Laboratory and Field Evaluation of a Pretreatment
System for Removing Organics from
Produced Water
Soondong Kwon\ Enid J. Sullivan^ Lynn E. Katz^ Robert S. Bowman^ Kerry A. Kinney^*
ABSTRACT: Co-produced water from the oil and gas industry
accounts for a significant waste stream in the United States. This
"produced water" is characterized by saline water containing a variety of
pollutants, including water soluble and immiscible organics and many
inorganic species. To reuse produced water, removal of both the
inorganic dissolved solids and organic compounds is necessary. In this
research, the effectiveness of a pretreatment system consisting of
surfactant modified zeolite (SMZ) adsorption followed by a membrane
bioreactor (MBR) was evaluated for simultaneous removal of carbox-
ylates and hazardous substances, such as benzene, toluene, ethylbenzene,
and xylenes (BTEX) from saline-produced water. A laboratory-scale
MBR, operated at a 9.6-hour hydraulic residence time, degraded 92% of
the carboxylates present in synthetic produced water. When BTEX was
introduced simultaneously to the MBR system with the carboxylates, the
system achieved 80 to 95% removal of BTEX via biodégradation. These
results suggest that simultaneous biodégradation of both BTEX and
carboxylate constituents found in produced water is possible. A field test
conducted at a produced water disposal facility in Farmington, New
Mexico confirmed the laboratory-scale results for the MBR and
demonstrated enhanced removal of BTEX using a treatment train
consisting of SMZ columns followed by the MBR. While most of the
BTEX constituents of the produced water adsorbed onto the SMZ
adsorption system, approximately 95% of the BTEX that penetrated the
SMZ and entered the MBR was biodegraded in the MBR. Removal rates
of acetate (influent concentrations of 120 to 170 mg/L) ranged from 91
to 100%, and total organic carbon (influent concentrations as high as
580 mg/L) ranged from 74 to 92%, respectively. Organic removal in the
MBR was accomplished at a low biomass concentration of 1 g/L
throughout the field trial. While the transmembrane pressure during the
laboratory-scale tests was well-controlled, it rose substantially during the
field test, where no pH control was implemented. The results suggest
that pretreatment with an SMZ/MBR system can provide substantial
removal of organic compounds present in produced water, a necessary
first step for many water-reuse applications. Water Environ. Res., 83, 843
(2011).
' Mine Reclamation Corp., Seoul, Republic of Korea.
•^ Los Alamos National Laboratory, Chemical Diagnostics and Engineer-
ing Group, Los Alamos, New Mexico.
^ University of Texas-Austin, Department of Civil, Architectural and
Environmental Engineering, Cockrell School of Engineering, Austin,
Texas.
* New Mexico Institute of Mining and Technology, Department of Earth
and Environmental Sciences, Socorro, New Mexico.
•University of Texas-Austin, Department of Civil, Architectural and
Environmental Engineering, Cockrell School of Engineering, TX 78712;
e-mail: kakinney@mail.utexas.edu.
September 2011
KEYWORDS: produced water, membrane bioreactor, surfactant
modified zeolite, carboxylate, benzene, toluene, ethylbenzene, and
xylenes (BTEX).
doi:10.2175/106143011X12928814445212
Introduction
Co-produeed water is the high-volume wastewater stream
generated during oil and gas produetion. In the United States
alone, it is estimated that as mueh as 9.1 million m^ (57 million
barrels) per day of water are produced from both onshore and
offshore faeilities (Clark and Veil, 2009). As disposal eosts rise
and water resourees beeome searee, treatment and reuse of this
waste stream at onshore faeilities beeomes more feasible (Darby
et al., 2007). Reeent interests inelude reusing produeed water for
hydraulie fraeturing and biofuel production. Produeed water is
eharaeterized by high total dissolved solids (TDS), dissolved
organies, dissolved formation minerals, and oil and grease. A
variety of treatment options have been investigated to' remove
the eomplex mixture of pollutants present in produeed water.
For offshore facilities, which are constrained by size limitations,
physical/chemical methods are preferred, while, for onshore
facilities, a wider range of alternatives, including biological
treatment, are possible (Fakhru'1-Razi et al., 2009). Among the
organics present in the water, the concentration of hazardous
substances, such as benzene, toluene, ethylbenzene, and xylenes
(BTEX) ean reaeh 600 mg/L, and the concentration of non-
hazardous carboxylates can be as high as 10 000 mg/L
(American Petroleuhi Institute, 2002). To improve the cost-
effectiveness of salt removal proeesses, sueh as reverse osmosis,
the eoneentration of dissolved organie eompounds in the
produeed water needs to be redueed.
Current methods used to remove organies after initial oil-
water separation inelude teehniques such as hydrophobic
filtration or aetivated earbon treatment. While these methods
are effeetive at removing nonpolar organies (Miller et al., 1997;
Santos and Wiesner, 1997), they are less effeetive at removing
polar organie eompounds, sueh as aleohols or earboxylates.
Beeause organie eompounds and the mierobial growth that
results from the degradation of these eompounds are
signifieant sources of fouling in reverse osmosis membrane
systems (Amiri and Samiei, 2007; Greenlee at al., 2009;
Richardson et al., 2007), a pretreatment system to remove
organics from produced water should reduce cleaning and
843
Kwon et ai.
maintenance costs and extend the lifetime of membranes used
in reverse osmosis systems.
Surfactant-modified zeolite (SMZ) has been evaluated for the
removal of a number of dissolved contaminants from aqueous
solutions, particularly for BTEX compounds (Altare et al, 2007;
Bowman et al, 1995; Janks and Cadena, 1992; Neel and
Bowman, 1992; Ranck et al, 2005). Zeolites are hydrated
aluminum tectosilicates characterized by cage-like structures
having high internal and external surface areas and high cation
exchange capacities. Low organic carbon contents (<0.5%) in
natural zeolite limit the sorption of organic compounds. The
organic carbon content and organic sorption affinity is enhanced
greatly by adding a surfactant, such as hexadecyltrimethylam-
monium cation (HDTMA), to the natural zeolite to create an
SMZ. The HDTMA is commonly used in products such as hair
conditioner, mouthwash, and fabric softener and is bound
strongly to zeolite surfaces (Li and Bowman, 1998). Once SMZ is
saturated with volatile organic compounds (VOCs), it can be
regenerated using air-sparging (Li and Bowman, 2001). Ranck et
al. (2005) reported successful removal of BTEX from produced
water by adsorption on both virgin and regenerated SMZ.
Related testing verified that there was no significant reduction of
BTEX sorption capacity over at least 50 sorption/regeneration
cycles (Altare et al., 2007). This ability to regenerate SMZ and its
low cost (approximately $450 per metric ton) make it
a promising sorbent for the treatment of produced water.
Although the regeneration process produces a gas stream
contaminated with VOCs, a relatively low-cost vapor-phase
bioreactor can be used to remove the volatile compounds
present in the gas stream (Kwon, 2007).
While SMZ has excellent adsorption properties for BTEX, the
removal of polar carboxylates, such as acetate and malonate, is
not expected in SMZ systems. One option for removing both
polar and nonpolar organics from produced water is to use
a biological treatment system. For example, Tellez et al. (2005)
operated a field-scale activated sludge system and achieved 92%
removal of chemical oxygen demand (COD) from produced
water containing 34,110 mg/L TDS at a 12-hour hydraulic
retention time (HRT) and a 20-day solids retention time (SRT).
Dalmacija et al. (1996) enhanced the performance of an activated
sludge system treating oil-field brine wastewater by diluting the
wastewater with river water and adding powdered activated
carbon (PAC). Lu et al. (2009) operated a field-scale hydrolysis
acidification/bio-contact oxidation system (HA/BCO) and
achieved removal efficiencies of 63.5% for COD and 68.0% for
total petroleum hydrocarbons (TPH) at a 32-hour HRT.
Membrane bioreactors (MBRs) also have been used successfully
to treat municipal wastewater and drinking water (Marrot et al.,
2004), although application to industrial wastewaters is still under
development because of the significant variations in wastewater
composition (Chen and Chen, 2004). Nevertheless, treatment of
saline-produced water with an MBR is promising for several
reasons. The MBRs can be operated at longer SRTs, which may
improve the degradation of recalcitrant pollutants (Livingston,
1993) and improve biological treatment in harsh environments,
such as in briny wastewater. Bakx et al. (2000) observed greater
than 83% removal of COD in oil-contaminated water (sea water)
from naval warships using an MBR, and Scholz et al. (2005)
obtained 88% removal of COD and 99% removal of biochemical
oxygen demand (BOD) in an MBR treating a briny tannery effluent.
844
The objective of this research was to investigate the feasibility
of using a combined physicochemical/biological pretreatment
system to remove the organic constituents present in saline-
produced water. The investigation focused on two classes of
organic compounds that are commonly present in produced
water—carboxylates that often are present at high concentra-
tions, and BTEX, which is representative of the hazardous'
constituents present. The capacity of an MBR to treat the
carboxylate and BTEX contaminants present in produced water
was evaluated first in the laboratory as a stand-alone unit and
then in the field, where the MBR was coupled with an SMZ
system treating produced water at a site in New Mexico.
Methods and Materials
Laboratory-Scale Membrane Bioreactor System. The ex-
perimental MBR (Figure 1) was 8 L in volume, rectangular in
shape (10 cm X 22 cm X 49 cm high), and constructed of 1.3 cm
(0.5-in.) Plexiglass. Preliminary testing confirmed that adsorp-
tion of the target organics to the bioreactor was negligible. The
system was aerated at 10 L/min via an air diffuser located
directly beneath the bioreactor membrane. The aeration system
provided sufficient oxygen (>3.5 mg/L dissolved oxygen) to
sustain the microorganisms and provided membrane scouring to
minimize fouling. A flat sheet microfiltration membrane
(Enviroquip, Inc., Austin, Texas) consisting of a 0.4-|i.m-pore-
size, ultrasonically welded polyethylene sheet was suspended in
the MBR, as shown in the schematic. The dimensions of the
membrane plate were 22.5 cm X 32 cm X 0.6 cm, yielding
a total membrane area of 1170 cm^. The experimental bioreactor
was designed with a cap that could be sealed to enable collection
of gas-phase effluent samples.
A synthetic produced water solution with a TDS level of
approximately 10 g/L was provided to the MBR at a rate of 14
mL/min, yielding an HRT of 9.6 hours in the system (Table 1).
The system was inoculated with biomass obtained from an
activated sludge sample collected from the South Austin
Wastewater Treatment Plant (Texas). The SRT was maintained
at 100 days by withdrawing 80 mL of biomass solution daily
from the MBR. The synthetic produced water used in the
laboratory experiments contained 0.10 g/L NH4CI, 0.10 g/L
KNO3, 0.12 g/L MgSO4, 0.22 g/L CaClz, 0.15 g/L KCl, 9 g/L
NaCl, 0.46 g/L NajSO*, and 0.10 g/L KH2PO4. Acetate'and
malonate concentrations in the synthetic produced water
influent were maintained at 260 and 170 mg/L, respectively,
throughout phases 1 to 4 of the laboratory testing period
(Table 1). The composition of the synthetic produced water was
selected to mimic the composition of the produced water found
at the New Mexico field site. The influent carboxylate feed to the
MBR was supplemented with gas-phase BTEX during phase 2
and dissolved BTEX introduced with the liquid influent phase
during phase 3. Each BTEX component was introduced at
concentrations consistent with their proportions in the pro-
duced water at the field site (Kwon, 2007). For the gas-phase
supply, BTEX was provided through the aeration line located
beneath the membrane, while, for the liquid-phase supply,
a mixing chamber was installed upstream of the bioreactor to
mix the BTEX with the carboxylates before injection to the
bottom of the MBR. In field applications, gas-phase VOCs are
present during produced water storage, although most BTEX
would be dissoived in the influent-produced water. In the final
Water Environment Research, Voiume 83, Number 9
 Kwon et al.

Aqueous .
BTEX Feed

Waste
water -•Permeate (Effluent)
Mixing Suction
Chamber Pump
Off gas/Overflow
Submerged
membrane
Bio eactor

Gas Phase
Syringe Pump
BTEX Feed

Air filter Compressed air

Airdiffuser

Figure 1—Sciiematic diagram of tiie expérimentai membrane bioreactor system. The gaseous BTEX feed was used only in pbase 2,
wbiie tbe aqueous BTEX feed was used only in pliase 3 of tbe experiments.

Table 1—Operating and feed conditions for tiie laboratory-scaie MBR experiments.

Feed conditions
Compounds Phase 1 Phase 2 Phase 3 Phase 4
Carboxylates (mg/d)
Malonate 3427 3427 3427 3427
Acetate 5221 5221 5221 5221
BTEX (mg/d) Gaseous teed Aqueous teed
Benzene 460 460
Toluene 840 840
Ethylbenzene 50 50
p<Sm-xylene - 310 310 -
o-xylene 140 140

Operating conditions
Parameter Phases 1 to 4
MBR volume (L) 8
Flowrate (mL/min) 14
Aeration rate (L/min) 10
HRT (hours) 9,(
SRT (days) 100
Temperature (°C) 21

September 2011 845

Kwon et ai.

phase of experimentation (phase 4), the BTEX supply to the Table 2—Composition ot produced water used in the field test.
MBR was terminated to determine whether the presence of
BTEX affected the removal of the carboxylates in the MBR. Anaiyte Concentration (mg/L)
Periodically throughout the experiment, the pH of the influent
TDS 10717.00
produced water solution was adjusted by adding a dilute HNO3 TOC 571.00
solution to evaluate the effect of influent pH on the treatment Oil & grease 45.40
process.
Voiatiie organics
Field-Scale SMZ-MBR System. A test of the coupled SMZ
2- Hexanone 0.47
adsorption and MBR system was performed at a salt water 1.07
Benzene
disposal facility in Farmington, New Mexico. Most water Carbon disultade 0.15
delivered to the site is from gas production wells, with 50% or Ethylbenzene 0.46
less from oil production locations. Produced water delivered to Toluene 4.74
the site is pretreated using oil-water separation, sand filtration, Xylene (total) 4.63
and flltration with fiber-wound 5- and 1-micron filters before Acetone 2.17
deep well re-injection. The water used for this test was selected Semi-volatiie organics
randomly from the post 5-micron filtered stream and was stored 0.26
Phenoi
in a sealed plastic 1900-L (500-gal) tank before our treatment Napiithalene 0.05
tests. The temperature of the influent water varied between 21 2-Methylnaphthaiene 0.06
and 24°C. bis(2-Etiiylbhxyi)phthaiate 0.36
The chemical composition of the produced water used in the m,p-Cresols 0.11
field test was analyzed by GEL laboratories LLC (Charleston, o-Cresole 0.11
South Carolina), and the results are summarized in Table 2. The Anions
TDS level of 10,717 mg/L was similar to the value reported in Bromide 18.10
our previous research (Kwon, 2007). The TOC concentration Suifate 484.00
was determined to be 571 mg/L, and several VOCs and Ciiloride 5540.00
semivolatile organic compounds (SVOCs) were detected, with Acetate 150.00
BTEX comprising the major percentage by mass. Several anions Cations
were identified, including chloride, sulfate, acetate, and bromide. Barium 4.06
Metals and cations, such as sodium, calcium, potassium, Calcium • 108.00
magnesium, and barium, also were identified in the produced iron 1.37
water samples. The acetate concentration in the produced water Magnesium 28.80
was determined to be 150 mg/L. Manganese 0.44
Potassium 104.00
The zeolite used in the study was obtained from the St. Cloud Sodium 4160.00
mine near Winston, New Mexico. It was crushed and sieved to
a size range of 1.4 to 0.4 mm (14 to 40 mesh). Sullivan et al.
(1997) characterized the mineral composition of the zeolite as before entering the MBR (Figure 2). The produced water
follows: 74% clinoptilolite, 5% smectite, 10% quartz/cristobalite, flowrate through the SMZ column was set at 25 mL/min. Only
10% feldspar, and 1% illite. The HDTMA-Cl was used as the a portion of the SMZ effluent was directed to the MBR, which
surfactant in the production of HDTMA-zeolite, as described by was operated at a fiowrate of 14 mL/min, an HRT of 9.6 hours,
Bowman et al. (2001), v^áth 14 to 40 mesh zeolite particles similar and an SRT of 100 days. External nutrients (Table 3) were
to material used in previous laboratory and field testing. The supplied directly to the MBR, as shown in Figure 2. Compressed
loading of HDTMA onto the zeolite surface was 180 mmoL of air was supplied at a flowrate of 7.5 L/min to an air diffuser
HDTMA/kg zeolite, similar to that used in previous field and located directly beneath the bioreactor membrane.
laboratory tests (Altare et al., 2007). Because of the accumulation of foulants on the membrane,
A CuUigan fiberglass tank (35.5-cm internal diameter, 121.9- the effluent flowrate slowly decreased with time, resulting in an
cm height) was packed with SMZ (bottom 65%) and raw zeolite unbalanced flowrate between the influent and effluent streams.
(top 35%) to a total packed capacity of 104.7 L. With this packing To address this problem, a water-level controller (vertical-
method, any surfactant potentially desorbed from the SMZ mounted liquid level switch. Omega Engineering Inc., Stamford,
would be captured by the raw zeolite placed downstream. Connecticut) was installed to control the influent pump rate and
Dissolved surfactant can be biocidal and therefore was maintain a constant water level in the MBR. To reduce
scavenged from the treatment stream before contact with the membrane fouling, daily brushing of the membrane surface
biological system in the MBR. was used during the initial 14 days of operation. Subsequently,
The same MBR (i.e., 8-L total reactor volume) and poly- the daily brushing was supplemented with periodic submersion
ethylene membrane (0.4-|xm pore size) used in the laboratory in one of the following cleaning solutions to further reduce the
tests was used in the field tests. The biomass used in laboratory transmembrane pressure (TMP): (1) a 0.5% hypochlorite
tests was transported to the field site to reduce the acclimation (NaOCl) solution, (2) a 1% citric acid (C6H8O7) solution, or
period required for the field testing. (3) a 1% nitric acid (HNO3) solution.
Table 3 summarizes the operating conditions of the SMZ/ After the system reached stable operating conditions, 2 to 5 g/
MBR treatment system during the field test. During the test, L of PAC (NUCHAR SA-T 1320-R-05, MeadWestvaco Inc.,
produced water passed through the SMZ adsorption column Covington, Virginia) was added into the MBR (2 g/L on day 27

846 Water Environment Research, Voiume 83, Number 9

 Kwon et al.

Table 3—Operating conditions of the SMZ/MBR system during and 0.5 mM from 40.5 to 44 minutes. For the analysis of BTEX,
the field test. aqueous and gaseous samples were collected individually. Gas
samples were collected with 0.5-mL gas-tight syringes from
Operational parameters Values sampling ports and analyzed immediately. A Hewlett-Packard
SMZ column volume (L)
5890 gas Chromatograph (GC) (Agilent Technologies, Santa Clara,
105
MBR volume (L) 8
California) fitted with a 30-m Restek capillary column (RTX-624;
internal diameter = 0.53, film thickness = 3.0) and flame-
Flowrate (mL/mIn)
ionization detector (FID) was used to analyze BTEX.
Through SMZ colunnn 25 p-xylene and w-xylene were not resolved by this method and
Through MBR 14 were treated as a single compound. Five-mL aqueous samples
Aeration rate in MBR (L/min) 7.5 were collected from sampling ports and placed in 22-mL
HRT in MBR (hours) 9.6 headspace vials (HP5182-0837,' AgUent Technologies), which
SRT in MBR (days) 100 were loaded onto a Tekmar 7000 headspace autosampler for
PAC amount (g/L) 2-5 analysis on the GC/FID. Total suspended solids (TSS) and volatile
pH of influent 8.5
suspended solids (VSS) concentrations of mixed-liquor samples in
Temperature (°C) 21
the MBR were measured according to Standard Methods (APHA
Nutrient addition (L/d) 1
et al, 1995) sections 2540D and 2540E, respectively. The TMP
NH3CI (g/L) 4
was measured in-line with a manometer connected to the tubing
KNO3 (g/L) 4
KH2PO4 (g/L) 4 on the suction side of the permeate pump.
Field-Scale Experiments. Treatment system monitoring in-
cluded both off- and on-site analyses. Off-site analyses of the
produced water were conducted at the University of Texas-
and another 3 g/L on day 29) to investigate the effect of PAC on Austin, as described above, for the carboxylates, TOC, TSS, and
the performance of the MBR, particularly for organic removal VSS. Analyses of VOCs, SVOCs, cations, and anions were
and potential flux increase. An average PAC particle size of conducted by DHL Analytical (Round Rock, Texas). The on-site
100 |xm was obtained by passing the material through a 120X200 field analyses included measuring aqueous phase BTEX concen-
mesh sieve. trations in the influent and effluent and gas-phase BTEX
Analytical Techniques. Laboratory-Scale Experiments. concentrations in the MBR offgas. The on-site aqueous and
Carboxylate concentrations in the influent and effluent of the gaseous BTEX concentrations were measured using a Hewlett-
MBR were measured using a Dionex AS 40 auto-sampler Packard model 5890A gas Chromatograph (Agilent Technologies)
(Thermo Fisher Scientific, Sunnyvale, California) attached to with a 10-m, 0.53-mm internal diameter HP-5 capillary column
DX-600 ion Chromatograph. The ion Chromatograph was and FID. For analysis of the BTEX concentrations in aqueous
equipped with a Dionex CS25A conductivity detector, an ASRS samples, 2.5-mL aliquots of each water sample were placed in
ULTRA 4-mm suppressor, an EG50 eluant generator, and an a 10-mL vial fitted with a Teflon-faced butyl septum. The vial was
IonPac ASll-HC analytical column (Thermo Fisher Scientific). placed in a heating block and equilibrated at 80°C for 15 minutes.
The oven temperature was maintained at 30°C for each run, the A 0.5-mL gas-tight syringe was used to extract gaseous samples
suppressor current was set at 300 mA, and the flowrate of the from the headspace for subsequent analysis on the gas
eluant (KOH) through the column was 1 mL/min. The eluant Chromatograph. The BTEX concentrations in gaseous samples
concentration was set as follows: 1 mM for the first 4 minutes, from the sampling ports of the MBR were analyzed by direct
2 mM from 4.2 to 13.2 minutes, 10 mM from 13.5 to 28 minutes, injection to the same gas Chromatograph. Additional on-site
2 mM from 28.5 to 30 minutes, 30 mM from 30.5 to 40 minutes. analyses included TMP and temperature of the produced water.

Nutrient Solution

•a—i^
Desalination
Process
Natural
Zeolite

SMZ

aeration
Produced SMZ MBR
water Column
Figure 2—Schematic diagram of the SMZ/MBR treatment system used to treat produced water at the field site near Farmington,
New Mexico.

September 2011 847

Kwon et al.

Results and Discussion 100 -immmmmm * * t » * # • • • • • • • • • • • • • • » » • • • • » • • • • • •

Laboratory-Scale Membrane Bioreactor System. Carbox- 90
ylate Removal in Phases 1 and 2. The MBR system used in this
researeh yielded more than 99% removal of aeetate from the O 80
produeed water feed and 85% removal of the influent malonate
70
(Figure 3a) during the first 43 days of operation. The pH of the
influent stream was 4.8 (beeause of the malonie aeid in the feed), s: £0
while the pH of the outlet stream inereased to 8.0 during this
50
period, as a result of the mierobial oxidation of aeetate and 10 20 30 40 SO 60 70 80 90
malonate. To determine whether the removal of malonate eould Days
be improved by adjusting the pH, the pH of the mixed liquor in
the MBR was adjusted to 7.0 by the addition of dilute HNO3 on • Acetace DMalonntc
day 43. The removal of malonate inereased to 95% when the pH
was adjusted to 7.0 and subsequently deereased back to (A)
approximately 85% removal when the pH adjustment was
discontinued on day 63. One possible reason for the enhaneed
100 100
removal of malonate at pH 7.0 is a ehange in malonate
speeiation as a funetion of pH. To investigate this possibility, 80 80
malonate speeiation was ealeulated as a funetion of pH using " • •
«0
O •
MINEQL+ (Seheeher and MeAvoy, 1992), whieh uses the Davies ••••
equation to eorreet for ionie strength. However, the speeiation 40 40
ehange at pH 7 and pH 8 was minimal (data not shown), •
20 oo o o o 20
indieating that it is not responsible for the inerease in malonate
removal. Nevertheless, the results indieate that pH affeets o o O ^
malonate removal, but not aeetate removal (whieh remained 60 70 75 80 85 90
essentially eonstant during the pH adjustment period). These
Davs
results also suggest that the biodégradation of earboxylates in
produeed water is quite feasible, despite the high salinity
• % blo-degraded OEfliuen
eonditions.
BTEX Removal During Phase 2. A gaseous BTEX mixture (B)
was provided to the MBR at a rate of 1800 mg/d from day
55 through day 90; the corresponding gas-phase concentration
of eaeh of the BTEX constituents was as follows: benzene =
10.0 ppmv, toluene = 15.5 ppmv, ethylbenzene = 0.8 ppmv,
p&w-xylene = 5.0 ppmv, and o-xylene = 2.2 ppmv. As shown in
Figure 3b, the amount of BTEX in the liquid-phase effluent I
deereased to <5 ng/L as the experiment continued. With the
exception of benzene, which had a maximum effluent concen-
tration of 88 ng/L (which exceeds the U.S. Environmental
Protection Agency [Washington, D.C] [U.S. EPA] Maximum
Contaminant Level [MCL] of 5 |ig/L), the maximum concentra-
tions of the aromatic hydrocarbons detected in the liquid-phase
10 20 30 40 50 60 70 80 90
effluent at the beginning of test (230.5 |xg/L toluene, 48.8 ng/L
ethylbenzene, and 182.70 ng/L total xylenes) were far below the
respective MCLs set by U.S. EPA for drinking water (i.e.,
1000 |ig/L for toluene, 700 ng/L for ethylbenzene, and o Biomass (mg/L) -TMP (kPa)
10 000 ng/L for total xylenes). By the end of the experiment,
(C)
all of the effluent BTEX constituents were below their respective
MCLs. Figure 3—Laboratory-scale experimental results during phases 1
The difference between the quantity of BTEX introduced to and 2: (a) removal of acetate and malonate in tbe MBR during
the MBR and the measured quantities exiting in the liquid and phases 1 and 2. Note that tbe pH in tbe MBR was adjusted to 7.0
gas phases were used to estimate the BTEX removal in the from 8.0 by tbe addition of HNO3 (from day 43 to day 63). (b)
system resulting from biodégradation. When BTEX was in- Effiuent BTEX concentrations and % BTEX biodegraded in tbe
troduced via the gas phase, 19.6% of the BTEX mass introdueed MBR during phase 2. (C) Biomass concentration (MLVSS) and
to the MBR was emitted in the offgas, and 80.3% of the BTEX TMP in the MBR during phases 1 and 2.
supplied was biodegraded (Figure 3b). The results of ' this
experiment verify that simultaneous BTEX and earboxylate suspended solids [MLVSS]) of approximately 1 g/L were
biodégradation can occur in an MBR treating produced water. maintained in the MBR when only carboxylates were supplied
Biomass Concentration and Trans-Membrane Pressure During to the reactor (day 1 through day 55, Figure 3c). For comparison,
Phases 1 and 2. Biomass concentrations (mixed-liquor volatile a second MBR was operated at the same HRT (9.6 hours) and

848 Water Environment Resaarcli, Volume 83, Number 9

 Kwon et al.

influent carboxylate concentrations, but in a low-ionic-strength 100 »» • • • • • • • • • • »•• 5000

nutrient solution (0.55 g/L TDS compared with 10 g/L TDS used
in this research) (Garcia, 2007). This MBR achieved similar 90 4000 =ä
carboxylate removal, but produced higher biomass concentra-
tions of approximately 4.5 g/L. Because high biomass concen- 80 3000 i
trations will tend to yield higher biofouling rates, it is of interest
to note that treating briny produced water in an MBR resulted in BTEX supply
70 terminated &
lower biomass concentrations. This result is not unexpected, CD bioinass diluted
^
because microorganisms in high-ionic-strength solutions have to O
60 1000
expend greater energy to maintain their internal osmotic _o
pressure within acceptable limits and thus have less energy
50
available for biomass production (Kempf and Bremer, 1998).
10 15 20 25 30 35
While the biomass concentration in the MBR was quite low
Days
when only carboxylates were present in the bioreactor, the
biomass concentrations did increase (up to 3 g/L) after the • Acetate DMalonate 0 MLVSS
introduction of the BTEX compounds to the MBR on day 55
(phase 2). (A)
Membrane fouling, resulting from the formation of a layer
or cake on the membrane and/or the intrusion of molecules,
100 500
colloids, and particles in the porous structure, is one of the «••-,
main drawbacks of MBR systems (Marrot et al., 2004). As • •_•
80 400
expected, the TMP in this MBR system increased with time, as • •
shown in Figure 3c, and it was suspected that the formation of o •
S 60 300 .
inorganic precipitates was responsible. One way to decrease •
0
membrane fouling resulting from the formation of precipitates 40 200 T
is to decrease the pH of the MBR solution. As shown in •
0
Figure 3c, the TMP initially decreased (25 kPa) when the pH 20 o
of the MBR was adjusted from 8.0 to 7.0 (day 43 through day oo oOOo
• 0
63), suggesting that pH control can help minimize the TMP. ^.^ o o.
However, note that the biomass concentration in the MBR 10 15 20 25
increased when BTEX was added to the system and the TMP Davs
began to rise again. To investigate the pH effect on TMP, the
pH of the MBR solution was decreased sequentially to 2.5, by • Vo bio-degi-aded O Efnuent -
adding dilute HNO3 directly to the MBR reactor at the end of
experiment; as a result, the TMP decreased dramatically from (B)
88 kPa at pH 7.6 to <0.1 kPa at pH 5.0. Although maintaining Figure 4—Laboratory-scale experimental results during phases 3
the pH of the MBR solution below 5.0 would greatly reduce and 4: (a) Carhoxylate removal and biomass concentration in the
the TMP, additional experiments will be necessary to de- MBR during phases 3 and 4. Note that the BTEX supply was
termine the optimal pH level that simultaneously maintains terminated and biomass was diluted on day 25. (b) Liquid-phase
biological activity and reduces membrane fouling and TMP to effluent BTEX concentrations and % biodegraded in the MBR
acceptable levels. during phase 3.
Other applicable options to reduce membrane fouling are
increasing aeration in the vicinity of the membranes (Gui et al., Biomass Concentrations and Carboxylate Removal during
2003; Kishino et al., 1996; Ognier et al, 2002), high-frequency Phases 3 and 4. During Phase 3, liquid phase BTEX was
backpulsing, or chemieal washing (Hu and Stuckey, 2007; Ng supplied simultaneously with acetate (260 mg/L) and malonate
and Fane, 2006; Park et al., 1999; Seo et al., 2004; Yoon et al., (170 mg/L). The biomass concentration (MLVSS) increased
2005). In addition, coagulants, flocculants, and surfactants (Deng gradually to 3 g/L, similar to the level measured in phase 2, in
et al, 2005; Deriszadeh et al., 2010; Fakhru'1-Razi et al, 2009; which the gas-phase introduction of BTEX (Figure 4a) led to an
Zhou et al., 2000) commonly are used to reduce membrane increase in biomass from 1 to 3 g/L. In phase 4, the, liquid phase
fouling. In this research, 10 L/min of air was supplied via a line BTEX supply was disconnected (on day 25), and the biomass
diffuser located directly beneath the membrane to reduce the concentration was also diluted to 1 g/L manually (phase 4). Only
membrane fouling and supply oxygen to the MBR. Also, the carboxylates were provided to the MBR, and the biomass
membrane was cleaned every week by submersion in a 0.5% concentration was monitored. As shown in Figure 4a, the
hypochlorite (NaOCl) solution for 2 hours. As a result, the TMP biomass concentration in the MBR remained at nearly 1 g/L
increases were periodic in nature; after each cleaning, the until the end of the test. To estimate the biomass production
pressure dropped to approximately 0 kPa and subsequently rose resulting from the two different types of substrate, the
to 60 kPa over the next week of operation. Submerged-type theoretical yield coefficients {Y, mass of cell synthesized per
MBRs typically have TMP values of approximately 50 kPa mass of substrate consumed) were calculated using a bacterial
(Marrot et al., 2004). Thus, the MBR treating the produced water energetics approach (Rittman and McCarty, 2001). Results from
in this research was within this range. this analysis indicate that the K-values for BTEX (average

September 2011 849

 Kwon et al.
1,02 mg cell/mg substrate) are several times higher than those
for the carboxylates (0,35 mg cell/mg substrate for acetate and
0,30 mg cell/mg substrate for malonate). However, the amount
of BTEX introduced to the MBR was 4,8 times less than the
amount of carboxylate introduced (Table 1), Thus, the biomass
production in the MBR resulting from BTEX biodégradation
should be approximately 40% of the total production, and the
remaining biomass production should be the result of the
biodégradation of the carboxylates. Thus, the 3-fold increase in
biomass concentration in the bioreactor following the in-
troduction of BTEX cannot be explained solely by the increase
in biomass resulting from BTEX consumption, although it
certainly contributed.
Carboxylate removal in phases 3 and 4 was similar to the
previous phases, with more than 99% removal of the acetate in
the produced water feed and 88% removal of the influent
malonate (Eigure 4a), These carboxylate removals (averaging
95% overall removal) were not affected by the biomass
concentration change or presence or absence of BTEX supply,
suggesting that the MBR could be used effectively to remove
carboxylates from produced water,
BTEX Removal During Phase 3. Figure 4b summarizes the
BTEX removal in the MBR during phase 3, when the liquid-
phase BTEX (90 mg/L) and carboxylates were provided
simultaneously to the MBR. As shown in the figure, the amount
of BTEX in the liquid phase effluent decreased to below 5 ng/L
as the experiment continued. Mass-balance calculations indicate
that the fraction of the dissolved BTEX that was removed as
a result of biodégradation increased to approximately 95% as the
experiment continued. This removal was higher than that
observed in phase 2, when BTEX was provided in the gaseous
phase, a result which is not surprising given the volatility of
BTEX, Removal of BTEX via volatilization into the offgas stream
was 5.21% during the aqueous feeding phase, which was lower
than that observed in phase 2 (19,62%), where BTEX was
provided in the gaseous phase,
Field-Scale SMZ-MBR System. Biomass concentrations
(MLVSS) of approximately 1 g/L were maintained during the
entire field trial, comparable with the levels observed in the
• laboratory MBR pretesting. Considering the fact that a typical
activated sludge system has biomass concentrations of 3 g/L
while MBRs typically have even higher biomass concentrations
of up to 30 g/L (Jefferson et al,, 2000; Yamamoto et al„ 1989),
this biomass concentration is very low. Because high biomass
concentrations tend to yield higher biofouling rates, it is of
interest to note that treating briny-produced water in an MBR
resulted in lower biomass concentrations. The influent pH of the
produced water was 8,5 and increased slightly (pH = 8,8) during
the MBR operation period. The dissolved oxygen concentration
in the MBR was maintained at approximately 2,5 mg/L,
Carboxylate Removal. One of the important objectives of
the field test was to remove carboxylates from produced water.
The predominant organic anion detected in the produced water
at the site was acetate, and its concentration was measured
before and after the SMZ column, and after the MBR, The
influent acetate concentration varied from 120 to 170 mg/L
during the experiment. As expected, the SMZ column had little
effect on the removal of acetate from produced water (Figure 5
a), because acetate is polar in nature. However, consistent with
the laboratory-scale test, acetate was removed to below detection
850
limits in the MBR, indicating that the MBR system is an effective
treatment for carboxylates in produced water. Because a range of
other organic compounds are also present in produced water
(Table 2), TOC concentrations were monitored throughout the
treatment system. Results provided in Figure 5b show that both
the SMZ column and the MBR contributed to the overall
removal of organics. The influent produced water contained an
average TOC of 580 mg/L, which was reduced to 350 mg/L in
the SMZ column. However, as the SMZ column became
saturated, the TOC level exiting the SMZ column increased to
480 mg/L, The TOC level in the effluent from the MBR
decreased to approximately 150 mg/L, providing an overall TOC
removal of 74% in the SMZ/MBR system. Following PAC
addition to the MBR on day 27, the MBR effluent TOC
concentration decreased to 45 mg/L (Figure 5b), yielding an
overall TOC removal of 92%,
The high salinity of produced water and water scarcity in
many oil-and-gas-producing areas makes reverse osmosis
systems an attractive option for producing water suitable for
reuse. The level of pretreatment required will depend on the
reverse osmosis membrane; in general, a turbidity less than 1,0
NTU, Silt Density Index (SDI) less than 3,0 or 4,0, and oil-and-
grease levels less than 1,0 mg/L are desirable (Alawadhi, 1997),
Even though the acceptable organic level in reverse osmosis feed
water varies, some reverse osmosis membrane manufacturers
(e,g., Filmtec [Dow Chemical, Midland, Michigan] and Hydra-
nautics [Oceanside, California]) recommend TOC levels less
than 3.0 mg/L for efficient reverse osmosis system operation.
Although the current MBR system achieved 74 to 92% removal
of the influent TOC, the final effluent concentration exceeded
this level. Nevertheless, the SMZ/MBR system did provide
substantial organic removal and could reduce the burden on
conventional pre-treatment technologies to reduce organic
fouling (Prihasto et al„ 2009).
BTEX Removal. Benzene, toluene, ethylbenzene, and xylenes
are classified as hazardous pollutants, even at low concentra-
tions. For discharge or reuse applications, removal of these
VOCs is strongly recommended. The laboratory-scale MBR
experiment revealed that the MBR could remove these BTEX
compounds in synthetic produced water, but BTEX removal in
actual produced water may vary because of the other
constituents present (Table 2), Figure 6a shows the BTEX
concentrations in the produced water at the field site before
and following SMZ and MBR treatment. As shown in the figure,
the BTEX concentration in the influent-produced water to the
SMZ system decreased as the experiment progressed (from 70 to
10 mg/L), This decrease resulted from the increase in headspace
(and subsequent BTEX volatilization) in the produced water-
storage tank used to supply water to the system. The BTEX
concentrations in the SMZ treatment column effluent increased
gradually, as shown in the figure, as a result of the slow
penetration of BTEX through the SMZ, Individual analysis of
BTEX compounds showed that only benzene exhibited complete
breakthrough of the SMZ during the field test. The BTEX was
allowed to break through to provide a means for monitoring the
BTEX reductions within the MBR, because BTEX removal
efficiencies for SMZ were determined previously (Altare et al.,
2007; Kwon, 2007; Ranck et al„ 2005),
A maximum BTEX concentration of approximately 5 mg/L in
the SMZ column effluent occurred at the end of the field test. The
Water Environment Research, Volume 83, Number 9
 Kwon et ai.

B
I'iO . m

•a 1^ • 9 •B 1 i • t ••
•
Î
100 - •

50 •

A
0 - —AAA -AT!^ AA A -A-ib-A- - A - •A--A--A-- A - r-A- - A - -A- - A - -A 1
10 15 20 25 30 35
Days

* Pre-SMZ B Post-SMZ/Pne-MBR A Post-MBR

(A)

700

600 •
• • • • • • • •
m
500
• •
'S) 400
A m
• B • m •
«300

200 A
A A
A A A
100
A
A A A
0
10 15 20 25 30 35
Days

• Pre-SiVlZ m Post-SiVIZ/Pre-MBR A Post-MBR

(B)
Figure 5—Organic removals during SMZ/MBR fieid test: (a) Acetate concentrations, and (b) TOC concentrations. Note the etfect ot PAC
addition on day 27 to post-iVIBR results.

BTEX concentration exiting the MBR ranged from 0.01 to 0.55
mg/L, with an average value of 0.117 mg/L (Figure 6b). With the
exception of benzene, the maximum concentrations of the
aromatic hydrocarbons detected in the liquid-phase effluent from
the MBR were below the MCLs set by U.S. EPA for drinking
water. These low BTEX concentrations in the MBR effluent
resulted from a combination of volatilization and biodégradation.
To provide a basis for determining the relative contribution of
each of these mechanisms to BTEX removal, gas-phase BTEX
concentrations from the MBR were measured in addition to the
aqueous phase concentrations. Figure 6b shows the total mass of
BTEX introduced to the MBR (all liquid-phase) per day and the
total mass of BTEX (liquid and gas phase) exiting the reactor per
day. The difference between these two values was attributed to
BTEX removal by biodégradation. As shown in Figure 6b, up to
95% of the BTEX introduced to the MBR was biodegraded,
indicating that the MBR could be used effectively to remove
BTEX from produced water. Removal of BTEX by volatilization
was 2.9%, resulting in an overall removal efficiency of 97.8%.
Transmembrane Pressure. One of the main drawbacks of the
MBR system is membrane fouling, which reduces the flux
through the membrane and increases the TMP. As described
before, there are several possible methods to reduce the TMP in
an MBR, including physical removal techniques and chemical
washes (Gui et al, 2003; Hu and Stuckey, 2007; Kishino et al.,
1996; Ng and Fane, 2006; Ognier et al., 2002; Park et al., 1999;
Seo et al., 2004; Yoon et al., 2005). During the initial 14 days of
operation of the field MBR test, daily brushing of the membrane
surface was used to prevent excessive membrane fouling and
maintain the flux through the membrane (Figure 6c). This
method was sufficient to maintain the TMP levels below 30 kPa
after brushing. However, after 2 weeks of operation, this simple
brushing technique was not always capable of reducing the TMP
level to below 30 kPa, and the TMP increase accelerated.
While brushing still was partially effective (see days 18 and 24,
in particular), several membrane washing methods also were
investigated to determine if they could clean the membrane and
further reduce the TMP during operation. The different
methods used in the field included submerging the membrane
for several hours in one of the following solutions: (1) 0.5%
hypochlorite (NaOCl) solution, (2) 1% citric acid (C6H8O7)
solution, or (3) 1% nitric acid (HNO3) solution. However, these

September 2011 851

Kwon et al.

70

60

3- 50 5 00 J

£ 40 4 sâ
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S 2iÄ
o. 20 --•—•^
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I A A A ^ A A A A A A ^ A A A A

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• Pre-SMZ • Post-SMZ/Pre-MBR A Post-MBR

(A)

100 -I 100
A *
80 80
•D
V
•O
5, 60 60
• • ÍS
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(B)

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D
D
• D D
20 - * n
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10 15 20 25 30 35
Days

• Before-Brushing DAfter-Bmshing

(C)
Figure 6—Removal of VOCs and TMP during SMZ/MBR field test: (A) Liquid-phase BTEX concentrations. Note that the influent BTEX
concentration (left scale) decreased with time as evaporation occurred from the source water tank. Post-SMZ concentrations (right
scale) were allowed to increase to test the MBR capability to remove BTEX. (B) BTEX degraded by biomass in MBR. (C) TMP in the
MBR system.

852 Water Environment Researcb, Volume 83, Number 9


washing techniques had little effeet on TMP levels and
membrane elogging. On day 27, 2 g/L of PAC was added to
the MBR, and another 3 g/L was added 2 days later. Adding PAC
to the MBR ean enhanee the removal of organie matter through
eontaminant adsorption. Also, in some systems, PAC addition
has been shown to deerease the TMP by inereasing the average
floe size and providing a shear foree on the membrane (Ng and
Fane, 2006; Park et al, 1999; Seo et al, 2004). However, PAC
addition to the MBR had little effeet on membrane elogging in
this field test.
During the laboratory-seale evaluation of the MBR, it was
found that deereasing the pH of the influent below 7.0 deereased
the TMP to below 25 kPa (Figure 3e). In the field, the pH was
not controlled, and the pH of the mixed liquor in the MBR rose
to 8.8, which enhanced the potential for forming inorganic
precipitates that would foul the membrane and raise the TMP.
Future studies with specific field-sourced produced waters will
be required to evaluate the effeet of pH reduetion or frequent
membrane baekwashing on TMP. Any eleaning regimen should
be matehed to the quality and inorganie ion eomposition of the
treated water.
Conclusions
The effeetiveness of a submerged MBR for simultaneous
removal of earboxylates and hazardous BTEX eonstituents
from saline-produeed water was evaluated through laboratory-
and field-scale experiments. Laboratory testing showed that an
aerobic, submerged MBR aehieved 92% removal of earboxylates
(100% aeetate and 85% malonate removal) at a 9.6-hour HRT.
Adding BTEX to the produeed water feed inereased the
biomass eoneentration in the MBR, but did not affeet the
earboxylate removal. Approximately 80 to 95% of the BTEX
eonstituents were biodegraded in the MBR, implying that
MBRs ean aehieve high removal of earboxylates and BTEX
eonstituents simultaneously in briny wastewater. A eoupled
SMZ/MBR system ean be used to simultaneously remove the
earboxylate and BTEX eonstituents present in produeed water
under field eonditions. Acetate (the predominant organic anion
detected in the produced water at the field site in New Mexico)
was not removed in the SMZ column; however, it was removed
to below detection limits in the MBR. The SMZ column
removed most of the BTEX constituents in the produced water
during the field trial; however, approximately 95% of the BTEX
that penetrated the SMZ and entered the MBR was
biodegraded in the MBR. These results confirm that an MBR
can be used to remove BTEX constituents from produced
water that has moderate TDS levels (e.g., 10 g/L). Overall, the
combined SMZ/MBR system achieved TOC removal efflcien-
cies ranging from approximately 74 to 90%. The results of the
laboratory and field experiments suggest that the range of
possible pre-treatment options for saline wastewater reuse
applications can be expanded to include SMZ and MBRs. One
drawback associated with the MBR system was membrane
fouling by inorganic precipitates. Deereasing the pH of the
solution was effective at reducing the TMP, but the optimal pH
that maximizes biological activity while minimizing the TMP
still must be determined. Additional studies are required to
optimize the field system to reduce membrane fouling through
either pH eontrol or an alternative approaeh to reduee
membrane fouling.
September 2011
Kwon et al.
Credits
This work was fimded by the U.S. Department of Energy
(Washington, D.C.) under eontraet number DE-FC26-
04NTI5546. SMZ for the field experiments was provided by
the St. Cloud Mine, Winston, New Mexieo. Josh Simpson of
New Mexieo Teeh (Soeorro, New Mexieo) and Chia-Chen Chen
of the University of Texas-Austin assisted with the field
experiments.
Submitted for publication July 26, 2010; revised manuscript
submitted Deeember 8, 2010; aeeepted for publieation February
16, 2011.
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Water Environment Research, Volume 83, Number 9