Journal of Membrane Science 344 (2009) 39–54

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Hybrid membrane bioreactor technology for small water treatment utilities:

Process evaluation and primordial considerations
Varadarajan Ravindran, Hsun-Hao Tsai, Mark D. Williams 1 , Massoud Pirbazari ∗
Department of Civil and Environmental Engineering, Viterbi School of Engineering, University of Southern California, 3620 S. Vermont Avenue, Kaprielian Hall (KAP) 260,
Los Angeles, CA 90089-2531, USA

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

Article history: A hybrid membrane bioreactor (MBR) technology was investigated for treatment of natural waters
Received 22 April 2009 containing natural organic matter (NOM), nitrate, alachlor and viruses. The NOM are precursors to
Received in revised form 9 July 2009 disinfection byproducts (DBPs) such as trihalomethanes, and potential cause for microbial growth in
Accepted 20 July 2009
distribution systems. Batch bioreactor studies optimized the carbon-to-nitrogen (C/N) ratio, tempera-
Available online 28 July 2009
ture and pH for biological denitrification. Mini-pilot MBR studies with ethanol as electron donor were
conducted under three scenarios: no powder activated carbon (PAC) or biomass, biomass alone, and com-
Keywords:
bination of PAC and biomass. The removals of nitrate, alachlor, total organic carbon (TOC), trihalomethane
Hybrid membrane bioreactor
Nitrate
formation potential (THMFP) and MS-2 virus were revaluated. Nitrite and ethanol residuals were well
Alachlor below their detection limits in the MBR effluent under steady-state conditions. Using biomass alone, the
Natural organic matter removal efficiencies for NOM (as TOC), alachlor, and THMFP were 60, 36 and 61%, respectively; whereas,
Membrane fouling on combining PAC and biomass they increased to 84, 99.8 and 98%. The virus rejection mechanisms pos-
Disinfection byproducts tulated were size exclusion, sorption to membrane surface, attachment to bio-particles, and sorption
Microbial regrowth onto foulant or cake layers. The MS-2 removals exceeded 3.8-logs under optimal process conditions.
Trihalomethane formation potential Membrane fouling and flux decline patterns under the three experimental scenarios were well described
MS-2 virus
by the resistance model. The flux decline was characterized by three distinct stages, namely, initial con-
ditioning fouling, rapid fouling, and slow fouling. The Tustin groundwater was associated with lower
organic fouling but higher inorganic fouling than the Fountain Valley groundwater.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction

Problems in drinking water supplies are often attributed to

Abbreviations: AOC, assimilable organic carbon; ATCC, American type cul-
ture collection; BDOC, biodegradable dissolved organic carbon; BOC, biodegradable
organic carbon; BOM, biodegradable organic matter; BOD, biochemical oxygen
demand; DBP, disinfection byproduct; DO, dissolved oxygen; DOC, dissolved
organic carbon; DOM, dissolved organic matter; EPS, exo-polymeric substances;
FVGW, Fountain Valley groundwater; GAC, granular activated carbon; GC-MS, gas
chromatography-mass spectrometry; GC-ECD, gas chromatography with electron
capture detector; GC-FID, gas chromatography with flame ionization detector;
HAA, haloacetic acid; HAN, haloacetonitrile; MAC, maximum acceptable concentra-
tion; MBR, membrane bioreactor; MCL, maximum contaminant level; MLSS, mixed
liquor suspended solids; MS-2, male specific species 2 virus strain; NOM, natural
organic matter; PAC, powdered activated carbon; PFU, plaque formation unit; PP,
polypropylene; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; SDR, specific
denitrification rate; SMP, soluble microbial product; SOC, synthetic organic chemi-
cal; SRT, solid retention time; TDS, total dissolved solids; TGW, Tustin groundwater;
THM, trihalomethane; THMFP, trihalomethane formation potential; TMP, trans-
membrane pressure; TOC, total organic carbon; USEPA, United States Environmental
Protection Agency; UV254 , ultraviolet absorbance measured at 254 nm.
∗ Corresponding author. Tel.: +1 213 740 0592; fax: +1 213 744 1426.
E-mail address: pirbazar@usc.edu (M. Pirbazari).
1
Mark Williams is currently the President of McCaron-Williams, Inc., Consulting
Engineers, Long Beach, California. At the time of research he was an engineer with
the Metropolitan Water District of Southern California, La Verne, California 91750,
and also doctoral candidate at the University of Southern California.
contaminants in ground and surface waters. The most common
contaminants associated with these problems include the follow-
ing: synthetic organic chemicals (SOCs) exemplified by pesticides,
herbicides, industrial solvents and chemicals; inorganic pollutants
such as nitrate, arsenic and toxic metals; natural organic matter
(NOM) such as taste and odor causing compounds, and disin-
fection byproduct (DBP) precursors measured as total organic
carbon (TOC); and microorganisms such as protozoa, bacteria and
viruses. In recent years, the United States Environmental Protection
Agency (USEPA) has intensely regulated the water supply indus-
try for controlling organic and inorganic contaminants, pathogenic
microorganisms, and DBP formation after disinfection by chlorina-
tion or advanced oxidation processes. The new Enhanced Surface
Water Treatment Rule and the Disinfectant/Disinfection Byprod-
uct Rule mandate lower allowable levels of selected DBPs, and over
4-logs reductions in virus concentrations [1,2]. It must be noted
that NOM removal from natural waters has several advantages
including reduction in undesirable DBPs such as trihalomethanes
(THMs) and haloacetic acids (HAAs) during chlorination, and con-
trol of microbial regrowth in distribution systems attributable to

0376-7388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2009.07.032
40 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
biodegradable organic matter (BOM) [3–6]. Integrated membrane
technologies such as the hybrid membrane bioreactor (MBR) pro-
cess would be effective in providing finished water safe from
microbial pathogens, low in DBP precursors, and free from harm-
ful organic or inorganic contaminants. Furthermore, MBR systems
using ultrafiltration or microfiltration membranes with bioactive
powder activated carbon (PAC) could achieve high contaminant
removals, and simultaneous control of membrane fouling and flux
decline.
The present work evaluates the hybrid MBR process as a viable
water purification technology for removing inorganics such as
nitrate, organics such as alachlor, NOM (TOC) that could lead to
DBP formation and microbial growth, and pathogens exemplified
by viruses. Mini-pilot-scale MBR investigations were conducted
under different process conditions to investigate the removal effi-
ciencies of target contaminants, namely, nitrate, TOC, alachlor,
trihalomethane formation potential (THMFP), and viruses. The
bacteriophage MS-2 (male specific type 2 virus) was used as an
indicator and model organism to evaluate virus removals. The MBR
tests also investigated membrane fouling and permeate flux decline
as functions of operation time under three operational scenarios:
(i) no biomass or PAC (control), (ii) biomass only without PAC,
and (iii) biomass with PAC. These scenarios were chosen to obtain
information on the relative contributions of adsorption, biodegra-
dation and membrane separation towards contaminant removals.
Furthermore, permeate flux decline patterns under these scenarios
could shed light on the nature of membrane fouling for developing
appropriate control strategies.
2. Background information
2.1. Applications of membrane bioreactor processes
The MBR process is more typically associated with wastewater
treatment than water treatment because it effectively integrates a
suspended growth biomass similar to that in traditional activated
sludge process with a membrane system that replaces sedimenta-
tion systems but effectively retains biomass and clarifies the treated
effluent. Recently, the technology appears more promising for
water treatment owing to significant declines in membrane costs,
and dramatic reductions in fixed costs and operating expenses.
The MBR systems offer several advantages over activated sludge
and fixed biofilm processes generally used for biological treatment,
including the following: small reactor sizes or footprints, suitability
for water reclamation and reuse, and ability to retain most par-
ticulate and colloidal matter. Furthermore, the treated effluent is
low in total suspended solids, turbidity levels, biochemical oxygen
demand (BOD), total organic carbon (TOC), and most pathogens.
The membrane filter retains all the biomass leading to performance
enhancement of “slow growing” microorganisms with low yield
factors. In wastewater treatment applications, enhanced biomass
retention leads to high mixed liquor suspended solids (MLSS) lev-
els of 10–20 g/L in MBR systems versus the low levels of 3–4 g/L
in typical activated sludge or other biological treatment systems.
In addition to allowing long solids retention times (SRTs), high
biomass concentrations lead to reduction in reactor sizes. More
importantly, modern, programmable logic control systems have
made MBR systems compact, efficient, economical and versatile
not only for wastewater treatment and water reclamation, but also
for drinking water treatment.
The MBR technology is more widely employed in wastewater
treatment, water reclamation and water reuse scenarios owing to
good retention of microbial biomass and electron donors. Several
electron donors have been employed for biological denitrification
including acetic acid [7], methanol [8], ethanol [9,10], hydrogen
[11] and sulfur [12], specially designed to promote the necessary
heterotrophic or autotrophic conditions. However, water treat-
ment and water reclamation represent a completely different
scenario due to low microbial biomass and electron donor levels.
The MBR effectively replaces a conventional activated sludge pro-
cess in which microbial biomass concentrations are on the order of
3000–20,000 mg/L, while electron donors and contaminants are in
the levels of 100–2500 mg/L. Additionally, biofilm thickness must
be specifically tailored to optimize the process efficiencies. Nev-
ertheless, in water treatment situations, the target contaminants
(organic or inorganic) are generally at the 1–100 mg/L levels, while
microbial biomass requirements are in the 40–400 mg/L range
[6,8,10]. In fact, low concentrations of electron donors such as NOM
or other constituents are often able to sustain low levels of micro-
bial populations associated with thin biofilms. Some advantages of
the MBR technology over conventional processes that are experi-
enced in wastewater treatment can be realized in water treatment
as well.
In water supplies NOM present several problems including bac-
terial growth in distribution systems, formation of DBPs during
chlorination, and permeate flux decline in membrane processes
due to membrane fouling. Bacterial growth in distribution systems
is attributed to NOM constituting assimilable organic carbon (AOC)
or biodegradable organic matter (BOM), the natural substrates for
microbial growth and sustenance [3–5]. More recently, Williams
and Pirbazari [6] demonstrated that hybrid MBR processes could
efficiently control DBP formation and bacterial regrowth. Further-
more, these investigators demonstrated that MBR systems using
bioactive PAC could reduce NOM and BOM levels and amelio-
rate membrane fouling and permeate flux decline. Other studies
showed that the technology could achieve high treatment levels
for waters contaminated with petroleum hydrocarbons [13], and
nitrate [10]. An important feature of the hybrid MBR technology
is the effective control of membrane fouling and permeate flux
decline by a combination of PAC sorption and fluid management.
2.2. Removals of NOM, TOC and DBP precursors from water
supplies
The NOM in potable water supplies are mostly attributed to bio-
logical degradation of organic substances such as amino acids, fatty
acids, phenols, steroids, sugars, hydrocarbons, urea, porphyrines
and organic polymers such as polypeptides, lipids, polysaccharides,
and humic substances. The NOM levels in drinking water sources
are usually 2–10 mg/L (as TOC), although much higher levels are
sometimes reported [14]. Humic substances are the most signif-
icant among NOM constituents because they can yield over 300
different types of DBPs during chlorination, many of which raise
public health concerns such as THMs, HAAs, and haloacetonitriles
(HANs) [14]. Although the regulated MCLs for THMs and HAAs are
80 and 60 ␮g/L, future standards would lower these limits to 40 and
30 ␮g/L, respectively [1,2,6]. The present study investigates nat-
ural waters from two sources: the Fountain Valley groundwater
(FVGW), and the Tustin groundwater (TGW). The FVGW has aver-
age NOM levels of 3.5–4.0 mg/L (as TOC) with THMFP levels around
350 ␮g/L which was well above the MCL; and therefore, removal
of THM precursors shall be required before chlorination. The TGW
has a low NOM level of less than 0.1 mg/L as TOC, and therefore its
THMFP is not of much concern. A major objective of the present
study is to control the DBP formation potential by removing NOM
that are well recognized as DBP precursors. Physico-chemical pro-
cesses including coagulation, physical settling, deep bed filtration,
or membrane processes achieve relatively low removals of DBP
precursors [14,15]. Reverse osmosis and nanofiltration are energy
intensive membrane processes, while ultrafiltration is not cost-
effective. Microfiltration, however, can be economical but cannot
 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
reliably remove NOM and DPB precursors as it only rejects certain
NOM fractions [5]. In comparison, a hybrid MBR process employing
microfiltration and bioactive PAC could effectively remove a broad
spectrum of SOCs, most NOM fractions and DBP precursors [6].
2.3. Removals of nitrate and alachlor from water supplies
Several studies have indicated that nitrate contamination of
potable waters has serious public health implications, notably,
methemoglobinemia (“blue-baby” syndrome) and various forms of
cancer [9]. Croen et al. [16] studied exposures of women to nitrate
in drinking water and examined health risks associated with neural
tube defects. Weyer et al. [17] articulated that nitrate levels in water
supplies as low as 10 mg/L caused bladder cancer in elderly women
in Iowa. The USEPA set MCLs for nitrate as nitrogen (NO3 − -N) and
nitrite as nitrogen (NO2 − -N) of 10 and 1 mg/L [10], respectively; the
Ministry of Environment for Canada established the same standards
for the maximum acceptable concentrations (MACs) of nitrate and
nitrite [18]; and the European Union set more stringent limits of
10 and 0.03 mg/L [10–19]. Nitrate removal technologies include ion
exchange, reverse osmosis, and electrodialysis, besides biological,
chemical and catalytic denitrification [20]. Nevertheless, MBR pro-
cesses could be more economical and efficient for nitrate removal
as established by several studies [7,10,21–23].
Alachlor or 2-chloro-2 ,6 -diethyl-N-(methoxymethyl)-
acetanilide has been the most commonly used pre-emergence
crop herbicide in Europe, North America and Japan; and in fact,
its residues have been detected in ground and surface waters at
levels of 0.1–10 ␮g/L [24]. It is classified as a B-2 carcinogen and
suspected endocrine disruptor [25,26], and the toxicity levels of
many of its degradation products and metabolites are unclear
[24,27]. The World Health Organization has recommended an MCL
of 20 ␮g/L for alachlor in drinking water supplies, while the USEPA
has set a lower MCL of 2 ␮g/L [28]. Several researchers evaluated
conventional processes for alachlor removal from potable water
supplies. Miltner et al. [29] stated that chemical coagulation, floc-
culation and sedimentation in a full-scale plant were inefficient;
whereas clarification, filtration, softening, recarbonation, and
chlorination achieved low removals. Nanofiltration and reverse
osmosis were effective but too expensive in energy requirements.
Pirbazari et al. [30] observed that non-bioactive granular activated
carbon (GAC) adsorbers were effective but expensive owing to
short operational life spans. Nevertheless, Badriyha et al. [24]
noted that bioactive GAC adsorbers were more economical and
efficient for removing alachlor and other SOCs, a major factor
behind the use of a hybrid MBR process with bioactive PAC.
2.4. Mechanisms for virus removals in membrane processes
The MBR system can exclude a broad spectrum of pathogenic
microorganisms such as protozoa and bacteria, besides viruses that
are the most difficult to remove [31,32]. Owing to difficulties expe-
rienced in assaying animal viruses, bacteriophages such as MS-2
are suggested as viral indicators. This is because bacteriophages
exemplified by MS-2 have similarities with enteric strains such as
hepatitis A and polio viruses in structure, morphology, size and
behavior, and find application in most water pollution control and
public health studies [33]. The rationale behind choosing MS-2 as
model virus is predicated upon the fact that it is one of the smallest
strains (20–25 nm in size), and that its rejection generally ensures
exclusion of larger strains.
Membrane rejection mechanisms for viruses are important from
the standpoint of MBR process design. Although viruses are gen-
erally smaller than the pores of microfiltration membranes, some
researchers have observed their high removals after biofilm for-
mation [34,35]. Shang et al. [36] concluded from their bench-scale
41
studies that of MS-2 removals occurred through three important
steps: physical filtration by the membrane itself, biomass activ-
ity in the bioreactor, and biofilm filtration on membrane surface.
Zheng and Liu [31,32] employed MBR processes equipped with
polyvinylidene fluoride (PVDF) and polypropylene (PP) membranes
with pore sizes 0.22 and 0.1 ␮m, respectively, and observed good
rejections even for virus strains smaller than the membrane pores.
They hypothesized that a dynamic layer was formed on the mem-
brane surface as well as in the pores in two stages: the initial pore
fouling or pore blocking stage, and subsequent cake and gel forma-
tion stage arising from biofilm growth. They noted that the dynamic
cake and gel layers often enhanced virus screening, although their
formations were considerably reduced under turbulent conditions.
They further observed that internal pore fouling due to organic
gel deposition or sorption contributed to pore constriction and
promotion of virus screening. Zheng and Liu [32] suggested that
virus rejections by new membranes were initially controlled by
their sieving ability, but after a few hours of operation was mainly
influenced by the formation of a dynamic foulant layer. Addition-
ally, they noted that extra-cellular polymeric substances (EPS) on
biofilms enhanced microbial attachment to membranes. They fur-
ther demonstrated that chemical cleaning of membranes reduced
rejections of T4 virus due to breakages and losses of cake and
gel layers. They concluded that cake filtration contributed to virus
rejection significantly more than membrane screening or gel layer
rejection.
3. Membrane fouling and permeate flux decline
3.1. Fouling in the membrane bioreactor processes
The hybrid MBR process discussed here integrates membrane
filtration, activated carbon adsorption and microbial degradation,
as shown in Fig. 1 (detailed description is presented in a later
section). A major factor affecting process performance and eco-
nomics is membrane fouling and permeate flux decline. Factors
influencing membrane fouling include biomass, colloids, NOM,
inorganic precipitates or scalants, and extracellular polymers, and
they are dependent upon operating conditions. Membrane fouling
is a complex phenomenon, and its predominant causes can be sum-
marized are as follows: (i) Macromolecular and colloidal sorption,
(ii) biofilm growth and attachment; (iii) inorganic matter precipita-
tion or scaling; and (iv) general material aging. Membrane fouling
can be further classified as follows: (a) reversible fouling that can
Fig. 1. Schematic diagram of the hybrid MBR system.
42 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
be removed by physical cleaning; (b) irreversible fouling that can
be removed by chemical cleaning; and (c) irrecoverable fouling
that cannot be removed by any cleaning [37]. Membrane fouling
can be strategically controlled by concentration polarization sup-
pression, optimization of physical and chemical cleaning protocols,
pre-treatment of feed wastewater, and modification of biologi-
cal content [37]. Concentration polarization can be reduced either
by turbulence promotion or permeate flux reduction. Side-stream
MBR processes provide shear through pumping which increases
cross-flow velocity, whereas immersed processes employ aeration
around the membrane to provide shear stresses.
Several components of the MBR system can contribute to mem-
brane fouling including sorption onto and within membrane pores,
and deposition of cake layer or gel layer on the external membrane
surface. Nonetheless, the best approach for problem analysis and
identification of fouling mechanisms is to investigate classical foul-
ing models, as discussed by Ho and Zydney [38–40]. These include
the standard pore blockage model, the intermediate pore blockage
model, the pore constriction model, and the cake filtration model. In
the complete pore blockage model, the volumetric permeate flow
rate is assumed to decline as the effective membrane area available
for filtration decreases. The cake formation is considered negligi-
ble, and the pore blockage rate is proportional to convective flow
of foulants. The intermediate pore blockage model accounts for the
possibility that certain particles land on top of other particles dur-
ing deposition on membrane surfaces, and assumes pore blockage
to be proportional to the uncovered membrane area. Further, multi-
layer sorption of foulants is important because it would not lead to
further reduction in the permeate flow. In the cake filtration model,
a uniform deposit of cake or gel is assumed to form on the mem-
brane surface. The rate of increase in hydraulic resistance of the
deposit is assumed to be directly proportional to the rate of particle
convection to the membrane.
In MBR systems, membrane fouling could be caused by EPS
that are heterogeneous macromolecules found outside micro-
bial cells. The EPS predominantly contain carbohydrates, proteins,
humic substances and nucleic acids. They constitute the primary
infra-structure for biofilms and bacterial flocs, provide mechani-
cal stability for cell structures, and facilitate biofilm adhesion to
surfaces [37]. They can be generated by cell lysis, active excretion
by microorganisms, spontaneous production of integral cellular
components from the outer membrane of gram-negative bacteria,
and hydrolysis of NOM present in feed waters [37]. Their domi-
nant components are polysaccharides and certain proteins, and so
they can potentially develop foulant gel layers and severely restrict
membrane transport. Another group of biological substances are
soluble ESP that are soluble metabolic products (SMPs) or soluble
microbial products arising from biodegradation of organic materi-
als. The chemical composition and molecular weight distribution
of EPS depend upon the properties of feed water, microbial species
distribution and environment, nutritional status of bioreactors, and
certain operating parameters that influence EPS formation such as
substrate composition, organic loading, and solids retention time
[37].
Permeate flux decline in MBR systems can be caused by bio-
logical and organic fouling attributed to proteins, polysaccharides
and various NOM [38–40]. The fouling behavior can be explained
by the combinatorial model of Ho and Zydney [40] involving
both pore blockage and cake filtration. This model assumes that
foulants are at first deposited on bare membrane surfaces, reduc-
ing the area available for unhindered permeate flow. The initial
deposits allow partial fluid flow, while a small fraction of the
flow occurs through blocked pores. Subsequently, more membrane
fouling occurs and the foulant species accumulate on the origi-
nal layer, progressively increasing the hydraulic resistance. The
fouling process indeed becomes more complex in the presence
of NOM, PAC, biomass and exo-polymeric enzymes. Nystrom et
al. [41] observed that positively charged inorganic membranes
were easily fouled by negatively charged humic molecules due
to electrostatic interaction. Yuan et al. [42] observed rapid initial
fouling of microfiltration membranes due to electrostatic interac-
tions between humic molecules and membrane surface, but also
noted that deposition ceased when permeate flux dropped below
the critical flux. They further stated that cessation in the growth
of the cake or gel layer could arise from back-transport of humic
molecules from membrane surfaces either due to inertial lift or
shear-induced diffusion induced by fluid mechanical effects, or
from intermolecular electrostatic interactions pertaining to PAC
sorption. When the MBR system with a cross-flow membrane mod-
ule is operated with some fluid turbulence (Reynolds numbers of
14,000 to 15,000) using PAC sorbent, it facilitates membrane back-
transport of organic or inorganic species, and mitigates membrane
fouling.
The MBR systems are generally operated under constant flux
conditions. Since fouling rates often increase exponentially with
the permeate flux, MBR plants using microfiltration or ultrafiltra-
tion operate at modest fluxes below the so-called “critical flux”
defined as the highest flux under which a prolonged filtration with
constant permeability is possible. It is widely accepted as an oper-
ating guide that below this critical value, permeability decline does
not occur with time, and above this flux level membrane fouling
occurs rapidly. However, several researchers have shown that foul-
ing could be encountered even under sub-critical flux conditions
[43–46]. Zhang et al. [46] observed that sub-critical fouling under
wastewater treatment conditions was characterized by three dis-
tinct stages: (i) initial conditioning fouling occurring during the first
exposure of the membrane to the liquid phase; (ii) slow fouling
and flux deterioration under constant trans-membrane pressure
(TMP); and (iii) rapid fouling leading to more flux decline under
constant TMP, or to a sudden TMP jump under constant flux. The
first stage or initial conditioning fouling was rapid (measured in
hours), irreversible by nature, and prevalent under low flux or “zero
flux” conditions. The second stage or “slow fouling” phase involved
gradual coverage of the membrane surface by biopolymers such as
EPS [46]. This coverage resulted in changes in membrane surface
properties, promoting microbial attachment and growth. The pore
blocking was expected to be inhomogeneous since the air and the
liquid flow were distributed unevenly in MBR. Zhang et al. [46] also
noted that within the regions of membrane surface more fouled
than others, the flux varied locally, exceeding the critical flux in
some areas, and leading to a sudden jump in TMP. They stated that
changes in cake properties due to compression could also cause
this sudden jump in TMP. Some distinct pattern of flux decline
was expected in the present study wherein the MBR system was
employed for water treatment and the foulants included micro-
bial biomass, PAC sorbent, NOM constituents (including EPS and
microbial enzymes) and SMP components.
Membrane fouling in MBR systems described herein is mainly
attributable to particulate, organic and biological fouling with inor-
ganic fouling deemed relatively insignificant. Most organic and
biological foulants are typically in the molecular weight range of
500–2000 Da, although humic acids and exo-polymeric enzymes
could be in the range of 2000–500,000 Da [37–40]. The complex
composition of NOM makes evaluation of organic fouling mem-
brane processes more difficult. In general, biological fouling leading
to severe losses in permeate fluxes is often attributed to BOM and
EPS. Particulate fouling due to colloidal and biomass deposits can
be eliminated by mechanical and chemical cleaning with substan-
tial flux recoveries. However, internal pore fouling due to gel and
organic or bio-organic sorption, cannot be reduced by mechani-
cal cleaning, and in some cases can only be mitigated by chemical
cleaning. Nonetheless, even intense chemical cleaning cannot com-
 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
pletely eliminate internal pore fouling, and therefore only partial
flux recovery is realizable.
3.2. Membrane fouling models and permeate flux decline patterns
A conceptual rendering of a PAC–biomass layer formed on the
surface of a tubular cross-flow membrane is shown in Fig. 2. The
TMP applied across the membrane is on the order of 10–25 psia
(0.7–1.8 bars). A combination of a PAC–biomass layer progressively
forms a dynamic cake on the membrane surface (membrane film
thickness ranges from 5 to 50 ␮m) as shown in the figure. The scan-
ning electron micrograph on the inset illustrates the morphology
of the PAC–biomass cake formed on the membrane surface. The
schematic of permeate transport through the cake layer and the
membrane also highlights the qualitative nature of concentration
profiles for electron donor and target contaminant (organic or inor-
ganic) in the membrane vicinity. The concentrations of the electron
donor and the target contaminant(s) are represented by the nota-
tions Ce and Cc , respectively, while the subscripts “bu”, “ca” and
“pe” denote the bulk liquid phase, cake layer and permeate stream,
respectively. In the hybrid MBR process, the concentrations of the
electron donor and target contaminant (non-fouling constituent)
in the bulk liquid, Ce,bu and Cc,bu manifest a gradual reduction in
the cake layer, as shown in Fig. 2. The permeate concentrations of
these components, Ce,pe and Cc,pe are assumed very low because
the electron donor (ethanol) and the target contaminant (nitrate
or alachlor) are considered completely biodegradable under ideal
conditions.
Membrane fouling in water treatment applications can be esti-
mated by using the resistance model, wherein the permeate flux (J)
is described by Darcy’s relationship as follows [47]:
driving force P
J= = (1)
viscosity × total resistance RT
where P is the differential pressure across the membrane and rep-
resents the total driving force. The total resistance RT denotes the
total resistance to permeate flow through the membrane, and  is
the feed solution dynamic viscosity. The total resistance is the sum
of various resistances given by the resistance-in-series approach as
RT = RM + RCP + RC + RGE + RIN (2)
In the above relation, RM , RCP , RCA , RGE and RIN are resistances
associated with the membrane material, concentration polariza-
tion, cake formation, gel formation, and internal pore fouling,
respectively. The osmotic pressure can be considered negligible in
ultrafiltration or microfiltration systems [47]. The resistance RM is
an intrinsic characteristic of the membrane, and therefore remains
constant; the resistance RCP is caused by the concentration gradient
of the component separated. The resistance RCA is attributed to the
deposition of the cake layer on the membrane surface. The resis-
tance RGE denotes the impedance to permeate transport caused by
gel formation on the membrane surface due to outer surface sorp-
tion of organic and bio-organic macromolecules and enzymes. The
resistance RIN denotes the transport impedance associated with
pore constriction or pore deposition of organic and bio-organic
macromolecules and enzymes. It is indeed very difficult to clearly
separate out the resistances RCP , RCA, and RGE . However, some qual-
itative assessments can be made on the basis of the resistance
model.
Qualitative and quantitative assessments of permeate flux dete-
rioration in MBR processes can be made based on resistance models.
Choo and Lee [48] compared the relative magnitudes of these
resistances in a typical anaerobic MBR process, and made certain
observations relevant to this study. They noted that combinations
of concentration polarization resistance and resistance, RCP and
RCA , respectively contributed to nearly 99% of overall transport
43
resistance. The intrinsic membrane resistance RM and the internal
fouling resistance RIN each contributed to about 0.5% of the total
resistance RT . The combination of concentration polarization and
cake resistances is attributed to colloidal and bio-particles. The
internal pore fouling resistance RIN is mainly caused by organic
deposition or pore sorption, while the gel resistance RGE is con-
tributed by the surface sorption of organic molecules. It must be
noted that the intrinsic membrane resistance, RM , is governed by
the hydrophobic or hydrophilic properties of the membrane, and
therefore cannot be reduced by chemical cleaning. A combination
of chemical and mechanical cleaning can eliminate substantial por-
tions of the transport resistances RCP and RCA , but in most situations
even efficient chemical cleaning can only partially reduce the resis-
tance RIN . Nevertheless, in the MBR system, major resistances are
RCP and RCA , and so a cycle of chemical and mechanical cleaning can
achieve substantial permeate flux recovery.
Membrane fouling generally attributed to concentration polar-
ization, gel formation and cake formation can be controlled by
combining fluid management and adsorbent use. Turbulent flow
regimes within membrane modules can create flow instabilities
and vortices that can depolarize dissolved solids and re-entrain col-
loids or suspended particles from the viscous sub-layer (part of the
gel layer). In synergism with fluid management, the PAC discharges
several functions discussed in the earlier studies by Pirbazari and
coworkers [9,49,50]. Firstly, it depolarizes the membrane surface
by promoting back-diffusion (or back-migration) of organic solutes
from the membrane–fluid interface to the bulk fluid, depleting
the solute concentration by PAC sorption. Secondly, it serves as
a filter aid by forming an incompressible particulate layer on the
membrane, and thereby enhances fluid permeability. Thirdly, its
dynamics reduces the thicknesses of mass-transfer and hydrody-
namic boundary layers.
In the MBR system described herein, without biomass or PAC
the permeate flux decline could be mainly attributed to organic
fouling due to NOM, as colloidal substances such as soil, clay and
silt would be insignificant owing to the low turbidity of the source
waters. In the case where biomass alone is employed without PAC,
permeate flux decline might be caused by organic fouling due to
the combination of NOM, microbial enzymes and SMPs, besides
biomass. While biomass could predominantly lead to surface foul-
ing and cake formation during biological fouling, organic fouling
might significantly contribute to internal pore fouling. When PAC is
employed with biomass, organic fouling can be mitigated (depend-
ing on adsorbent dosage), while biological fouling may not be as
effectively controlled. Nonetheless, combination of PAC and micro-
bial biomass would reduce transient state flux decline but would
not significantly affect steady-state flux decline.
The resistance model stated above represents one of the
methods for membrane fouling classification due to different phe-
nomena for wastewater treatment applications. This approach
relies on a phenomenological classification of fouling that uses the
resistances RM , RCP , RCA , RGE and RIN associated with the membrane
material, concentration polarization, cake formation, gel formation,
and internal pore fouling, respectively. In the case of a hybrid MBR
process used for water treatment, especially where an adsorbent
such as PAC and microbial biomass are employed (as in this study),
classification of membrane fouling based on the foulant types will
be more appropriate. The rationale behind the choice of foulant
type classification above phenomenological classification is based
on certain advantages the method offers in water treatment situ-
ations. Evidence suggests that in wastewater treatment scenarios,
phenomenological aspects such as concentration polarization, gel
formation, cake formation and internal pore sorption are impor-
tant, but somewhat indistinguishable. However, in water treatment
situations, it is easier to distinguish between different classes of
foulants. For example, inorganic anions can potentially contribute
44 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54

Fig. 2. Sketch of a PAC–biofilm layer (illustrated with an actual scanning electron micrograph) and the concentration profiles of the target contaminant and electron donor
in the membrane module of the hybrid MBR process.

to inorganic fouling due to formation of precipitates such as cal-
cium carbonate and calcium sulfate. Furthermore, identification
of foulant classes offers certain advantages in analyzing permeate
flux and component rejection data with reference to a number of
factors. These are evaluating component rejections under various
conditions, identifying foulants of maximum concern based on flux
decline patterns, investigating foulants that can increase rejections
of target contaminants, and formulating cleaning strategies or pro-
tocols for optimizing membrane performances. According to the
new approach, the total resistance RT may be written as
RT = RM + RI + RO + RB = RM + RF
where RI , RO and RB are resistances in the MBR process attributed
to inorganic, organic and biological fouling, respectively, and RM
is the intrinsic membrane material resistance. Here, RT can also
be represented as the sum of RM and RF , where the fouling resis-
tance RF represents the sum of RI , RO and RB . Furthermore, RF shall
be denoted differently for two types of MBR process operations:
RFP when microbial biomass and PAC are used, and RFW when
biomass alone is employed. In this scenario, RO denotes fouling
due to NOM, EPS, SMP and other organics microbially generated,
RI denotes inorganic fouling due to precipitate formations or scal-
ing, and RB represents biological fouling due to microbial particles
(3) and biofilms. The resistance RT can be estimated from permeate
 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54 45

Table 1 then dried at 105 ◦ C, desiccated to room temperature, and stored

Characteristics of the groundwaters used.
in airtight glass containers. The particle sizes of the PAC ranges from
Component and Fountain Valley Tustin 30 to 50 ␮m.
concentration groundwater groundwater
(FVGW)a (TGW)b
4.3. Nutrient solution
Nitrate (NO3 − ) (mg-N/L) 0.3 20
Sulfate (SO4 2− ) (mg/L) 8.3 220 The composition of nutrient solution was as follows:
Bicarbonate (HCO3 − ) (mg/L) 80 308
FeCl3 ·6H2 O, 0.2 mg/L; Na2 MoO4 ·2H2 O, 0.02 mg/L; K2 HPO4 ,
Chloride (Cl− ) (mg/L) 15 185
Sodium (Na+ ) (mg/L) 84 125 21.7 mg/L; KH2 PO4 , 26.9 mg/L. The denitrification process required
Calcium (Ca2+ ) (mg/L) 8.1 138 the addition of a nutrient solution and an external carbon source
Magnesium (Mg2+ ) (mg/L) 1.1 39 such as ethanol to sustain the microbial population.
Total organic carbon (TOC) (mg/L) 3.5–4.0 <0.1
Ultraviolet absorbance at 254 nm (UVA254 ) 0.19–0.22 <0.005
(cm−1 ) 4.4. Microbial cultures
Dissolved Oxygen (mg/L) ∼0 8.9
Turbidity (NTU) <1 <0.1 The microbial culture used in the denitrification studies was
pH 7.9–8.3 7.8 obtained from a water reclamation plant. The culture was added
a
Data obtained from the Orange County Water District. to the source water containing essential nutrients and ethanol (the
b
Data obtained from the Municipal Water District of Orange County. electron donor). The acclimation conditions were controlled at a pH
of 7.8 ± 0.3, dissolved oxygen of zero, and temperature of 20 ± 2 ◦ C.
Pure cultures of Escherichia coli and bacteriophage MS-2 [51] (ATCC
flux data, and certain conclusions can be drawn from these data
15597-B1) used in these studies were obtained from the Micro-
acquired for the three MBR operational scenarios at various instants
biology Division Laboratory of the Metropolitan Water District of
of time.
Southern California, La Verne, California. The bacteriophage MS-2
(male specific virus) was chosen as indicator organism to evaluate
4. Materials and methods the MBR process for pathogen removal.

4.1. Water sources 4.5. Nitrate, nitrite, and dissolved oxygen analyses

Two types of groundwaters were used in the research: one with
high TOC and low nitrate concentration, and another with low
TOC and high nitrate content. The high TOC water was obtained
from a deep well in Fountain Valley, California, while the low
TOC water was collected from a well located in Tustin, Califor-
nia. Both groundwaters were collected in clear airtight containers,
transported to the laboratory, and stored at 20 ◦ C. The chemical
compositions and characteristics of the two groundwaters are pre-
sented in Table 1. The Fountain Valley groundwater (FVGW) had a
nitrate level of approximately 0.3 mg/L and was low in total dis-
solved solids (TDS), while the Tustin groundwater (TGW) had a
higher average nitrate concentration of 20 mg/L, and was high in
TDS including sulfate, bicarbonate, chloride, calcium, sodium and
magnesium ions. The FVGW had a significantly higher NOM con-
tent than the TGW as reflected by the TOC and UVA254 (ultraviolet
absorbance at 254 nm) levels, and therefore had a higher poten-
tial for organic membrane fouling. The TOC and UVA254 levels for
the FVGW were 3.5–4.0 mg/L and 0.19–0.22 cm−1 , while the cor-
responding values for TGW were below 0.1 mg/L and 0.005 cm−1 ,
respectively. Obviously, the FVGW exhibited a higher potential for
membrane organic fouling of membranes. However, the TGW had
a significantly higher TDS content than the FVGW, and therefore
manifested a higher potential for membrane inorganic fouling. The
FVGW was low in nitrate content, and so it was spiked with appro-
priate nitrate levels of 16–18 mg/L for all studies. Additionally, the
FVGW was spiked with 99.7% pure alachlor (Fisher Scientific, North
Kingstown, Rhode Island) at a concentration of 60–100 ␮g/L. In the
present study, batch biokinetic studies and MBR studies evaluated
the removals of target contaminants using the FVGW, whereas lim-
ited MBR tests investigated the permeate flux decline patterns for
both source waters.
4.2. Activated carbon adsorbent
The nitrate and nitrite concentrations were determined by the
cadmium reduction method using a UV–visible spectrophotometer
(Perkin–Elmer Lambda 4A) with a detection limit of 0.01 mg-N/L
for both nitrate and nitrite (Method 4500-nitrate E of Standard
Methods [52]). The concentration of dissolved oxygen was deter-
mined by the membrane electrode technique (Method 4500-O) as
described in Standard Methods [52], and the detection limit for
these measurements was 0.1 mg/L.
4.6. Ethanol analysis
The ethanol analysis was conducted by gas chromatography
using a Perkin-Elmer Sigma 2B gas chromatograph equipped with
a flame ionization detector (GC-FID), and a 6-foot glass column
packed with 0.1% SP-1000 on 80/100 CarboPak C (Supelco Inc.,
Bellefonte, Pennsylvania), and interfaced with a data processor.
The instrument was operated under isothermal conditions with
injector, oven and detector temperatures of 200, 80 and 250 ◦ C,
respectively. The detection limit for this technique was 0.1 mg/L.
4.7. Alachlor analysis
Alachlor was analyzed according to Method 6630 of Standard
Methods [52], wherein the samples were subjected to liquid–liquid
extraction method using pentane. The extracts were analyzed by
a Hewlett Packard 5790A series gas chromatograph with a 63 Ni
electron capture detector (GC-ECD) (Hewlett Packard, Palo Alto,
California) and a 30 m × 0.53 mm DB-5 capillary column (Supelco,
Inc., Bellefonte, Pennsylvania). The GC-ECD system employed a car-
rier gas mixture of 95% argon and 5% methane at a flow rate of
3.1 mL/min. It was operated isothermally with injector, oven and
detector temperatures of 225, 240 and 300 ◦ C, respectively. The
detection limit for alachlor using this technique was 1 ␮g/L.

The powder activated carbon (PAC) employed was Calgon WPH 4.8. Trihalomethane formation potential measurements
(Calgon Carbon Corp., Pittsburgh, Pennsylvania). The PAC was
washed several times with deionized-distilled water to eliminate The THMFP measurements were conducted according to
leachable organics, inorganics and fine particles. The carbon was Method 5710 B for chlorinated DBPs [52]. Samples were collected
46 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54

Table 2
Conditions for the MBR mini-pilot-scale experiments.

Condition Run 0 Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 7 Run 8 Run 9

Water used Ultra-pure water FVGW FVGW FVGW FVGW FVGW FVGW TGW TGW TGW

Influent TOC (mg/L) 0 3.5 3.1 3.1 4.0 4.3 4.2 ∼0.1 ∼0.1 ∼0.1
Influent nitrate (mg/L) 0 17.2 17.4 17.8 16.6 17.8 17.2 17.2 17.5 17.4
Initial biomass (mg-MLSS/L) 0 – 343.3 342.6 – 343.6 360.8 – 344.1 343.5
PAC slurry (mg/L) 0 – – 500 – – 500 – – 500
Influent alachlor (␮g/L) 0 98.0 93.4 84.8 88.6 92.6 102 98 96 98
Influent virus (PFU/mL) × 105 – – – – 3.83 3.30 5.63 – – –

in duplicates in 125 mL borosilicate glass bottles with Teflon septa
screw caps. These samples were buffered to pH 7.0 using a phos-
phate buffer and chlorinated at a 3-to-1 Cl2 -to-TOC ratio using a
5 mg/mL Cl2 stock solution, and were subsequently incubated in
the dark at 20 ◦ C for 24 h. After incubation, the chlorine residual
was tested and then quenched using sodium sulfite solution. The
extraction of THMs from aqueous samples was accomplished by a
liquid–liquid extraction method using high-purity pentane, and the
extracts were analyzed for THMs by gas chromatography accord-
ing to Method 6232 D [52]. The detection limit for THM formation
potential measurements using this technique was about 0.1 ␮g/L.
4.9. Total organic carbon analysis
The TOC analysis was conducted in accordance with Method
5310 B outlined in Standard Methods [52] using a Shimadzu Model
TOC-5000 analyzer (Shimadzu Scientific Instruments, Columbia,
Maryland). The TOC analyzer was quipped with a non-disperse
infrared detector, and its detection limit was about 20 ␮g/L.
4.10. Virus concentration measurements
The MS-2 virus measurements were based on a standard,
double-layer agar assay technique with E. coli Famp (ATCC 15597
[51]) as the host. Experimental procedures relating to E. coli prepa-
ration and inoculation with MS-2 are described by Madaeni [53].
The MS-2 concentrations were measured in terms of plaque counts
per unit volume or plaque formation units per milliliter (PFU/mL).
All samples were assayed in triplicate for each dilution and exam-
ined. The average number of plaques present in the most countable
dilution was used to estimate plaque counts per unit volume.
4.11. Batch biokinetic studies
Completely mixed batch bioreactor studies were performed in
a glass reactor with a capacity of 7 L for evaluating denitrifica-
tion kinetics. These experiments were conducted under different
initial C/N ratios, pH and temperatures to determine the optimal
conditions, using the groundwater employed for the MBR stud-
ies, per procedures described by Tsai [9] and Tsai et al. [10]. The
reactor system was equipped with a pH control electrode, a dis-
solved oxygen electrode, an agitator, and a pump delivery system
for acid, base, nutrients and feed water. The temperature was main-
tained at a desired level via a built-in circulating water bath. At the
start of each experiment, the acclimated denitrifying microbial cul-
ture was added to the fermenter, the solution was deoxygenated
with nitrogen gas to maintain anaerobic conditions, and the pH
controlled at a pre-determined level. The reactor mixing was pro-
vided by a paddle-blade rotator operated at 400 rpm. For each
set of experiments, only the tested parameter was varied within
a desired range, while other conditions were constant. The dura-
tions of batch experiments were in the range of 100–540 min. The
biomass concentrations varied from 270 to 790 mg/L with average
values ranging from 390 to 590 mg/L [9]. The initial nitrate concen-
trations were in the range of 65–90 mg N/L [9]. The experiments
were conducted at different temperatures in the 10–40 ◦ C range.
Samples were periodically taken and analyzed for nitrate, nitrite,
ethanol and biomass concentrations.
4.12. Mini-pilot-scale MBR studies
Mini-pilot-scale MBR studies were conducted using two source
waters, namely, the FVGW and the TGW. A schematic of the exper-
imental mini-pilot-scale MBR process is presented in Fig. 1. The
MBR system consisted of a completely stirred tank reactor, a tubu-
lar cross-flow membrane module, and a recirculation pump. The
membrane module consisted of six ceramic tubes (1 cm o.d.) of
gamma-alumina (-Al2 O3 ) membranes having a nominal pore size
of 0.2 ␮m and a total area of 0.03 m2 . The MBR process was operated
in a continuous mode, where the deoxygenated source water was
continually supplied to the reactor using feed pumps controlled by
level switch within the reactor. The mixed liquor in the reactor was
fed through the membrane lumen using recirculation pump where
some of liquid passes through the membrane as product water,
and the membrane concentrate was recirculated. Ethanol was used
as the electron donor for anoxic biological denitrification. A con-
stant TMP of 20 psi (1.4 bars) and cross-flow rate of 20 L/min was
used. The pH in bioreactor was monitored and adjusted as required.
Samples from the permeate stream were periodically collected for
measuring the concentrations of nitrate, nitrite, ethanol, biomass,
TOC, THMFP, alachlor, MS-2 virus, and dissolved oxygen, as well
as for determining the flow rates and permeate fluxes as functions
of time. Nine sets of experiments were conducted, and their salient
features are presented in Table 2: Runs 1–6 used the FVGW as water
source, whereas Runs 7–9 employed the TGW.
5. Results and discussion
5.1. Batch biokinetic optimization studies
Biological denitrification is an oxidation–reduction reaction
wherein microorganisms utilize carbon source as electron donor
to reduce nitrate ions to nitrogen gas. As the groundwater to be
treated lacked sufficient amount of readily biodegradable organic
constituents, ethanol was added as external carbon source to facil-
itate the redox process, and the rationale for choosing ethanol was
discussed earlier.
Batch biokinetic studies were conducted and the specific deni-
trification rate (SDR) was estimated under different conditions such
as temperature and pH for FVGW. The nitrate and ethanol removal
efficiencies were determined as a function of the C/N ratio. The
results of biokinetic studies are summarized in Fig. 3(a)–(c). Fig. 3(a)
shows that the optimal initial C/N ratio was 0.8 mg-C/mg-N with the
pH and temperature maintained at 7.8 and 20 ◦ C. Above this value,
nitrate was completely removed, but ethanol residuals increased;
and below this value, the denitrification efficiency sharply declined.
For instance, nitrate removal was only 74% corresponding to a C/N
ratio of 0.5 mg-C/mg-N. The results showed that a shortage in sup-
ply of carbon source would limit denitrification efficiency, and an
 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
excess in supply would decrease ethanol removal. Therefore, the
preliminary determination of the optimal C/N ratio was not strictly
based on SDR considerations. At the favorable C/N ratio of 0.8, more
biokinetic experiments were conducted to evaluate the effects of
temperature and pH on denitrification kinetics. Fig. 3(b) shows that
the SDR was only 0.36 mg-N/mg MLSS-day at 20 ◦ C while it was 1.24
mg-N/mg MLSS-day at 40 ◦ C. A temperature of 20 ◦ C was chosen
as a favorable value in view of economics based on reaction ener-
getics, compatibility with ambient conditions, and overall process
energy requirements. It was indeed uneconomical to conduct den-
itrification tests at 30 or 40 ◦ C owing to the energy need to increase
the temperature of the treated water to those levels. The advan-
tages of faster reaction kinetics were greatly offset by the higher
energy requirements. The results depicted in Fig. 3(c) indicate that
the optimal pH based on SDR considerations was 7.8, given that the
most optimal C/N ratio was 0.8 and the most favorable tempera-
ture was 20 ◦ C. In short, optimization of biological denitrification
process was not based on biokinetics alone, but also on energy
utilization as well as on nitrate and ethanol residuals.
Fig. 3. Batch reactor biokinetic studies for denitrification of Fountain Valley ground-
water (adapted from Tsai [9]): (a) removal efficiencies of nitrate and ethanol as a
function of C/N ratio (optimal temperature 20 ◦ C and pH 7.8), (b) specific denitrifi-
cation rate as a function of temperature (optimal pH 7.8 and C/N ratio 0.8), and (c)
specific denitrification rate as a function of pH (optimal temperature 20 ◦ C and C/N
ratio 0.8).
47
Fig. 4. Concentrations of nitrate, nitrite, ethanol and biomass as functions of time
in batch reactor studies for Fountain Valley groundwater.
Typical biokinetic data showing the biomass, nitrate, nitrite,
and ethanol concentration profiles as functions of time for FVGW
are presented in Fig. 4. These data indicate that biological den-
itrification occurred in a one-step reaction in which nitrate was
converted to nitrogen gas without significant nitrite accumulation.
The maximum nitrite concentration detected in the effluent was
0.06 mg-N/L, which was below the recommended MCL of 1 mg/L
NO2 -N. Meanwhile, ethanol was consumed, and the biomass con-
centration gradually increased. The biomass profile showed that
there was a growth phase of about 15 h during which the biomass
concentration increased from about 92 to 106 mg/L, which was fol-
lowed by a stationary phase between 15 and 20 h. Subsequently,
the biomass levels started decreasing as microbial lysis occurred.
The batch bioreactor studies facilitated process optimization
with respect to the C/N ratio, temperature and pH. The optimal
C/N ratio was 0.8 g C/g N-NO3 , and this value was employed in sub-
sequent MBR mini-pilot-scale studies. As biological denitrification
was constrained by temperature limitations due to reaction ener-
getics and compatibility with ambient conditions, a near-optimal
temperature of 20 ◦ C was preferred. In summary, the optimal
process conditions were as follows: C/N ratio of 0.8 C/g N-NO3 , tem-
perature of 20 ◦ C, and a pH of 7.8. Similar results were obtained from
biokinetic tests for TGW as reported by Tsai [9].
5.2. Mini-pilot-scale MBR studies
5.2.1. Removals of nitrate and nitrite
The nitrate and nitrite removals under different MBR process
conditions (Table 2) for the FVGW are presented in Fig. 5. These pro-
cess conditions included the application of biomass alone, biomass
with PAC, and direct membrane filtration without biomass or PAC
(to serve as control), as previously discussed. The PAC slurry was
added to the MBR system only at the commencement of operation,
and was not continuously employed throughout the experimen-
tal run. The MBR experiments showed that high nitrate removals
could be achieved using this technology, and that no differences
in removals were observed under either transient-state or steady-
state conditions for the two scenarios—biomass alone, and PAC with
biomass. A turning point was observed after the first 6 h when the
nitrate removals improved from about 86% to over 99% for Run
5 (only biomass), and from 88% to almost 100% for Run 6 (com-
bination of PAC and biomass). These results indicated that the
biomass was well acclimated for denitrification after 6 h of pro-
cess operation. Under either scenario (Run 5 or Run 6), the effluent
48 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54

Fig. 5. Nitrate removal in the MBR system from Fountain Valley groundwater under
various MBR process conditions.
as evidenced from Figs. 6(b), 6(c), 7(b) and 7(c). After 35 h of MBR
operation with biomass alone, the ethanol TOC and non-ethanol
TOC removals were 100% and 70%, respectively (Fig. 6(b)); and, the
corresponding THMFP and alachlor removals were 61% and 35%
(Fig. 7(b)). A combination of PAC and biomass further increased the
removal efficiencies for non-ethanol TOC and THMFP to 84% and
98%, and those for ethanol TOC and alachlor to nearly 100%, respec-
tively, corresponding to a PAC dosage of 500 mg/L, as depicted in
Table 2 and Figs. 6(c) and 7(c).
A noteworthy feature of the results was that the resid-
ual ethanol (electron donor for biological denitrification) in the
effluent was below the detection limit of 0.1 mg/L. Further-
more, no non-ethanol TOC was observed due to metabolic end
products of ethanol biodegradation, and this was established
by gas chromatography–mass spectrometry (GC–MS) analysis of

nitrate concentrations steadily decreased and approached almost

zero after 8 h. An important consideration was that no nitrite resid-
uals were observed in the treated MBR effluent. The contribution of
PAC sorption to nitrate removal was insignificant owing to negligi-
ble sorption of the species on activated carbon [9,10]. Nonetheless,
PAC was employed in the MBR process for other reasons. Firstly,
PAC could serve as a buffer to prevent the biological inhibition of
denitrification due to toxic organics that possess strong affinity for
carbon adsorption. Secondly, it could remove NOM, reduce DBP
formation potential (THMFP), and prevent microbial regrowth in
distribution systems (due to BOM removal). Thirdly, it was believed
that PAC could possibly ameliorate membrane fouling and perme-
ate flux decline [6].

5.2.2. Removals of NOM, TOC, alachlor and THMFP

The effects of membrane filtration as well as PAC and biomass
addition to the MBR process on the removals of various organic
components of interest as functions of time are presented in
Figs. 6 and 7. These components include ethanol TOC, non-ethanol
TOC (predominantly NOM), THMFP, and alachlor. As the total
TOC represents a combination of NOM and ethanol concentrations
(ethanol is the electron donor for biological denitrification), the
TOC attributable to NOM is referred to as non-ethanol TOC and is
distinguished from the TOC arising from ethanol.
Figs. 6(a) and 7(a) indicate that steady-state removals of ethanol
TOC and alachlor due to membrane separation alone (control runs
without PAC or biomass) were insignificant. In comparison, the
removals of non-ethanol TOC and THMFP were about 63% and 18%,
respectively; and these removals could be solely attributed to the
partial NOM rejection by the membrane. It must be noted that non-
ethanol TOC of the FVGW included relatively high molecular weight
NOM fractions. The characteristics of this water were reported by
Tan and Amy [54] who indicated that the relative distributions of
NOM molecular weight fractions (measured as TOC) were as fol-
lows: <0.5 kDa, 28%; 0.5–1 kDa, 18%; 1–5 kDa, 13%; 5–10 kDa, 21%;
10–30 kDa, 14%; and, >30 kDa, 6%. Their study reported that 41% of
the NOM (non-ethanol TOC) consisted of compounds whose molec-
ular weights were well above 5–10 kDa. Additionally, the MBR test
results showed that after the first hour, the rejection of non-ethanol
TOC by the membrane rapidly increased from 0 to 50%, and after
the second hour, increased to nearly 63%. This indicated that pro-
gressive gel formation and internal pore fouling possibly caused
a steady increase in NOM rejection. These observations were also
supported by the membrane fouling and flux decline patterns, dis-
cussed in a later section (Figs. 9 and 10; membrane permeate flux
data for FVGW when no PAC or biomass was used).
The MBR test results showed that the removals of all the com-
Fig. 6. Ethanol and non-ethanol TOC removals in the MBR system for Fountain Valley
ponents exhibited increases with the use of biomass alone, and groundwater: (a) no biomass or PAC (Run 4), (b) biomass alone (Run 5), and (c)
further improvements with a combination of biomass with PAC, biomass and PAC (Run 6).
 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
the degradation products. Therefore, complete mineralization of
ethanol (electron donor) during biological denitrification was con-
cluded. This is an important factor because residuals of ethanol
and/or its organic metabolite(s) would lead to microbial regrowth
in distribution systems and increase in THMFP during chlorina-
tion. A comparison of results depicted in Fig. 6(a)–(c) led to certain
important observations. Membrane filtration alone accounted for
a non-ethanol TOC removal of 63%, while the addition of microbial
degradation improved the removal by over 7%, and a combina-
tion of PAC sorption and microbial degradation further enhanced
the removal by another 14%. In the best-case scenario (Fig. 6(c)),
the non-ethanol TOC level in the effluent was well below 0.7 mg/L
The high THMFP removal of 98% corresponding to an influent
level of 450 ␮g/L would reduce the residual level below 10 ␮g/L,
easily meeting the DBP control objective. The results depicted
in Fig. 7(a)–(c) emphasize that PAC sorption and biodegradation
Fig. 7. Alachlor and THMFP removals in the MBR system for Fountain Valley ground-
water: (a) no biomass or PAC (Run 4), (b) biomass alone (Run 5), and (c) biomass
and PAC (Run 6).
49
Fig. 8. Virus MS-2 removals for Fountain Valley groundwater under various MBR
process conditions.
achieve higher alachlor removals. The use of biomass resulted in
alachlor removals of 36%, principally due to bacterial sorption,
while combination of PAC with biomass however increased the
removals to nearly 100%. These findings indicate that the MBR pro-
cess could achieve alachlor residuals well below drinking water
standards (0.2 ␮g/L) even at influent levels exceeding 100 ␮g/L.
The results of the present investigation can be compared to
those of an earlier study by Tian et al. [55] who employed a mem-
brane bioreactor process with PAC and biomass for NOM removal
from drinking water supplies. Tian et al. [55] observed dissolved
organic carbon (DOC) removals (non-ethanol TOC removals in our
context) of 19.4% and 37.5% when they employed an MBR system
with biomass alone and biomass and PAC, respectively. In our study,
the non-ethanol TOC removals corresponding to these two cases
were 70% and 84%, which are indeed significantly higher than those
reported by Tian et al. [55]. However, it must be noted that direct
comparison of our studies with those of Tian and coworkers would
not be appropriate owing to differences in material properties and
pore size distributions of the membranes employed, and in the
characteristics of the raw water treated. Tian et al. [55] employed
a polyvinyl chloride (PVC) ultrafiltration membrane of pore size
0.01 ␮m as compared to the present study that used a gamma-
alumina (-Al2 O3 ) microfiltration membrane of pore size 0.2 ␮m.
Additionally, the PVC membrane was generally more hydrophobic
than the gamma-alumina (-Al2 O3 ) membrane, and was therefore
more susceptible to organic fouling. Furthermore, the raw water
used by Tian et al. [55] had an NOM content of 5.6 mg/L as DOC,
6.2 mg/L as TOC, and 0.07 cm−1 as UVA254 (ultraviolet absorbance
at 254 nm), and a turbidity level of 2.4 NTU. In comparison, the
NOM content of the FVGW had a TOC level of 3.5–4.0 mg/L, and
a UVA254 level of 0.19–0.22 cm−1 , and a low turbidity of 0.1 NTU.
Nevertheless, the FVGW apparently consisted of higher molecular
weight NOM, as discussed earlier. Therefore, higher NOM removals
could be expected in our study as compared to those of Tian and
coworkers, due to the combination of factors stated above.
5.2.3. Removals of viruses
The MS-2 removal efficiencies were evaluated under the three
MBR process conditions (Table 2: Runs 4–6), and the experimental
results are presented in Fig. 8. The feed water spiked with MS-2
virus contained additional non-NOM type TOC (0.6–0.8 mg/L) from
the Tryptone broth used in its preparation. The MS-2 viral counts in
the influent were in the range (3.30–5.86) × 10+5 PFU/mL (Table 2).
In the control study (Run 4) with neither PAC nor biomass, MS-2
removal of about 3.7-logs was experienced after 2 h of process oper-
ation. When biomass alone was employed (Run 5), the removals
were initially low during the first 9 h of testing at 2.7-logs, and then
gradually improved to 3.5-logs at steady state. When biomass and
PAC were employed in combination (Run 6), the MS-2 removals
50 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54

were 3.6-logs after the first 10 h, and further improved to 3.8-logs.

These results indicated that certain mechanisms were operative in
MS-2 virus removals under the three testing conditions.
The MS-2 virus is relatively small (about 0.025 ␮m or 25 nm
in size and 3.6 × 106 Da in molecular weight), and its rejec-
tion by a 0.2-␮m pore size microfiltration membrane cannot be
solely attributed to mechanical sieving and size exclusion; other
mechanisms including membrane sorption, gel sorption, and cake
sorption could be operative. Initially, under the control scenario
(Run 4 with no biomass or carbon), the NOM in the water could lead
to gel formation and internal pore plugging, potentially enhancing
the membrane virus rejection. In Run 5, when biomass alone was
employed, the role of biomass was initially insignificant, because
it possibly hindered gel formation owing to some biodegradation
of the NOM that would have caused pore blocking. However, at
later stages, a combination of gel and biomass layers might have
improved virus rejection due to increased fouling and pore block-
ing. In Run 6, when biomass and PAC were used, the MS-2 virus Fig. 9. Permeate flux profiles for Fountain Valley and Tustin groundwaters under
rejection was more efficient possibly due to the PAC–biomass cake various MBR process conditions.
formation. Therefore, the following virus removal mechanisms
can be proposed: (i) rejection by NOM gel layer, (ii) rejection by
The highest initial flux decline rates were observed for the con-
microbial biomass layer, (iii) rejection due to internal pore block-
trol run with TGW where no PAC or biomass was employed (Run
ing by NOM molecules, (iv) sorption on the membrane surface,
7); the flux declined from 600 to 350 L/(m2 h) during the first 6 h
PAC, and/or bio-particles (groundwaters have low turbidity), and
and subsequently to 285 L/(m2 h) at steady state. When biomass
(v) a combination of these mechanisms. Nonetheless, a caveat
alone was employed without PAC, the flux declined from 150 to
must be added that these results are applicable to MS-2 or similar
77 L/(m2 h), initially, and further deteriorated to a steady-state
viruses and cannot be generalized to all strains owing to differ-
value of 60 L/(m2 h) after about 6 or 7 h (Run 8). When PAC was used
ences in sizes, shapes, morphologies, surface charge and adhesion
in combination with biomass, the initial flux declined from 300 to
characteristics.
160 L/(m2 h) within 6 or 7 h, and eventually reached 100 L/(m2 h) at
steady state (Run 9). The results for FVGW exhibited patterns qual-
5.2.4. Membrane permeate fluxes and flux decline patterns
itatively similar to those for TGW, although the fluxes were lower.
An important consideration in the operation of MBR processes is
When no biomass or PAC was employed, the flux for FVGW was ini-
effective control of membrane fouling and mitigation of permeate
tially 450 L/(m2 h), but declined to about 180 L/(m2 h) after about
flux decline. In order to evaluate the effects of PAC and microorgan-
7 h, and later reached a steady-state value of 160 L/(m2 h) (Run 1).
isms on membrane fouling and permeate flux decline, the flux data
When biomass alone was employed, the flux for FVGW decreased
were obtained for FVGW and TGW under three testing scenarios as
from an initial value of 160 to 80 L/(m2 h) after about 7 h, and further
previously described: (i) no biomass or carbon, (ii) biomass alone
declined to 60 L/(m2 h) at steady state (Run 2). With the applica-
without PAC, and (iii) combination of biomass and PAC. Analyses
tion of biomass and PAC, the flux for FVGW (Run 3) declined from
of permeate flux data generally facilitate comparisons of process
200 to 90 L/(m2 h) within the first 7 h, and further to 60 L/(m2 h) on
operating conditions, raw water quality and membrane character-
approaching steady state. Furthermore, the flux decline patterns
istics with regard to the nature of membrane fouling and patterns
were apparently unaffected by the MS-2 virus populations, as the
of flux decline. Additionally, flux decline patterns could suggest
fluxes for Runs 4, 5 and 6 (with viruses) were nearly identical to
possible fouling mechanisms and prescriptions for flux improve-
those for Runs 1, 2 and 3, respectively.
ment such as devising pre-treatment techniques, choosing cleaning
agents, developing cleaning procedures, and determining cleaning
frequencies. More importantly, these data can provide information
on the choice of membrane materials, pore characteristics, pore
size distributions, and modular configurations. The permeate flux
data and profiles for the aforementioned experiments presented in
Fig. 9 illustrate certain fouling and flux decline patterns. The per-
meate flux decline rate as a function of operation time is depicted
in Fig. 10. Qualitative and quantitative analyses of data presented in
Figs. 9 and 10 illustrate characteristic patterns of membrane fouling
and flux decline in three distinct stages: initial conditioning foul-
ing, rapid fouling and fast flux deterioration (under constant TMP),
and slow fouling and insignificant flux decline (under constant
TMP). These fouling patterns also reflected the differences between
the two source waters with regard to short-term and long-term
impacts. Generally, higher permeate fluxes were observed for TGW
versus FVGW under similar conditions, and this could be explained
by their NOM levels (TOC levels of <0.1 mg/L versus 3.5–4.0 mg/L
and UVA245 levels of <0.005 and 0.19–0.22 cm−1 ). The TGW with
significantly lower NOM content exhibited a lower organic fouling
potential. The NOM levels also influenced the membrane fouling
patterns from initial process operation (time zero) to subsequent Fig. 10. Permeate flux decline rates for the Fountain Valley and Tustin groundwaters
transient-state and approximate steady-state operations. under various MBR process conditions.
 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
The permeate flux data illustrate the importance of initial mem-
brane exposure to the feed water, and highlight that preliminary
surface fouling or internal pore fouling could be substantial. In fact,
the results (Fig. 9) indicate a lower preliminary membrane fouling
potential for TGW as compared to FVGW owing to its lower NOM
content. In the case where no biomass or PAC was employed (Runs 1
and 7), the initial permeate flux J0 for TGW was high at 600 L/(m2 h),
and low at 450 L/(m2 h) for FVGW. In the second case where only
biomass was employed (Runs 2 and 8), the initial fluxes for the
TGW and FVGW were 150 and 120 L/(m2 h), respectively. In the
third case where both biomass and PAC were used (Runs 3 and 9),
the corresponding fluxes were 300 and 160 L/(m2 h), respectively.
These results suggested that under similar experimental conditions
the differences in initial permeate fluxes for the two source waters
were attributable to their NOM levels. Furthermore, the initial foul-
ing during the first stage was the highest when biomass alone was
used without PAC (Runs 2 and 8).
A comparison of results (Fig. 9, Runs 3 and 7) showed that
without biomass or PAC the permeate fluxes were significantly
higher for the TGW. When biomass was used alone (Runs 2 and
8), the fluxes were relatively higher for TGW. However, when both
biomass and PAC were employed (Runs 3 and 9), the transient-state
fluxes were higher for TGW, although the steady-state fluxes were
nearly the same for both waters. These observations could again be
explained by the fact that the TGW had a lower NOM and hence
manifested a lower potential for initial gel formation and organic
fouling. Nevertheless, this effect diminished as steady state was
approached and the fouling levels were similar for both waters. This
aspect was illustrated by the flux data for two situations, namely,
operation without biomass or PAC, and that with PAC alone. Never-
theless, when biomass and PAC were combined (Runs 3 and 9), the
differences in fluxes were not pronounced for both waters because
most of the NOM was possibly sorbed by the PAC, and to some
extent by the biomass.
The permeate flux decline patterns observed in this study
highlight some important comparisons between wastewater and
water treatment scenarios using MBR systems, and the quali-
tative/quantitative nature of membrane fouling. In wastewater
treatment situations, the three stages of membrane fouling are
characterized by initial membrane exposure and fouling, an inter-
mediate period of slow fouling, followed eventually by a period
of fast or rapid fouling. However, in water treatment situations,
membrane fouling is significantly lower with distinctly different
flux decline patterns. These differences in patterns can be rational-
ized on the basis of feed water quality and treatment conditions.
In wastewater treatment scenarios, contaminant concentrations
are significantly higher with high TOC levels of 100–1000 mg/L,
often using high biomass levels of 10,000–20,000 mg/L. In water
treatment situations, contaminant concentrations are relatively
low with the TOC and biomass levels in the ranges of 0–10 and
40–400 mg/L, respectively [6,8,10].
Membrane fouling and flux decline patterns are indeed better
reflected by the permeate flux decline rates (−dJ/dt) as a func-
tion of the operation time t, as depicted in Fig. 10. Apparently,
the second stage of rapid or fast fouling occurs between 0.1 and
1 h as flux decline rates decrease from 100–350 L/(m2 h2 ) to about
2–5 L/(m2 h2 ); and later, during the third stage, the rates are fur-
ther reduced to 0–1 L/(m2 h2 ). These results indicate that most of
the membrane fouling and flux decline occurred during the first 0.5
to 1 h of operation for both source waters in the three operational
scenarios previously described. The flux decline rates are maximum
at 60 L/(m2 h2 ) after 1 h for FVGW without biomass or PAC, and are
relatively lower for the cases using biomass alone and biomass in
combination with PAC. This is so because biological and organic
fouling occur during the initial phase of membrane exposure to the
feed water. The flux decline rates during this initial period are lower
51
for both source waters when biomass or PAC or both are employed.
This is so because the initial fluxes are themselves lower for these
cases as compared to filtration without biomass or carbon. The flux
decline patterns observed herein are relevant to hybrid MBR sys-
tems that use microorganisms and adsorbents in water treatment
situations.
The permeate fluxes for both waters (FVGW and TGW) under
the three previously described scenarios were investigated on the
basis of the resistance model to highlight three characteristic stages
of membrane fouling. The fluxes at times 0, 1 and 30 h (t = 0, 1 and
30 h) as well as the corresponding total resistances RT are presented
in Table 3. The selection of these times was based on membrane
fouling and permeate flux decline patterns observed in this study.
The fluxes at start (t = 0 h) illustrate the effect of membrane expo-
sure to feed in the first stage, wherein flux decline is very rapid.
The fluxes after 1 h (t = 1 h) represent the second stage of fouling,
wherein flux decline is not as fast as that experienced during the
first hour. The fluxes after 30 h of operation (t = 30 h) represent the
third stage characterized by approach to steady sate with slow
fouling. The membrane permeate flux data for ultra-pure water
was also measured as a control for comparison with other oper-
ating conditions. The ultra-pure water was prepared by passing
deionised-distilled water through a GAC column for the removal
or all trace organics (Run 0 in Tables 2 and 3). The flux decline
patterns yield some interesting information regarding membrane
fouling rates. It is important to note that most of the fouling occurs
during the initial period of membrane exposure to the feed, a factor
indicated by the high rates of increase in resistance RT as a func-
tion of time. The rates of change in RT become relatively slow after
the first hour, and the fouling follows a slower pattern afterwards.
These results are substantiated by the permeate flux decline rates
at various times, namely t = 0, 1 and 30 h (Table 3).
The total resistances RT (Eq. (3)) estimated from the experimen-
tal runs were of the range 0.66 × 10−13 to 8.26 × 10−13 m−1 and
their values were inversely related to the permeate fluxes, assum-
ing a constant TMP of 20 psi (137.8 kPa or 1.4 atm or 1.4 bars) and a
liquid phase viscosity of 0.01 Poise. The resistance RT correspond-
ing to ultra-pure water was the intrinsic membrane resistance RM
of 0.66 × 10−13 m−1 . The RT value corresponding to TGW with-
out using PAC or biomass at t = 0 (Run 7) of 0.83 × 10−13 m−1 is
essentially a combination of RM and RI (resistance due to inor-
ganic fouling) because the feed water has practically no NOM, but
has only inorganic foulants including silica and other salts and no
biomass. Therefore the resistance RI for TGW can be estimated at
t = 0 as 0.17 × 10−13 m−1 by noting the difference corresponding
to ultra-pure water. In the case of FVGW, the inorganic con-
stituents are low while the TOC level is high, so that by using
the RT of 1.10 × 10−13 m−1 for t = 0 when no biomass or PAC is
used, and neglecting inorganic foulants, the organic fouling resis-
tance RO can be estimated by comparison with ultra-pure water
as 0.44 × 10−13 m−1 . Determining the RT values at t = 0 for the two
waters when biomass alone was used (Runs 2 and 8), and calculat-
ing the differences in values with those for the no biomass or PAC
case (Runs 1 and 7), the biological fouling components RB for FVGW
and TGW can be estimated as 3.01 × 10−13 and 2.26 × 10−13 m−1 ,
respectively. These results support the view that the biological
fouling contributions are slightly higher for FVGW during the ini-
tial start-up phase. With the addition of PAC to biomass, the total
resistances for the FVGW and TGW decrease to 2.47 × 10−13 and
1.65 × 10−13 m−1 , respectively, at t = 0 (Runs 3 and 9). Similarly,
qualitative and quantitative assessments of resistances can be
made at various times such as t = 1 and 30 h, based on the results
presented in Tables 3 and 4.
The membrane fouling resistance RF was estimated for both
source waters (FVGW and TGW) at the operating times t of 0, 1
and 30 h by deducting the membrane resistance RM from the total
52 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54

Table 3
Permeate fluxes and total membrane transport resistances corresponding to the three stages of fouling.

Process conditions Run 0a Run 1a Run 2a Run 3a Run 7a Run 8a Run 9a

Source water

Ultra-pure FVGW FVGW FVGW TGW TGW TGW

Ultra-pure No biomass Biomass Biomass and No biomass Biomass Biomass
water or PAC alone PAC or PAC alone and PAC

Permeate flux at t = 0 h (L/(m2 h)) 750 450 120 200 600 160 300
Permeate flux at t = 1 h (L/(m2 h)) 750 265 70 95 500 110 180
Permeate flux at t = 30 h (L/(m2 h)) 750 120 60 65 230 60 75
Resistance, RT × 10−13 at t = 0 h (m−1 ) 0.66 1.10 4.11 2.47 0.83 3.09 1.65
Resistance, RT × 10−13 at t = 1 h (m−1 ) 0.66 1.86 7.05 5.20 0.99 4.49 2.74
Resistance, RT × 10−13 at t = 30 h (m−1 ) 0.66 4.11 8.27 7.59 2.15 8.27 6.58
a
Experimental run.

resistance RT . As mentioned earlier, the fouling resistances were
designated as RFW for operation with biomass alone without PAC,
and as RFP for the case with both biomass and PAC, and these values
are presented in Table 4. In qualitative and quantitative terms, the
RFW values were 30–50% lower than the RFP values, highlighting the
fact that PAC alleviates membrane fouling for both source waters
by reducing the organic and biological fouling to some extent. Addi-
tionally, the RFP values at the three characteristic operating times
(t = 0, 1 and 30 h) suggest that PAC reduced the fouling resistance
to lower levels for TGW, because this water had a lower potential
for organic fouling due to NOM. A comparison of the RFW values
for both waters presented in Table 4 shows that fouling resistances
were higher for FVGW at t = 0 and 1 h, but almost identical at t = 30 h.
These results demonstrated that during the first two stages of foul-
ing, namely, initial fouling and rapid fouling phases, the fouling
resistances were of higher magnitude for FVGW, but when the
slow fouling third stage (approximate steady state condition) was
approached, the fouling was almost the same as that experienced
without PAC application. Nonetheless, when PAC was employed,
the fouling resistance was lower for TGW than for FVGW, and this is
indeed an important factor regarding the function of PAC. A possible
explanation might be that owing to the higher NOM content (mea-
sured as TOC) in FVGW, the PAC reduced some gel formation and
internal pore sorption attributable to NOM. The permeate flux data
and the estimated transport resistances presented in Tables 3 and 4
illustrated certain qualitative aspects of membrane fouling. The
fouling resistances were consistently higher for FVGW as com-
pared to the TGW owing to the higher NOM content of the former.
Furthermore, the application of PAC increased the transient-state
fluxes but did not significantly improve the steady-state fluxes for
both source waters. These results highlighted that organic fouling
due to NOM initially influenced the transient-state fluxes but did
not significantly affect the steady-state fluxes. A plausible explana-
tion for this observation might be that biological fouling dominated
organic fouling during long-term operation, and that the initial
NOM fouling was superseded by biomass fouling at a later stage.
Additionally, the biomass-to-PAC ratio in this study was possibly
too high at 0.7 because the PAC slurry was not continuously fed to
the MBR after the initial addition. It is nevertheless possible that a
substantial portion of the biomass which was not attached to PAC
remained in suspension and caused more membrane fouling.
5.3. Some general observations on hybrid MBR technology for
water treatment
Several key issues must be addressed before the design and
operation of a pilot-scale or full-scale MBR process is to be con-
templated upon. These issues include the use of electron donors
for sustaining the denitrifying bacteria, the consideration of dis-
solved oxygen (DO), and control of membrane fouling or permeate
flux decline.
An electron donor such as ethanol was essential for biological
denitrification, and under ideal conditions the optimal C/N ratio
was 0.8 g C/g N-NO3 , when neither carbon nor nitrogen was reac-
tion limiting, complete denitrification was accomplished without
nitrite or ethanol residuals, and faster reaction rate was achieved.
Nevertheless, consistent maintenance of optimal C/N ratios in pilot-
scale or full-scale systems would be problematic due to variations
in source water quality as well as precision and accuracy limitations
of fluid flow and chemical metering systems. Furthermore, ethanol
residuals in the MBR effluent could promote microbial regrowth
and colonization in distribution systems.
Biological denitrification is an anoxic process wherein both reac-
tion rates and conversion efficiencies are adversely sensitive to
DO levels. When excess oxygen is available, heterotrophic bacteria
first utilize oxygen before nitrate as electron acceptor. Low process
efficiencies would require significantly larger reactor dimensions,
greater residence times, larger footprints, and higher operation
costs. This is an important factor because very high DO levels can
only be lowered by chemical addition (such as thiosulfate) or gas
purging, and chemical addition generally causes undesirably high
TDS levels.
Membrane fouling and permeate flux decline are important fac-
tors in MBR process operations, and so laboratory-scale testing and

Table 4
Membrane transport resistance components.

Fountain Valley groundwater (FVGW)a Tustin groundwater (TGW)a

Time (h)

t=0 t=1 t = 30 t=0 t=1 t = 30

Intrinsic membrane resistance RM (m−1 ) 0.66 × 10−13 0.66 × 10−13 0.66 × 10−13 0.66 × 10−13 0.66 × 0−13 0.66 × 10−13
Inorganic fouling resistance RI (m−1 ) – – – 0.17 × 10−13 0.33 × 10−13 1.49 × 10−13
Organic fouling resistance RO (m−1 ) 0.44 × 10−13 1.20 × 10−13 1.94 × 10−13 – – –
Biological fouling resistance RB (m−1 ) 3.01 × 10−13 5.19 × 10−13 4.16 × 10−13 2.43 × 10−13 3.50 × 10−13 6.12 × 10−13
Fouling resistance without PAC RFW (m−1) 3.45 × 10−13 6.39 × 10−13 7.61 × 10−13 2.43 × 10−13 3.83 × 10−13 7.61 × 10−13
Fouling resistance with PAC RFP (m−1 ) 1.79 × 10−13 4.54 × 10−13 6.93 × 10−13 0.99 × 10−13 2.08 × 10−13 5.92 × 10−13
a
Source water.
 V. Ravindran et al. / Journal of Membrane Science 344 (2009) 39–54
analysis of membrane flux data under various scenarios is primor-
dial before pilot-scale and full-scale design are undertaken. This
approach shall be important in evaluating membrane susceptibil-
ity to fouling, and shall play a significant role in selecting suitable
membrane material, type, configuration, and cleaning strategy.
6. Summary and conclusions
The hybrid MBR process with PAC and microorganisms was
effective in removing nitrate, NOM, THMFP, alachlor, and MS-2,
meeting the overall treatment objectives. The technology appears
to be ideally suited for small-scale systems such as well-head appli-
cations.
The alachlor removals could be attributed to the synergistic
effect of PAC and microbial sorption. The MS-2 removals at steady
state could possibly be attributed to the following mechanisms: (i)
rejection by NOM gel layer, (ii) rejection by microbial biomass layer,
(iii) rejection due to internal pore blocking by NOM molecules, (iv)
adsorption on the membrane surface, PAC and bio-particles, and
(v) combinations of these mechanisms.
The MBR tests provided valuable information on membrane
fouling and flux decline patterns that might prove beneficial in pro-
cess design for specific applications. The studies demonstrated that
fouling occurred in three distinct stages: the initial period when
fouling occurred due to the exposure of the membrane to the feed
with fast flux decline (during the first few minutes of process opera-
tion), the period of rapid fouling with substantial flux decline rates,
and slow fouling with low flux decline rates. The permeate flux
decline patterns observed were characteristic of a water treatment
scenario involving NOM, BOM, microbial biomass and colloids at
low concentrations.
The use of the foulant classification method instead of the
phenomenological classification approach in the resistance model
provided a more realistic portrayal of membrane fouling and flux
decline in MBR processes for drinking water applications.
The permeate flux data from MBR studies showed that although
PAC addition initially enhanced transient-state permeate fluxes, no
significant improvement was observed in steady-state fluxes.
Acknowledgments
The authors extend their appreciation to the Metropolitan
Water District of Southern California for providing in-kind con-
tribution at various stages of this project. Any statements made
or opinions expressed in this article are those of the individual
authors and do not necessarily represent or reflect the views of
the agency. Any reference made in this publication to any specific
method, product, process or service does not constitute or imply
endorsement, recommendation, or warranty thereof by the agency.
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