The impact of metallic coagulants on the removal of organic compounds from oil sands process-affected water.

Abstract

Coagulation/flocculation (CF) by use of alum and cationic polymer polyDADMAC, was performed as a pretreatment for remediation of oil sands process-affected water (OSPW). Various factors were investigated and the process was optimized to improve efficiency of removal of organic carbon and turbidity. Destabilization of the particles occurred through charge neutralization by adsorption of hydroxide precipitates. Scanning electron microscope images revealed that the resultant flocs were compact. The CF process significantly reduced concentrations of naphthenic acids (NAs) and oxidized NAs by 37 and 86%, respectively, demonstrating the applicability of CF pretreatment to remove a persistent and toxic organic fraction from OSPW. Concentrations of vanadium and barium were decreased by 67-78% and 42-63%, respectively. Analysis of surface functional groups on flocs also confirmed the removal of the NAs compounds. Flocculation with cationic polymer compared to alum, caused toxicity toward the benthic invertebrate, Chironoums dilutus, thus application of the polymer should be limited.

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Published:August 26, 2011
r2011 American Chemical Society
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pubs.acs.org/est
The Impact of Metallic Coagulants on the Removal of Organic
Compounds from Oil Sands Process-Affected Water
Parastoo Pourrezaei,†Przemyszaw Drzewicz,†Yingnan Wang,†Mohamed Gamal El-Din,†,*
Leonidas A. Perez-Estrada,‡Jonathan W. Martin,‡Julie Anderson,§Steve Wiseman,§Karsten Liber,§
and John P. Giesy§,||,^,#,3
†Department of Civil and Environmental Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G 2W2
‡Division of Analytical and Environmental Toxicology, University of Alberta, Edmonton, Alberta, Canada, T6G 2W2
§Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan, Canada, S7N 5B3
)
Department of Veterinary Biomedical Sciences, University of Saskatchewan, Saskatoon, Saskatchewan, Canada, S7N 5B3
^Department of Zoology, and Center for Integrative Toxicology, Michigan State University, East Lansing, Michigan, United States
#Zoology Department, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
3Department of Biology & Chemistry, City University of Hong Kong, Kowloon, Hong Kong, SAR, China
b
S Supporting Information
’INTRODUCTION
Coagulation/Flocculation (CF) is among the most widely
used processesto removesuspendedand colloidal particles from
waterandwastewater.Additionally,itisusedtodecreaseconcen-
trations of dissolved organic matter.1?3Because of their small
size and surface charge, without any pretreatment, suspended
particles are difficult to remove by filtration or sedimentation.
Moreover, suspended solids may interfere with ultraviolet light
(UV)-based advanced oxidation processes (UV/ozone, UV/
hydrogen peroxide) by scattering light, thus reducing the effi-
ciency of these processes.4Therefore, removal of the suspended
particles may improve the performance of filtration, advanced
oxidation, and membrane separation processes.4?6
CF is a potential pretreatment option for treating oil sands
process-affected water (OSPW) generated from oil sands opera-
tions in northern Alberta, Canada. OSPW, generated after Clark
hotwaterextraction,containsacomplexmixtureoforganiccom-
pounds, salts and a stable suspension of fine particles.5,7Among
the complex mixtures of organics in OSPW are a class of water-
soluble,alicycliccompounds,collectivelyclassifiedasnaphthenic
acids (NAs).8Their general formula is CnH2n+ZO2, where
nrepresentsthenumberofcarbonatomsandZisanegativeeven
integer representing the number of rings.9,10
Numerous studies have focused on the application of second-
ary and tertiary treatment technologies, including biological
treatments,advancedoxidationprocesses(AOP)andmembrane
filtration for treatment of OSPW.6,7,10?14Bioremediation has
recently been studied for the removal of organic compounds
fromOSPW.7,14,15Microbialdegradationhasprovedtobeavery
slow process due to the acute toxicity and persistency of NAs.10
Ozonation was shown to not only incompletely degrade NAs,
but alsoto generate more oxidizedNAs.10,13Some oxidized NAs
might resemble the sex steroids compounds that may show endo-
crinedisruptingactivity.16,17Nanofiltration successfullyremoved
more than 95% of NAs and divalent ions from OSPW without
any pretreatment.6However, reversible fouling caused by sus-
pended solids decreased the permeate flux and life cycle of the
Received:
Accepted:
Revised:
May 2, 2011
August 25, 2011
August 23, 2011
ABSTRACT: Coagulation/flocculation (CF) by use of alum
and cationic polymer polyDADMAC, was performed as a
pretreatmentforremediationofoilsandsprocess-affectedwater
(OSPW). Various factors were investigated and the process was
optimized to improve efficiency of removal of organic carbon
and turbidity. Destabilization of the particles occurred through
charge neutralization by adsorption of hydroxide precipitates.
Scanningelectronmicroscopeimagesrevealedthattheresultant
flocs were compact. The CF process significantly reduced
concentrations of naphthenic acids (NAs) and oxidized NAs
by 37 and 86%, respectively, demonstrating the applicability of CF pretreatment to remove a persistent and toxic organic fraction
from OSPW. Concentrations of vanadium and barium were decreased by 67?78% and 42?63%, respectively. Analysis of surface
functional groups on flocs also confirmed the removal of the NAs compounds. Flocculation with cationic polymer compared to
alum, caused toxicity toward the benthic invertebrate, Chironoums dilutus, thus application of the polymer should be limited.

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membrane,whichlimitedthepracticalapplicationofnanofiltration.6
It was expected that CF pretreatment of OSPW would decrease
the particle and organic loading on the subsequent treatment
processes and enhance the performance of remediation processes.
Chemical coagulants can be effective if they can destabilize
charged particles to facilitate agglomeration. Aluminum sulfate
(alum) is among the most commonly used coagulants in waste-
water treatment processes because of its availability and low
cost.3,18,19The successful use of iron salts and polyaluminum
chloride (PACl) was also reported.2,19?21PACl has been shown
to be a stable compound with the minimum effect on the pH
of the water.3Flocculants, which are mainly synthetic organic
polymers, have been extensively used to enhance coagulation
performance.18,22Among flocculants, cationic polymers have been
reportedtobemoreeffective thananionicornonionicpolymers.
Addition of the polymers may intensify membrane fouling,
whereas it could enhance the granular filtration performance by
increasing the particle attachment to the filter media.18
Depending on the coagulant concentration and water char-
acteristics, various mechanisms, such as charge neutralization,
adsorption, and sweep flocculation can be responsible for the
removal of organic compounds and particles.3,18Elevated con-
centrations of the residual ions in the treated water, arising from
coagulant addition, necessitate further treatments. Therefore,
carefulmonitoringofthecoagulantdoseisrequiredtoobtainthe
lowest concentration of the residual ions, which can be achieved
through measurement of charge and ion concentrations. Zeta
potential analysis is a critical evaluation for the characterization
andquantificationofthecharge,withwhichitispossibletobetter
understand the CF performance and identify the removal
mechanism.
In the present study, thehypothesisthat the application of CF
as a pretreatment for OSPW decreases the concentrations of the
various constituents present in OSPW was tested. In order to
achieve this, the effectiveness of using metallic salt coagulants of
alum, ferric sulfate, ferric chloride, and three organic polymers
(cationic, anionic, and nonionic) for the removal of the particles
and organic compounds and also changes in concentrations of
NAs were determined. Moreover, identification of coagulation
mechanismbyzetapotentialmeasurementandassessmentofthe
properties of the flocs, such as size and surface functional groups
were performed.
’MATERIALS AND METHODS
Sampling. OSPW was collected on October 2009 from the
west in-pit (WIP) tailings pond located at the Syncrude Canada
Ltd. facility, Fort McMurray, Alberta, Canada. OSPW was received
and stored at 4 ?C. Before conducting the experiments, OSPW
was slowly brought to room temperature. A complete character-
ization of the OSPW is presented in Table 1.
Coagulation and Flocculation. All the coagulation/floccula-
tionexperimentswereconductedatroomtemperature(19?22?C)
and the natural pH of the OSPW. Experiments were performed
in triplicate and parameters of the process water, detailed below,
were measured before and after treatment based on standard
methods.23Turbidity and TOC were measured before and after
the establishment of optimum condition. Quantification of NAs
and oxidized NAs, scanning electron microscopy (SEM) ima-
ging, surface functional groups characterization of the flocs, and
waterqualityanalysesweremeasuredfortheoptimumcondition.
Coagulants.Theinitialstepinoptimizationoftheprocesswas
selectionofthecoagulanttype.Metallicsaltcoagulantsofaluminum
sulfate(alum),ferricsulfate,andferricchloride(FisherScientific,
NJ) were separately applied in each jar to form a series of
concentration of: 0, 20, 50, 80, 100, 150, 200, 250, 300, 350,
400, 450, 500, 550, and 600 mg/L. Coagulantswere added at the
beginningoftheexperiments.Initialcoagulationconditionswere
30sofrapidmixingat120rpmfollowedby30minofslowmixing
at 30 rpm. Any flocs formed were allowed to settle for 60 min.
Based on the total organic carbon (TOC) removal and turbidity
reduction, alum and ferric sulfate showed superior performance
compared to ferric chloride (Figure S1 and S2 in the Supporting
Information). Alum and ferric sulfate resulted in the same
removalefficiencies.However,additionoftheferricsaltsresulted
in a reddish color of treated OSPW with higher color intensity at
higher coagulant concentration. OSPW contains organic com-
poundswhichactascomplexingagentstowardiron(III)toimprove
its solubility.24As a result of formation of these complexes, a
colorchangeintherangeofyellowtobrownisobserved.Because
the experiments were performed at pH higher than theoptimum
pH (∼7) and high concentration of ferric salts was added to
achieve satisfactory TOC removal, an increase in the intensity of
the yellow-brown color was observed. Since this might require
additional treatment for color removal, alum, the most commonly
used coagulant, was chosen for further optimization. Because the
increment ofthealum concentrationshowed anincreasingtrend
ofTOCremovalandturbidityreduction, toinvestigatetheeffect
of other factors, including organic polymer type, concentration
and addition time of organic polymer, as well as mixing intensity
and time, optimization experiments were performed at 100, 250,
and 500 mg alum/L.
Polymer. The cationic polymer polydiallyldimethylammo-
nium chloride (polyDADMAC), the anionic polymer polyacry-
lamide, and the nonionic polymer polyacrylamide (ClearTech,
Edmonton, Canada) were used as flocculants. PolyDADMAC is
a low molecular weight polymer with a 100% cationic content.25
There are two possible polymeric structures of polyDADMAC
including N-substituted piperidine and N-substituted pyrrolidine.26
Additionally, polyDADMAC has a stable positive charge below
Table 1. Complete Characterization of the Oil Sands
Process-Affected Water
parametersaverage value
pH
turbidity (NTU)
TOC (mg/L)
COD (mg/L)
NAs (mg/L)
NAs-oxidized (mg/L)
alkalinity (mg/L)
conductivity (μS/cm)
sodium (mg/L)
chloride (mg/L)
sulfate (mg/L)
ammonium (mg/L)
aluminum (mg/L)
iron (mg/L)
vanadium (mg/L)
barium (mg/L)
8.5
180
51
240
23.6
31.6
630
3750
827
515
513
22
8.5
3.3
0.018
0.35

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pH of 10,18thus a change in the pH during the process does not
affect the polymer charge.
To investigate the effect of the cationic polymer at each con-
centrationofalum,a32factorialdesignexperimentwasappliedat
three dosages and addition times. The three concentrations of
polymer were 2, 5, and 10 mg/L, and the polymer addition time
during the coagulation was 0, 15, and 30 s. A similar procedure
was utilized for the anionic and nonionic polymer.
Mixing Intensity and Time. Once the optimum conditions for
polymer were determined, the effect of rapid mixing intensity at
80, 120, and 220 rpm was investigated while other factors were
keptfixed.Atallthreeconcentrationsofalum,mixingat120rpm
resulted in higher TOC removal and turbidity reduction. The
effect of slow mixing time on the coagulation performance was
also investigated by varying this parameter from 0 to 60 min
while all the other factors were kept at the optimized condition.
Equipment.APhipps&Birdjartestapparatus,equippedwith
apaddlestirrerandsquarePlexiglasbeakers,wasusedtoperform
the coagulation experiments. Quantification of the NAs was
performed by ultra pressure liquid chromatography/high resolu-
tionmassspectrometry(UPLC/HRMS),asdescribedbyMartin
et al.10Zeta potential measurements were conducted using a
ZetaPALS, Brookhaven Inc. apparatus. All measurements were
performed in triplicate for nonfiltered samples. Diffuse Reflec-
tance Fourier Transform Infra Red (FT-IR, BioRad FTS 6000)
spectrophotometer was used to identify the surface functional
groups in the flocs. SEM of the flocs was performed using a
HITACHI S-2500 instrument. X-ray photoelectron spectrosco-
py (XPS) measurements were performed using a AXIS 165
spectrometer (Kratos Analytical). Details of the quantification
methods for pH, turbidity, TOC, alkalinity, major ions, trace
metals, and other water quality analyses are provided in the
Supporting Information.
Analysis of NAs by High-Resolution Mass Spectrometry.
Sampleswerefilteredthrough0.22μmsyringefilters(MillexGS,
Millipore). Tetradecanoic acid-1-13C (C14H28O2) was added to
each sample (0.2 μg/mL), as internal standard, to correct for
sensitivity and retention time drift. Instrumental analysis was
performed by a Waters Acquity UPLC System (Waters, MA),
employed for rapid and efficient chromatographic separation of
the NAs and their oxidized products. High-resolution measure-
ments were performed in-line with a high resolution (∼10000)
QSTAR Pulsar i mass spectrometer equipped with a TurboIon
Spray source (Applied Biosystem/MDS Sciex, Concord, ON,
Canada) operated in negative mode.
Chromatographic separations were run on an Acquity phenyl
BEH column (150 ? 1 mm, 1.7 μm i.d.) using a gradient mobile
phase of (A) 10 mM ammonium acetate solution prepared in
Optima-grade water and (B) 10 mM ammonium acetate in 50%
methanol and 50% acetonitrile, both Optima-grade. Gradient
elutionwas:1%Bfor2min,rampedto60%Bby3min,to70%B
by 7 min, to 95% B by 13 min, holding it until 14 min and finally
returnedto1%Bfollowedyanequilibrationtimeof5.8min.The
flowwasconstantat0.110mL/minandcolumntemperaturewas
50 ?C. The chromatographic system separated NA based on
carbon number (n), degree of cyclization(Z), and extent of alkyl
branching. Relative response to the internal standard for each
NA isomer class was plotted over time to determine the
concentration and NAs profile. A blank was run at the beginning
of the batch to subtract background effects from the samples. As
well, a blank was placed as the last sample batch to assess any
carry-over effect.
Invertebrate Toxicity Tests. Chironomus dilutus larvae
(13?14 days postoviposition) were exposed to fresh water as a
controlsample,OSPW,OSPWtreatedwith250mg/Lalum,and
OPW treated with 250 mg alum/L plus 5 mg cationic polymer
polyDADMAC/L. Prior to the initiation of exposures, the OSPW
and treated samples were aerated as required (3?4 weeks) to
minimize ammonia concentrations. Ten animals were randomly
assignedto300mLglassbeakers,containingapproximately1cm
of silica sand (particle size 200?400 μm) and 250 mL of the
respective water samples. Animals were fed 0.67 mg dry weight/
individual daily with TetraFin fish food slurry (Tetra Company,
Blacksburg, VA) and water changes (50% renewal) were per-
formed every 2 days. A constant stream of air was bubbled into
each beaker. Water samples were collected prior to the water
change for assessment of water chemistry. Temperature and pH
readings were taken daily from one randomly selected row of
beakers to monitor general water quality. The exposure was
performed for 10 days in an environmental chamber maintained
at 23 ?C and all exposures were performed in quadruplicate.
’RESULTS AND DISCUSSION
Optimization. The application of nonionic and anionic poly-
mers showed adverse or no effect on the TOC removal. The
optimal time for addition of cationic polymer was 15 s from
the beginning of the coagulation. Addition of the polymer at the
beginning of the coagulation may affect the performance of the
alumandalso its addition at 30 smightnotprovide thesufficient
interaction with the particles due to the charge neutralization
mechanism discussed later. For 100, 250, and 500 mg alum/L,
theoptimalcationicpolymerconcentrationswerefoundtobe10,
5, and 2 mg/L, respectively. Rapid mixing intensity at 80 rpm
might not be enough to provide necessary contact between the
chemicals andtheparticles,andhigh intensity mixingat 220 rpm
may cause the breakage of the flocs.21For slow mixing, TOC
removal was the same for all the mixing times less than 30 min.
Increasing the mixing time to higher than 30 min decreased the
TOC removal. This could be explained by the effect of the
prolongedmixingonthebreakageoftheflocsduetothecleavage
of the bonds in the precipitated hydroxides.27,28Therefore,
10 min was chosen for the slow mixing time at 30 rpm.
OSPW was characterized before and after CF treatment
(Table S1 in Supporting Information). The conductivity of the
samples did not change, indicating the inability of CF treatment
to remove inorganic dissolved solids. The pH value decreased
slightly after addition of the coagulant. Dissolved aluminum ion
has been suggested to contribute to the Alzheimer’s disease.18,29
However,aluminumconcentrationdecreasedupto96%fromits
initial concentration. Therefore, coagulation-flocculation treat-
ment did not increase its concentration in the OSPW, which
eliminate any possible link with Alzheimer’s disease. Turbidity
reduction was greater than 90% at all three concentrations of
alum and reached 99% at 500 mg/L of alum. The addition of the
cationicpolymerateachconcentrationofalumslightlyimproved
the removal of TOC.
OSPWtreatedwith250mgalum/L,250mgalum/Lplus5mg
polymer/L, and 500 mg alum/L were analyzed for concentra-
tionsofNAsandtheresultsshowednodifferencesintheremoval
of NAs andoxidizedNAs. Additionof500 mg/Lofalum increased
the salinity of OSPW by 50% after the process. There was no
differenceintheremovalofTOCandturbidityinOSPWtreated
with 100 mg alum/L, compared to OSPW treated with 250 mg

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alum/L. Nevertheless, 250 mg alum/L was chosen as the optimum
condition to allocate the safety range for suspended solids and
TOC fluctuations in OSPW.5
’REMOVAL MECHANISMS
Metallic Salt Coagulant. Distribution of aluminum species
depends on the pH of minimum solubility and total aluminum
concentration. Speciation distribution for aluminum after the
addition of 90 mg alum/L showed that over pH range of 4.5?9,
aluminum hydroxide precipitates (Al(OH)3) are the predomi-
nant species.18,30The surface charge of the precipitates is
determined by their isoelectric point,3which is approximately
8 for aluminum hydroxides. Thus, at the operational pH used in
this study, the surface of the precipitates was positively charged.
Positively charged hydroxide precipitates contribute to the
destabilization of the particles.3,22,30Destabilization occurs by
deposition of the hydroxides on the surface of the negatively
charged particles through adsorption and heterocoagulation.
Thisprocessresultsinchargeneutralizationoftheparticles.Dissolved
organic compounds could be also adsorbed and neutralized by
the positively charged precipitates resulting in their lower solubility
and precipitation.
Phenolicandcarboxylicfunctionalgroupsoforganiccompounds
could also be neutralized by the positively charged hydrolysis
products of alum (Al(OH)2+, Al(OH)2+), which exist in smaller
concentrations compared to hydroxides. This process results in
lower solubility and subsequent removal.3In addition, these
functional groups might form complexes with Al3+ions,18and
removaloftheorganiccompoundsandparticlescoatedwithorganic
compounds result in the reduction in their concentration.
Zeta potential measurement was used to characterize and
quantify the charge of the particles, to better understand the
performance of CF and determine the removal mechanism.
Measurement of changes in zeta potential and turbidity, caused
by the increase of alum concentration, showed that the zero zeta
potential point was not reached (Figure 1). Therefore, at the
optimum concentration of alum, only charge neutralization
through adsorption could be the removal mechanism.30How-
ever, to reach complete charge neutralization higher concentra-
tionofalumshouldbeapplied,whichwouldnotbeeconomically
and practically justifiable due to the additional associated pro-
blems including greater amounts of sulfate ions.
By increasing the concentration of alum, a reduction in the
turbidity was observed, yet the zeta potential remained negative
and slowly approached zero. A similar trend has been reported
previously.3The authors of that report proposed an adsorption
mechanism of the organic compounds on the surface of the
precipitates.30The zeta potential reached the point of charge
neutralization by adding 1000 mg alum/L, after which a slight
increase in the turbidity was observed. An increase in the
concentration of positively charged hydrolysis products may
cause the restabilization of the suspension.
Effect of Cationic Polymer Addition.Among the advantages
of cationic polymer application are the decrease in the concen-
tration of metallic salt coagulant, alkalinity consumption, and
sludge production.31Due to the high charge density and low
molecular weight of the polyDADMAC, charge neutralization is
the proposed removal mechanism. SEM images of the flocs,
(Figure 2) indicate that the flocs formed by the addition of both
alum and alum plus polymer are small and compact.32?34
Therefore, it can be concluded that charge neutralization is the
removal mechanism.34Although addition of the polymer re-
sulted in slightly greater removal of TOC, it also resulted in
greater toxicity of the treated OSPW (see the Toxicity to Inverte-
brates Section).
Removal of Trace Metals. Concentrations of vanadium and
barium decreasedby67?78% and42?63%, respectively. Removal
Figure 1. Zeta potential and residual turbidity ((std. of five replicates)
vs amount of alum added.
Figure 2. SEM images of the flocs formed by (a) 250 mg/L alum, (b) 250 mg/L alum with 5 mg/L cationic polymer.

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mechanisms of vanadium and barium might involve either
adsorption of soluble metals to the active sites of the hydroxide
or formation of complexes with organic compounds and cop-
recipitation.35Also, vanadium(V) could form insoluble precipi-
tates, such as AlVO4, with aluminum ions. Due to the high
concentration of added sulfate and the negligible solubility of
barium sulfate in water, barium removal could be related to the
formation of the insoluble salt.
Naphthenic Acids. CF is most suitable for removing sus-
pended solids. However, in the current study, it was found that
the concentration of dissolved NAs were significantly less in
OSPW treated by CF. Similar results for the removal of an
anionic surfactant (which had similar properties and structure to
NAs) using alum have been reported previously.36High-resolu-
tion MS analysis of NAs and oxidized NAs, before and after
treatment with 250 mg alum/L are shown (Figure 3). High
resolution MS analysis of NAs after CF treatment has not been
reported to date. OSPW is a complex mixture and the concen-
tration of its constituents may vary.5In this case, the concentra-
tionofoxidizedNAs(CnH2n+ZO3)was34%higherthantheNAs
(CnH2n+ZO2). Therefore, removal of both kinds of NAs should
be considered of similar importance.
After CF treatment, NAs and oxidized NAs were removed by
37%and86%,respectively.Presenceofadditionaloxygengroups
in oxidized NAs may play an important role in complexation
ability toward metals and oligomerization of the complexes, and
formation of flocs.37Residual concentration of NAs was
14.9mg/LforNAsand4.3mg/LforoxidizedNA.Removalsofthe
NAs for all the Z groups (number of rings) was 1.3?1.7 times;
except for the Z = 8 group of compounds where removal was
slightly higher, 2.2 times. Oxidized NAs were removed over the
range of all carbon numbers, and compounds with a higher Z
number were preferentially removed; removal of oxidized NAs
with Z = 2, 4, 6, 8, 10, and 12, was 2.2, 2.9, 20.5, 23.8, 8.7,
15.5?times, respectively. There were no differences in removal
of oxidized NAs withdifferent carbon numbers. The solubility of
NAs decreases as number of rings increases, which is beneficial
for the CF. In contrast, the carbon number does not affect the
solubilityofthecompoundsasmuchasthenumberofringsdoes.
These results are consistent with the fact that CF is generally
moreeffectivefortheremovaloforganiccompoundswithhigher
molecular weight.3
FT-IR Spectral Analysis. FT?IR spectroscopy was used to
characterize the surface functional groups present in the OSPW
and flocs. The spectra of dried OSPW and flocs formed after
treatment with 250 mg alum/L are presented (Figure 4). The
observed spectra of the dried OSPW and OSPW treated with
alum were similar, with a slight shift in peak positions, which
indicated the removal of the compounds from the OSPW into
the flocs.
Figure 3. Estimated total concentration (E.T.C.) of NAs for (a) fresh OSPW (b) after CF treatment with 250 mg/L alum, and oxidized NAs for
(c) fresh OSPW (d) after CF treatment with 250 mg/L alum.

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Thebroadabsorptionbandintheregionof3700?3000cm?1
indicated the presence of OH functional groups.38These might
be related either to water in the samples or the hydroxyl groups.
Although samples were air-dried, the absorption band may be
related to the presence of trapped water inside the flocs.
Alternatively, the broad absorption band indicating hydroxyl
groups could be related to the presence of the oxidized NAs in
the dried OSPW and flocs.
Spectra for carboxylic acids consist of three absorption
bands.38An absorption band near 1260 cm?1was characteristic
of C—O stretching vibration and the second was observed near
1670 cm?1, which was characteristic of CdO stretching vibra-
tion. These observations, together with the absorption band of
OH groups in the region of 3300?2500 cm?1indicated the
presence of the carboxylic groups in the compounds. It also
confirmedthepresence ofNAsandoxidizedNAsinthesamples.
Therefore, these findings confirmed the removal of these com-
pounds from OSPW to the formed flocs.
To confirm the removal of these compounds from OSPW to
the formed flocs, XPS analysis was performed on the flocs. XPS
spectraoftheflocsshowedapeakat∼74eV,whichindicatedthe
presence of the Al oxide?oxyhydroxides based on the informa-
tion from other researchers.39,40The peak at ∼532 eV indicated
the binding energy characteristic of the hydroxides and sulfates.
C—Hfunctionalgroupspresentinthehalogenatedcompounds,
hydrocarbon oil, and carboxylic acids are characterized by the
peak at ∼285 eV.41?45The presence of the carboxylic groups is
also indicated by the peak at ∼289 eV.43,45?49The chemical
composition analysis by XPS also showed that oxygen, carbon,
and aluminum were the major elements in the flocs by the mass
concentrationof46.2,17.5,and20%,respectively.Togetherwith
FT-IRanalysis,itindicatedthepresence oftheNAsaswellasthe
aluminum hydroxide and sulfates in the flocs. Moreover, the
removal of the NAs was confirmed by the analysis using the
UPLC/HRMS.
ToxicitytoInvertebrates.Growthandsurvivalofthebenthic
midge (Class Insecta, Chironomus dilutus) was assessed by exposing
animals to a fresh water control, untreated OSPW, OSPW treated
with 250 mg alum/L, and OSPW treated with 250 mg alum/L
plus 5 mg polyDADMAC/L. Survivals of C. dilutus (Figure S3 in
the Supporting Information) in fresh water and OSPW were not
significantly different (p = 0.05)50and were 97.5% and 100%,
respectively.SurvivalofC.dilutusexposed toOSPWtreatedwith
alum was 75%, but this was not significantly different (p = 0.05)
from the survival in the freshwater control or OSPW. However,
survival of C. dilutus exposed to OSPW treated with alum plus
cationic polymer was 42.5%, which is significantly less than
survival in the freshwater control and OSPW. In addition to
effects on survival, decreased growth of C. dilutus relative to the
control was observed following exposure to each of the OSPW
samples (Figure S4 in the Supporting Information). There was
nostatisticallysignificantdifferenceingrowthofanimalsexposed
toOSPWcomparedtoalum-treatedOSPW.However,growthof
C. dilutus exposed to OSPW treated with alum plus polymer was
significantly less than growth of midges in all other treatment
groups. These results indicated that the addition of the cationic
polymer significantly increased the toxicity of treated OSPW.
OSPW was also proved to be toxic to Daphnia magna based on a
48 h acute lethality test.51Cationic polymers with quaternary
amines including polyDADMAC were shown to be toxic to the
aquatic organisms such as rainbow trout (Oncorhynchus mykiss),
Daphniapulex,andfatheadminnow(Pimephalespromelas);52?54
there may be a synergistic effect of the cationic polymer or
monomer present in the polymer and NAs compounds which
induced toxicity.25Therefore, based on the relatively slight increase
in the contaminant removal from the OSPW by addition of the
polymer compared to the coagulant alone, it is recommended to
apply only the metallic salt coagulant.
Environmental Significance and Future Work. The results
of the current study demonstrate that CF is a reliable pretreat-
mentprocessandcouldreducetheimpactthatOSPWhasonthe
environment. This treatment could be combined with other
secondary and tertiary treatment processes to enhance the
performance and reduce the overall process time of the system.
In addition to complete turbidity reduction, organic compounds
were efficiently reduced. Moreover, application of alum over the
ferric salt coagulants is preferred in regards that it was shown to
not only enhance the treatment efficiency, but also to decrease
Figure 4. Infrared spectra of the flocs using (a) dried OSPW, (b) flocs formed after CF treatment with 250 mg/L alum.

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Environmental Science & Technology
ARTICLE
the concentrations of dissolved aluminum ions in the treated
waters eliminating any possible link with Alzheimer’s disease.
Morphology of the floc indicated that metallic salt coagulants
generated compact flocs. Further characterization of the flocs is
currently under investigation to examine regrowth ability of the
flocs after breakage. Toxicity is a major indicator for the usability
of a selected process for the remediation of OSPW. The toxicity
approach using an aquatic invertebrate showed that the pretreat-
ment does not significantly increase the toxicity of the treated
water. However, when the cationic polymer polyDADMAC was
added over the metallic salt coagulant greater toxicity was
observed. Therefore, this combination is not recommended in
order to reduce the environmental impact of this pretreatment.
’ASSOCIATED CONTENT
b
S
Supporting Information.
water quality analyses, complete water analysis results, detailed
methodologyfortoxicitytests,andrelatedgraphsareprovidedin
the Supporting Information. This material is available free of
charge via the Internet at http://pubs.acs.org.
Quantification methods for
’AUTHOR INFORMATION
Corresponding Author
*Phone: +1 780 492 5124; fax: +1 780 492 8198; e-mail:
mgamalel-din@ualberta.ca.
’ACKNOWLEDGMENT
We acknowledge the financial support provided by a research
grant (Martin and Gamal El-Din) from Alberta Innovates - Energy
andEnvironmentSolutions,aresearchgrantfromSyncrudeCanada
Ltd.,andtheresearchgrant(GamalEl-DinandMartin)provided
by Helmholtz-Alberta Initiative (HAI). We also acknowledge
an NSERC research grant (Gamal El-Din) for the research tools
and instruments. We also wish to acknowledge the support of
an infrastructure grant from the Canada Foundation for
Innovation (CFI). Dr. Giesy was supported by the Canada
Research Chair program, a large Chair Professorship at the
DepartmentofBiologyandChemistryandStateKeyLaboratory
inMarinePollution,CityUniversityofHongKong,TheEinstein
Professor Program of the Chinese Academy of Sciences and the
Visiting Professor Program of King Saud University. We also
acknowledge the Alberta Centre for Surface Engineering and
Science (ACSES), University of Alberta, for XPS analysis. Finally,
thanks go to technicians of the laboratories in the Department
of Civil and Environmental Engineering at the University of
Alberta.
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* Corresponding author email: mgamalel-din@ualberta.ca S1

SUPPORTING INFORMATION

The Impact of Metallic Coagulants on the
Removal of Organic Compounds from Oil Sands
Process-Affected Water

Parastoo Pourrezaeia, Przemysław Drzewicza, Yingnan Wanga, Mohamed Gamal El-Dina*,
Leonidas A. Perez-Estradab, Jonathan W. Martinb, Julie Andersonc, Steve Wisemanc, Karsten
Liberc, and John P. Giesyc,d,e,f,g

aDepartment of Civil and Environmental Engineering, University of Alberta, Canada; bDivision
of Analytical and Environmental Toxicology, University of Alberta, Canada; cToxicology
Centre, University of Saskatchewan, Canada; dDepartment of Veterinary Biomedical
Sciences, University of Saskatchewan, Canada; eDepartment of Zoology, and Center for
Integrative Toxicology, Michigan State University, USA; fZoology Department, College of
Science, King Saud University, Saudi Arabia; gDepartment of Biology & Chemistry, City
University of Hong Kong, China

Environmental Science and Technology
Date: 23/08/2011


Number of Pages (Including Cover): 6
Number of Tables: 1
Number of Figures: 4

Page 10

S2

Quantification Methods
pH was measured using an Accumet Research AR20 pH Meter, Fisher Scientific. An Orbeco-
Hellige 965 Turbidimeter, Orbeco Analytical Systems Inc. was used to measure the turbidity of
the samples based on the light scattering principle. An Apollo 9000 TOC Combustion Analyzer,
FOLIO Instruments Inc. was used to analyze TOC content of the samples. Each sample was
analyzed in triplicate and the average value with less than 5% standard deviation was considered
as the TOC. COD and CBOD5 were measured according to the Standard Methods for the
Examination of Water and Wastewater. Total alkalinity of the samples was measured by titration
with 0.02 N sulfuric acid. A Thermo Orion Portable 130A Conductivity Meter was used to
quantify the conductivity of the samples. Major cations and anions were analyzed using a Dionex
2500 and a 2000 IC system equipped with an AS50 auto-sampler with 25 µL injection loop,
GP50 gradient pump, CD25 conductivity detector, NG1, AG14A, AS14A columns, ASRS Ultra
П suppressor, eluent reservoir with 4×2L suitable plastic containers, and nitrogen 4.8
compressed gas. An Elan 9000 ICP Mass Spectrometer, PerkinElmer SCIEX was used to
quantify the concentration of the trace metals. To analyze the total metal contents, samples were
digested with concentrated nitric acid for 10 min. Digested samples were filtered through a 0.45
µm filter and diluted before injection into to the ICP-MS.

X-ray Potoelectron Spectroscopy Analysis. The XPS measurements were performed on AXIS
165 spectrometer (Kratos Analytical) at the Alberta Centre for Surface Engineering and Science
(ACSES), University of Alberta. The base pressure in the analytical chamber was lower than 3 x
10-8 Pa. Monochromatic Al Kα source (hν = 1486.6 eV) was used at a power of 210 W. The
analysis spot was 400 x 700 um. The resolution of the instrument is 0.55 eV for Ag 3d and 0.70
eV for Au 4f peaks. The survey scans were collected for binding energy spanning from 1100 eV
to 0 with analyzer pass energy of 160 eV and a step of 0.4 eV. For the high-resolution spectra the
pass-energy was 20 eV with a step of 0.1 eV. Electron flood gun was used to compensate the
sample charging. Vision-2 instrument software was applied to process the data. All spectra were
calibrated for C1s binding energy position at 284.8 eV. Compositions were calculated from the
survey spectra using the major elemental peaks and sensitivity factors provided by the database.

Page 11

S3

Fourier Transform Infra Red (FT-IR) Analysis. A Bio-rad diffuse reflectance FT-IR
spectrophotometer was used to identify the surface functional groups in the flocs. Dried flocs
were mixed with potassium bromide (KBr) (FT-IR grade, Sigma-Aldrich) in a 5% by weight
ratio and ground to form a very five powder. The mixture was then analyzed by the infra red
spectroscopy. Pure KBr was also used to collect the background spectra. The spectra were
recorded with 128 scans and 4 cm-1 spectral resolution.

SEM Analysis. Dried flocs were used for image analysis. The sample particles were scattered
onto the stub pasted with a thin layer of silicon, then the samples were sputter coated with a thin
layer of gold before it were examined with Hitachi SEM S-2500 (Tokyo, Japan). The samples’
images were examined in the SEM instrument by adjusting various parameters including
working distance, beam current, KV, contrast, and brightness to obtain the highest possible
quality for images. Photos were taken at 3K, 6K magnification at 8.0KV.

Page 12

S4

Table S1. Complete water analysis results for optimum conditions
Optimum Conditions pH
Turbidity Removal
(%)
TOC Removal
(%)
Conductivity
(µS/cm)
100 mg/L AS 7.4 96 8 3770
100 mg/L AS + 10 mg/L CP 7.4 98 12 3720
250 mg/L AS 7.1 97 12 3795
250 mg/L AS + 5 mg/L CP 7.0 99 14 3795
500 mg/L AS 6.5 98 14 3790
500 mg/L AS + 2 mg/L CP 6.5 99 17 3775


Table S1. Complete water analysis results for optimum conditions - Con’t
Optimum Conditions
Sulfate
Increase
(%)
Aluminum
Removal
(%)
Iron
Removal
(%)
Vanadium
Removal
(%)
Barium
Removal
(%)
100 mg/L AS 7 81 82 72 54
100 mg/L AS + 10 mg/L CP 23 96 87 67 56
250 mg/L AS 24 80 86 72 62
250 mg/L AS + 5 mg/L CP 24 95 89 72 63
500 mg/L AS 49 72 87 72 60
500 mg/L AS + 2 mg/L CP 50 94 91 72 63
- AS and CP indicate aluminum sulfate and cationic polymer.

Page 13

S5

0%
5%
10%
15%
20%
25%
0200400600800
TOC Removal (%)
Coagulant Concentration (mg/L)
Alum
Ferric Sulfate
Ferric Chloride

Figure S1. TOC removal by increasing the concentrations of alum, ferric sulfate, and ferric
chloride.


0%
20%
40%
60%
80%
100%
0 100 200300 400500600 700
Turbidity Reduction (%)
Coagulant Concentration (mg/L)
Alum
Ferric Sulfate
Ferric Chloride

Figure S2. Turbidity reduction by increasing the concentrations of alum, ferric sulfate, and ferric
chloride.

Page 14

S6

0
20
40
60
80
100
120
Fresh WaterOSPW250 mg/L AS250 mg/L AS+5
mg/L CP
% Survival
Treatment
A
A
AB
B

Figure S3. Effects of full-strength OSPW, OSPW treated by 250 mg/L alum, and 250 mg/L
alum+ 5 mg/L cationic polymer on the survival of C.dilutus relative to a freshwater control.
Data represent mean ± st dev of 4 independent replicates. Different letters represent significant
differences between different groups (1- way ANOVA with Tukey’s post hoc test, p < 0.05).

0
500
1000
1500
2000
2500
Fresh WaterOSPW250 mg/L AS 250 mg/L AS+5
mg/L CP
% Change in Mean Organism Wet Weight
Treatment
A
B
B
C

Figure S4. Effects of full-strength OSPW, OSPW treated by 250 mg/L alum, and 250 mg/L
alum+ 5 mg/L cationic polymer on the growth of C.dilutus relative to a freshwater control. Data
represent mean ± st dev of 4 independent replicates. Different letters represent significant
differences between different groups (1- way ANOVA with Tukey’s post hoc test, p < 0.05).