 C and was used for this experiment. For this run, NH4  N (or SNH), kg N m 3.0 (0.1) 3.4 (0.1)
the duration of a whole-cycle was equal to 24 h consisting NO 2  N (or SNOI), kg N m
3
0 0
NO  N (or S NOA), kg N m 3
0 0
of 4 h of anoxic conditions and 20 h of aerobic conditions. 3
TN–N, kg N m3 4.6 (0.1) 4.3 (0.05)
At the beginning of each cycle, 10 l of PW1 were added SS, kg O2 m3 5.2 (0.5) 6.0 (1.0)
in the reactor, leading to a working volume of 110 l and XS, kg O2 m3 14.1 (3.6) 23.9 (1.4)
a HRT equal to 11 days. At the end of each cycle the Inert COD, kg O2 m3 31.3 (3.4) 9.5 (1.4)
same amount of activated sludge was withdrawn. When Standard errors shown in parenthesis, n = 5.

Table 1
Summary of the conditions during the three experiments carried out with the pilot-scale modified SBR
Runs PW HRT (days) P1 (h) P2 (h) P3 (h) P4 (h) Observations
1 1 11.0 0.1 3.9 19.9 0.1 Effluent characterisation and study of a cycle
2 1 11.0 0.1 3.9 19.9 0.1 Study of a cycle (ammonium carbonate was added)
3 2 11.9 0.1 6.9 4.9 0.1 Effluent characterisation and study of a cycle
PW: piggery wastewater, P1: feeding phase, P2: anoxic phase, P3: aerobic phase, P4: withdrawal phase.
3308 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308
treatment using sequencing batch reactors. Water Res. 38, 3340–
3348.
Lee, S.M., Jung, J.Y., Chung, Y.C., 2000. Measurement of ammonia
inhibition of microbial activity in biological wastewater treatment
process using dehydrogenase assay. Biotechnol. Lett. 22, 991–994.
Nielsen, P.H., 1996. Adsorption of ammonium to activated sludge. Water
Res. 30 (3), 762–764.
Oh, J., Silverstein, J., 1999. Acetate limitation and nitrite accumulation
during denitrification. J. Environ. Eng. ASCE 125 (3), 234–242.
Orhon, D., 1998. Evaluation of industrial biological treatment design on
the basis of process modelling. Water Sci. Technol. 38 (4–5), 1–8.
Orhon, D., Okutman, D., 2003. Respirometric assessment of residual organic
matter for domestic sewage. Enzyme Microb. Tech. 32 (5), 560–566.
Orhon, D., Sozen, S., Artan, N., 1996. The effect of heterotrophic yield on
the assessment of the correction factor for anoxic growth. Water Sci.
Technol. 34 (5–6), 67–74.
Peu, P., Béline, F., Martinez, J., 2004. Volatile fatty acids analysis from
pig slurry using high performance liquid chromatography. Int. J.
Environ. An. Ch. 84 (13), 1017–1022.
Sollfrank, U., Gujer, W., 1991. Characterisation of domestic wastewater
for mathematical modelling of the activated sludge process. Water Sci.
Technol. 23, 1057–1066.
Villaverde, S., Fdz-Polanco, F., Garcia, P.A., 2000. Nitrifying biofilm
acclimatation to free ammonia in submerged biofilters: start-up
influence. Water Res. 34, 602–610.
Wiesmann, U., 1994. Biological nitrogen removal from wastewater.
Adv. Biochem. Eng. Biot. 51, 113–154.
Wilderer, P.A., Jones, W.L., Dau, U., 1987. Competition in denitrification
systems affecting reduction rate and accumulation of nitrite. Water
Res. 21, 239–245.
170 U. ABELING and C. F. SEYFRIED

TABLE 3. Operatinl: Results (Ayeral:inl: values 1988-1990.

INFLUENT AEROBIC STAGE EFFLUENT

anaerobic stage wash-water and
influent effluent domestic wastew.
mg/l mg/l mg/l mg/l

COD 16,000 - 18,000 5,000 - 10,000 1,400 80 - 140

BODS 10,700 - 12,000 2,000 - 5,000 700 5 - 15

In spite of the high loads from the anaerobic plant, until now a complete nitrification as well as large
reduction of the carbon compounds could be achieved. For the denitrification and the biological phosphorus
elimination (the sludge contact serves as anaerobic basin) the bad elimination rate of the anaerobic stage has
a positive effect, especially by the high content of organic acids.

As the insufficient anaerobic elimination rate must be improved for economical reasons (high energy
consumption and increased surplus sludge production in the aerobic stage), optimization of the
denitrification potential was indispensable. Thus, the process of nitrogen elimination by means of nitrate was
developed.

NITROGEN REMOVAL VIA NITRITE

Nitrification happens in two partial steps, i.e. nitritation (oxidation from ammonium to nitrite by
Nitrosomonas a.o.) and nitratation (oxidation from nitrite to nitrate by Nictobacter a.o.). Both organism
groups are aerobic and need CO2 as carbon source. They are characterized by low growth rates, high
sensibility to pH values and temperature deviations as well as toxic substances. Furthermore, there are
inhibitions because of the substrates ammonium and nitrite. In this respect, the substrate inhibition with
Haldane kinetics can be clearly described, where the non-dissociate forms, i.e. ammonia and nitric acid,
serves as substrates.

In practice, the product inhibition of Nitrosomonas is very important. It seems that inhibition of
Nitrosomonas by nitric acid can be described as non-competitive inhibition. Especially upon start-up of a
plant or appearance of load peaks, there are higher nitrite concentrations. A certain percentage comes out as
nitric acid, depending on temperature and pH value (Figure 4). Nitric acid then causes inhibition of the
Nitrosomonas, so that concentration of ammonium, respectively ammonia, increases. On the one hand,
ammonia can release a substrate inhibition of Nitrosomonas, on the other hand, it can start a non-competitve
inhibiton of Nitrobacter. In bad conditions, there may be a complete breakdown of nitrification.
 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308 3307

Appendix (continued)
Symbol Definition Default Run 1 Run 2 Run 3 Ref.
value
fp Fraction of biomass leading to inert 0.08 – – – Henze et al. (2000)
3308 F. Béline et al. / Bioresource Technology 98 (2007) 3298–3308
treatment using sequencing batch reactors. Water Res. 38, 3340–
3348.
Lee, S.M., Jung, J.Y., Chung, Y.C., 2000. Measurement of ammonia
inhibition of microbial activity in biological wastewater treatment
process using dehydrogenase assay. Biotechnol. Lett. 22, 991–994.
Nielsen, P.H., 1996. Adsorption of ammonium to activated sludge. Water
Res. 30 (3), 762–764.
Oh, J., Silverstein, J., 1999. Acetate limitation and nitrite accumulation
during denitrification. J. Environ. Eng. ASCE 125 (3), 234–242.
Orhon, D., 1998. Evaluation of industrial biological treatment design on
the basis of process modelling. Water Sci. Technol. 38 (4–5), 1–8.
Orhon, D., Okutman, D., 2003. Respirometric assessment of residual organic
matter for domestic sewage. Enzyme Microb. Tech. 32 (5), 560–566.
Orhon, D., Sozen, S., Artan, N., 1996. The effect of heterotrophic yield on
the assessment of the correction factor for anoxic growth. Water Sci.
Technol. 34 (5–6), 67–74.
Peu, P., Béline, F., Martinez, J., 2004. Volatile fatty acids analysis from
pig slurry using high performance liquid chromatography. Int. J.
Environ. An. Ch. 84 (13), 1017–1022.
Sollfrank, U., Gujer, W., 1991. Characterisation of domestic wastewater
for mathematical modelling of the activated sludge process. Water Sci.
Technol. 23, 1057–1066.
Villaverde, S., Fdz-Polanco, F., Garcia, P.A., 2000. Nitrifying biofilm
acclimatation to free ammonia in submerged biofilters: start-up
influence. Water Res. 34, 602–610.
Wiesmann, U., 1994. Biological nitrogen removal from wastewater.
Adv. Biochem. Eng. Biot. 51, 113–154.
Wilderer, P.A., Jones, W.L., Dau, U., 1987. Competition in denitrification
systems affecting reduction rate and accumulation of nitrite. Water
Res. 21, 239–245.