Article

pubs.acs.org/EF

Characterization and Comparison of Dissolved Organic Matter

Signatures in Steam-Assisted Gravity Drainage Process Water
Samples from Athabasca Oil Sands
Rajesh G. Pillai,*,† Ni Yang,† Steven Thi,† Jannat Fatema,† Mohtada Sadrzadeh,†
and David Pernitsky*,†,‡
†
Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada
‡
Suncor Energy Inc., P.O. Box 2844, 150 Sixth Avenue SW, Calgary, Alberta T2P 3E3, Canada
*
S Supporting Information

ABSTRACT: Steam-assisted gravity drainage (SAGD) process water contains high concentrations of dissolved organic and
inorganic matter. A wide range of analytical techniques including electrospray ionization mass spectrometry, gas
chromatography−mass spectrometry, Fourier transform infrared spectrometry, and fluorescence spectrophotometry have been
utilized for the identification and measurement of dissolved organic matter (DOM) in oil sands process-affected water. The
composition of DOM in the SAGD water is relatively complex, and thus one plausible method for its analysis is the fractionation
of DOM into hydrophilic and hydrophobic portions using suitable resin columns and the characterization of these fractions using
standard analytical methods. Comparing the fractionation and characterization of the SAGD produced water from different plant
sites can provide considerable insight into better management, recycle, and reuse of this process water. Also, a detailed knowledge
of the chemical composition of the SAGD produced water provides guidelines for identifying the constituents that are
responsible for scaling and fouling at various stages of the SAGD process. This study aims at developing a systematic approach
for the fractionation and characterization methods of SAGD process water samples.

■ INTRODUCTION
Steam-assisted gravity drainage (SAGD) is a thermally
enhanced heavy oil recovery method that is broadly practiced
for bitumen extraction from oil sands in Alberta, Canada. In
this process, steam is injected through a horizontal well into the
bitumen-containing formation to decrease the viscosity of the
bitumen and affect its extraction. An emulsion of steam
condensate and heated bitumen flows down along the
periphery of the steam chamber to the production well which
is located below the injection well. This emulsion is then
pumped to the surface where the bitumen and water are
separated.
Two methods of bitumen−water separation are used: the
diluted bitumen process and the high-temperature separation
process (also known as the inverted process). At typical
produced emulsion temperatures (120−170 °C), the density of
Athabasca bitumen and water are similar,1 making gravity
separation difficult. In the diluted process, a low-density
petroleum product such as naphtha or natural gas condensate
is added to the produced emulsion to “dilute” the bitumen and
reduce its density. The diluted bitumen then floats on the water
and is removed by gravity in a free water knockout vessel. The
lower-density diluted bitumen product can be tailored to meet
downstream pipeline and refinery specifications. The diluent
can be recovered at the SAGD facility and/or after pipelining
and reused.
In the high-temperature separation process, the produced
emulsion is heated to between 200 and 230 °C. At these
temperatures, bitumen is heavier than water1 and sinks in the
gravity high-temperature separator, hence the term “inverted”
separation. Typically the separated bitumen is kept hot and
pipelined offsite for further processing or blending. The
selection of the diluted or inverted separation process is
made on a site-specific basis considering heat integration,
pipelining, and final product destination considerations. Water
treatment process and boiler operation and overall water reuse
rates are independent of the separation process used.
After separation, the produced water is treated onsite for the
removal of free oil, hardness, and silica. Free oil is removed via
gravity skim tanks, gas flotation vessels, and/or media filters.
Silica and hardness are then removed in a warm or hot lime
softener. Final polishing steps are performed by media filtration
to remove the remaining particulates and ion exchange to
remove the remaining dissolved hardness. This treated water is
then used as boiler feedwater (BFW) for robust oilfield once-
through steam generators (OTSGs) capable of operating with
high salinity BFW (up to 8000 to 10 000 mg/L total dissolved
solids), and producing 70−80% steam quality. Steam enters a
steam separator, and dry steam is sent to the injection well, and
the liquid blowdown is sent for recycle and/or disposal. In the
current industrial practice, a portion of the boiler blowdown
(BBD) is recycled back to the warm lime softener, and the rest
is disposed of either by deep well injection, an onsite zero liquid
discharge facility, or to an off-site third-party waste manage-
ment company. The amount of recycle is set to maintain the
overall boiler feedwater specifications for total dissolved solids
Received: February 17, 2017
Revised: June 9, 2017
Published: June 21, 2017

© 2017 American Chemical Society 8363 DOI: 10.1021/acs.energyfuels.7b00483

Energy Fuels 2017, 31, 8363−8373
Energy & Fuels
(TDS), Si, Ca, Mg, and TOC. Overall, 80−90% of the
produced water is recycled as BFW. In some process
configurations, evaporators are used to desalinate the boiler
feedwater, allowing the use of drum boilers and higher water
recycle rates. A schematic view of a typical conventional plant is
included in Figure S1.
SAGD produced water contains high concentrations (200−
1000 mg/L) of dissolved organic carbon (DOC), and the
conventional deoiling, lime softening, and ion exchange water
treatment processes used in a typical SAGD plant do not
remove more than approximately 10−15% of this DOC. High
DOC in the SAGD process water is suspected to be implicated
in the formation of fouling deposits in heat exchangers and the
tubes of the OTSGs, leading to increased cleaning frequencies
and equipment failures,2−5 although the exact fouling
mechanisms are not entirely understood. The research work
described in this paper focuses on the characterization of the
DOC present in SAGD produced water. The information
gained from this investigation is intended to be used to better
understand the mechanisms of equipment fouling and the role
that DOC may play in that fouling.
A useful starting point for investigation of the dissolved
organic compounds present in SAGD produced water is an
examination of the nature of the bitumen in the producing
formation. The organic compounds found in the bitumen will
migrate to varying degrees into the hot steam condensate in the
producing SAGD formation. Athabasca bitumen chemistry is
well-studied,1 and it is known to contain organic acids, which
would be expected to partition into the produced water phase
to varying degrees. These organic acids have been shown to
include the naphthenic, carboxylic, and sulfonic acids typically
found in crude oil,6 as well as significant fractions of humic
acids.7 Majid and Ripmeester reported that these humic acids
were similar to typical coal humic acids, with relatively high
sulfur content and significant aromatic content (29−38% of the
carbon present). They also showed the presence of phenolic,
carboxylic, amide, ester, aldehyde, and ketonic functional
groups in these humic acids.7 Light hydrocarbons such as
benzene, toluene, ethylbenzene, and xylene (BTEX) can also
partition into the produced water from diluents that are added
during processing.
Nevertheless, it is important to note that the organic
characterization of source bitumen or crude oil, in general, has
been found to be an incomplete predictor of the character-
ization of the organic compounds found in produced water.8,9
In a detailed study of the water solubility of heavy crudes,
Stanford et al. found that the abundance of a particular
compound class in the parent oil did not directly relate to the
aqueous solubility of that compound class.9 Rather, it was
found that the increased presence of polar functional groups,
oxygenated functional groups, alkyl branching, and aromatiza-
tion increased aqueous solubility. The parent-oil heteroatomic
classes that showed significant aqueous solubility were found to
be the ones that contained functional groups that form strong
hydrogen bonds with water. For example, Ox and OxS
compounds were found to be the most water-soluble. Pyrrolic
(acidic nitrogen) compounds showed poor aqueous solubility.
Nitrogen-containing species exhibited aqueous solubility only if
an oxygenated functional group was present in combination
with a pyrrolic group (i.e., NOx classes). Sulfur-containing
organics showed similar trends; only O3S and O4S compounds
showed appreciable water solubility. Lower molecular weight
compounds present in the parent oil showed higher aqueous
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solubility than higher molecular weight compounds. Low
molecular weight, short-chain alkyl phenols were found to be
extremely water-soluble. Although similar studies have not been
done on Athabasca bitumen, similar trends would be expected.
As bitumen and crude oil characteristics alone are inadequate
to characterize the dissolved organics present in SAGD
produced waters, direct analytical studies are required. Heaton
et al. used a variety of analytical methods to examine Athabasca
SAGD deoiled produced water (DOW), boiler feedwater
(BFW), boiler blowdown water (BBD), and low-pressure-
separator flash blowdown samples from four oil sands
producers.8 Phenols and organic acids were the most significant
chemical classes recovered. BTEX, thiophenes, ketones, alkyl-
substituted benzenes and phenols, dimethylpyridine and
indanes, and some residual aliphatic and aromatic hydrocarbons
were also found. Petersen and Grade conducted a direct
evaluation of dissolved organics from SAGD process waters
using a two-dimensional gas chromatography (GC)/electro-
spray ionization time-of-flight (ESI-TOF) MS technique.10
Three primary groups of compounds were identified: saturated
aliphatics, aromatics, and polar compounds. Saturated aliphatic
hydrocarbons, both straight chain and branched, ranging from
C6 to C18 were found at relatively low concentrations, as
expected due to their low aqueous solubility. Low concen-
trations of aromatics such as benzene, alkylbenzenes, and
naphthalenes were identified. Polar species were much more
prevalent. These included carboxylates and naphthenic acids,
ketones, phenols, thiophenes, and oxidized sulfur-containing
species. Methyl- and ethyl-phenols were prevalent constituents.
Kawaguchi et al. used GC/MS to conduct a detailed analysis of
SAGD produced water samples and identified a wide variety of
organic compounds.11 Volatile organic compounds (VOCs)
such as acetone and 2-butanone predominated. Significant
amounts of polar compounds with carboxylic and phenolic
functional groups and trace amounts of polycyclic aromatic
hydrocarbons (PAHs), e.g., naphthalene and phenanthrene,
were also found. Organic acids and VOCs were found to be
major constituents in the produced water, deoiled water, and
softened water samples, whereas organic acids were most
abundant in the blowdown and recycle water samples.
Naphthenic acids were present in all process water samples.
As the water treatment progresses, the total concentrations of
organic acids and phenols increased, whereas PAHs and VOCs
decreased significantly. Pereira et al. analyzed SAGD boiler
blowdown using liquid chromatography followed by ESI
Orbitrap MS and found over 3000 elemental compositions
corresponding to a range of heteroatom-containing homologue
classes (Ox: x = 1−6, NOx: x = 1−4, SOx: x = 1−4, NO2S, N,
and S).7,12 The O2 species detected in the ESI negative mode
were chemically distinct from the corresponding species in the
ESI positive mode. This study also found distinct differences
between the organic compounds identified in the SAGD
sample and those of a process-affected water sample from an oil
sands surface mine. The higher temperature of the SAGD
process compared to mined bitumen extraction is most likely
responsible for the differences in the number and type of
dissolved organics found between these two sources. The
detailed, direct analytical studies reported above have shown
that SAGD produced water contains thousands of individual
compounds. Because of the large number of individual
compounds present in SAGD waters and because the
importance of every single compound in the fouling process
is unknown, alternate analysis schemes have been developed to
DOI: 10.1021/acs.energyfuels.7b00483
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Energy & Fuels Article

Figure 1. FEEMS peaks of various industrial waters from the research literature. Coal bed methane produced water,15 coal coking wastewater,16,17
refinery wastewater,18 OSPW and SAGD produced water.19

classify SAGD DOC on the basis of more general chemical Table 1. Characterization of Dissolved Organics by Resin
properties. These schemes allow the identification of groups or Fractionation14
families of compounds that have similar physicochemical
fraction abbreviation representative compounds
properties. Two indirect characterization techniques that have
been investigated are fluorescence excitation−emission matrix hydrophobic
acids
HPoA humic acids, fulvic acids, phenols, tannins,
medium-MW alkyl carboxylic acids
spectroscopy (FEEMS) and resin fractionation. hydrophobic HPoB proteins, aromatic and high-MW amines
FEEMS has been used to characterize and compare the types bases
of dissolved organic matter present in a wide variety of water hydrophobic HPoN hydrocarbons, aldehydes, alkyl alcohols
samples, from natural surface and ground waters to refinery neutrals
wastewaters and produced waters.13,14 The technique provides hydrophilic
acids
HPiA hydroxy-acids, low-MW alkyl carboxylic acids
a “fingerprint” of the dissolved organics present, based on their hydrophilic HPiB amino acids, low-MW alkyl amines
fluorescence properties. The fluorescence response can then be bases
compared to that of other samples or the response of known hydrophilic HPiN polysaccharides, low-MW alkyl alcohols,
reference compounds. The pioneering work in using FEEMS to neutrals aldehydes
characterize dissolved organics was conducted on fresh and
marine water samples and municipal wastewater effluents, and
Additionally, the DOC was fractionated based on size by
five standard response regions have been defined based on the
filtering through a series of membranes with increasingly tighter
principal components in those waters: aromatic proteins molecular weight cut-offs of 10, 3, and 0.5 kDa. FEEMs, specific
(regions I and II), fulvic acids (region III), soluble microbial UV absorbance (SUVA), and FTIR were used to characterize
byproducts (region IV), and humic acids (region V).13 In the water samples and the different fractions. The ion exchange
addition to natural water samples, the technique has been used fractionation revealed that the DOC contained a high level of
to analyze the organic compounds found in produced water and hydrophobic acids (39.0%) and hydrophilic neutrals (28.5%).
industrial wastewater samples. Figure 1 shows the FEEMS The different ion exchange fractions showed distinct
results from the analysis of several industrial water samples fluorescence excitation−emission (Ex/Em) signatures. The
overlaid on the five standard response regions. Although the fluorescence EEM spectra of the permeate samples from the
specific compounds found in the industrial and natural water membrane fractionation, on the other hand, were not
samples may differ, this figure can provide some insight into the significantly different, suggesting that the hydrophilic and
likely size and structure of the dissolved organics present in the hydrophobic constituents of the DOC could not be separated
industrial wastewaters. based on the molecular sieve property of the membranes.
Resin fractionation techniques have also been used to study Membrane filtration results showed that the majority of the
the characteristics of natural organic matter on the basis of their SAGD DOC was less than 500 Da, which is smaller than typical
adsorption on various ion exchange resins. Through well- aquatic natural organic matter and smaller than bitumen
established techniques, dissolved organics can be separated into asphaltenes and resins.
hydrophobic and hydrophilic fractions of acid, base, and neutral Thakurta et al. also used FEEMS to examine the individual
compounds. The types of compounds typically found in each fractions from the resin separation technique;20 these data are
resin fraction have been well studied, and are summarized in included in Figure 1. It can be seen that SAGD produced
Table 1. waters, Athabasca oil sands process-affected waters (OSPW),
The resin fractionation technique has been used to separate and refinery wastewater all contain some compounds with
the DOC in SAGD process water samples as described above.20 fluorescence responses that are similar to each other, and which
8365 DOI: 10.1021/acs.energyfuels.7b00483
Energy Fuels 2017, 31, 8363−8373
Energy & Fuels
are similar to the responses of phenol, cresol, and naphthenic
acid reference compounds. Although SAGD DOC is not
identical to that found in natural waters, the DOC present
exhibited Ex/Em signatures similar to those found in humic and
fulvic acids, suggesting that some components of SAGD DOC
have a similar molecular structure. This result is not surprising,
as humic and fulvic acids, which originate from the
decomposition of organic matter, have been found in oil
sands bitumen, as mentioned above.7 Humic acids are large,
complex molecules having a wide variety of components,
including phenol, catechol, carboxylic, and amine moieties.
Their polar nature will result in their partitioning into the
produced water during SAGD extraction. Oil-refinery waste-
water DOC characterization studies have also shown the
presence of lower molecular weight fulvic and humic acids.21
The present work involves the characterization and
comparison of three types of process water samples received
from four SAGD water treatment sites in the Athabasca Oil
Sands region of Alberta, Canada. Using a resin fractionation
method, the DOM in these water samples was separated into
six hydrophobic and hydrophilic fractions (HPoA, HPoB,
HPoN, HPiA, HPiB, and HPiN). The chemical characterization
of the process water samples and the resin fractions was
investigated using various analytical methods including gas
chromatography−mass spectrometry (GC-MS), electrospray
ionization Fourier transform ion cyclotron resonance mass
spectrometry (ESI-FT-ICR-MS), inductively coupled plasma
mass spectrophotometry (ICP-MS), TOC, SUVA, and
fluorescence excitation emission matrix spectroscopy
(FEEMS) analysis.
■ MATERIALS AND METHODS
Samples and Materials. Three types of process water samples
were received from four SAGD water treatment sites located in the
Athabasca Oil Sands region (Alberta, Canada). All four sample sites
use conventional SAGD water treatment consisting of deoiling, lime
softening, and weak acid cation exchange processes followed by
OTSGs, which produce high-pressure steam with 70−80% steam
quality. Approximately 40−50% of the resulting blowdown is recycled
back to the lime softener for these plants. All plants employed the
diluted bitumen separation process except Plant B, which employed
high-temperature separation. DOW, BFW, and BBD water samples
were collected from three different locations within each plant. The
DOW sample point was selected as a baseline sample that would
capture the differences in dissolved organics from each plant’s bitumen
formation after the removal of free oil. The BFW sample was selected
to capture any changes in the dissolved organics resulting from the
softening and ion exchange processes and to characterize the organics
entering the OTSGs. The BBD sample was intended to capture any
high-temperature transformations that may occur in the boiler. The
Plant B BFW sample was not obtained due to field logistics.
It should be noted that in the full-scale SAGD water treatment
process, fluids are kept at a temperature of 80−90 °C in a relatively
oxygen-free environment. Samples were collected from hot process
streams using a sample cooler and were placed into epoxy-lined, steel
containers with zero headspace. Exposure to oxygen during and after
sampling can cause chemical transformations to occur.22,23 These
effects were mitigated in this study by minimizing air exposure during
sample collection and maintaining a nitrogen blanket on the samples
during storage. Samples were stored at room temperature.
Three types of resins were purchased from Sigma-Aldrich, including
Supelite DAX-8 (adsorbent resin, moderate polarity), Dowex 50WX8
(cation exchange resin, strong acid), and Amberlyst A21 (anion
exchange resin, weak base). Deionized water (Millipore, 18.2 MΩ·cm)
was used for all sample preparation and dilution. Methanol (ACS
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Article
reagent, ≥ 99.8%) and diethyl ether (anhydrous, ACS reagent, ≥
99.0%) were purchased from Sigma-Aldrich and were used as received.
Standard Analysis. A TOC analyzer (Shimadzu, TOC-L) was
used to measure the dissolved total carbon (TC) and inorganic carbon
(IC). The TOC was calculated by subtracting IC from TC. The
dissolved organic carbon (DOC) was also determined by the TOC
analyzer after filtering the water samples through a 0.45 μm PVDF
membrane filter (Millex, EMD Millipore). Before TOC analysis, the
fractionated samples were stored at 4 °C for less than a week. The
measurement of pH was conducted using a pH meter (Fisher
Scientific, Accumet Excel XL60). A portable conductivity meter (Hach
HQ40d) was used for conductivity measurements and was calibrated
with conductivity calibration standard solutions (Fisher Scientific,
Traceable CRM). The pH and conductivity measurements of raw
water samples were performed without any filtration or dilution. UV
absorbance of the water fractions was measured at 254 nm wavelength
using a UV−vis spectrophotometer (Cary 50, Varian), after filtering
through a 0.45 μm PVDF membrane filter (Millex, EMD Millipore).
The specific UV absorbance (SUVA254) of the samples was calculated
by the corresponding DOC values by the following equation: SUVA254
= (Abs)254nm × 100/DOC.24 The total solids (TS) and TDS values
were measured by gravimetric analysis. TS and TDS were calculated by
using the mass of solid residue left after baking 10 mL of unfiltered and
filtered process water samples, respectively, dried to a constant weight
at 105 °C for TS and 180 °C for TDS. The mass of total solid was
measured using an analytical balance with 0.1 mg readability.
Resin Fractionation. The separation of DOM from the water
samples was performed using a slightly modified procedure of the
previously reported resin fractionation method.20 The details of the
resin fractionation method are provided in the Supporting
Information. Concisely, this method includes (1) cleaning the resins
by Soxhlet extraction, (2) preparing respective resin columns while
considering the TOC concentration of the sample solution, (3)
conditioning the resin columns by a standard procedure, prior to the
introduction of SAGD water samples, to ensure the TOC and
conductivity of the eluted DI water were minimized and within the
acceptable limit, (4) diluting the raw water samples and adjusting the
TOC within 50−70 mg/L, and finally (5) performing the
fractionation, as shown in Figure S2, to obtain three hydrophilic and
hydrophobic fractions.
Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
Elemental concentrations in the produced water samples were
determined by using a quadrupole inductively coupled plasma mass
spectrophotometer (ICP-MS) (PerkinElmer, Elan 600, USA). The
ICP-MS data were obtained with 1300W ICP RF power under dual
detector mode where bismuth, scandium, and indium were used as
internal standards. The sample uptake rate was 1 mL/min. The
concentrations were calculated from the corresponding calibration
curves.
Fluorescence Excitation Emission Matrix Spectroscopy
(FEEMS). Fluorescence excitation−emission contours of the water
samples were acquired using a fluorescence spectrophotometer (Cary
Eclipse, Varian). The excitation−emission spectra were obtained over
a wavelength range of 200−500 nm with 10 nm excitation intervals.
Water samples were diluted to a 20 mg/L TOC concentration to
minimize any inner filtration effects due to excessive concentra-
tion.19,25 The pH of all water samples was adjusted to 11 to minimize
any effect of pH changes on fluorescence.
Electrospray Ionization Fourier Transform Ion Cyclotron
Resonance Mass Spectrometry (ESI-FT-ICR-MS). Ultrahigh
resolution ESI-MS was performed using a Bruker Apex-De 9.4T
FTICR mass spectrometer (Bruker Daltonics, Billerica, MA). The
SAGD water samples were extracted with dichloromethane at pH 2.0.
These sample extracts were mixed with methanol and toluene before
ESI-MS analysis. The injection flow rate was 2 μL/min. Data were
collected over the mass to charge ratio (m/z) range of 150−2000.
Mass accuracy across the full mass range was around 2 ppm (RMS).
SAGD water contains a high concentration of salts. Because these
inorganic salts strongly suppress the ionization efficiency, the organics
were extracted with CH2Cl2.26 Approximately 10 mL DOW or BFW
DOI: 10.1021/acs.energyfuels.7b00483
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Table 2. General Analysis of SAGD Produced Water Samples

Plant A Plant B Plant C Plant D
parameters DOW BFW BBD DOW BBD DOW BFW BBD DOW BFW BBD
pH 9.1 10.1 11.4 7.9 11.1 7.6 9.4 11.3 7.1 9.8 11.2
conductivity (mS/cm) 1.8 2.6 12.9 1.9 15.2 1.5 2.7 11.2 2.7 5.6 19.2
TSS (mg/L) 210 307 367 290 2,313 30 5 1,467 47 3,930 5,878
TDS 1,820 2,217 11,710 5,483 36,807 2,452 2,729 27,333 2,560 3,670 51,665
(gravimetric, mg/L)
TOC (mg/L) 544 534 2,184 512 2,602 401 426 2,997 278 554 3,296
UV absorbance 0.67 0.70 0.87 0.68 0.72 0.77 0.84 0.62 0.51 0.56 0.55
(254 nm)
SUVA (254 nm) 3.34 4.37 5.21 2.90 4.81 3.85 4.20 3.10 2.55 2.80 2.75
color dark reddish black dark black dark reddish black dark reddish black
brown brown brown brown brown brown brown

Table 3. Elemental Concentrations (mg/L or ppm) in SAGD Produced Water Samples Measured Using ICP-MS
Plant A Plant B Plant C Plant D
analyte (mg/L) DOW BFW BBD DOW BBD DOW BFW BBD DOW BFW BBD
Na 402 620 3439 1935 11317 680 854 6741 685 2089 15261
K 20.99 26.26 142.21 35.18 201.92 22.25 26.08 201.06 30.31 79.76 569.91
Li 0.50 0.55 3.04 1.12 6.25 0.71 0.78 5.62 0.69 1.69 12.84
Ca 12.66 1.44 19.45 20.24 7.38 7.76 0.90 10.27 11.40 1.14 11.53
Mg 2.21 0.03 0.44 6.37 0.09 1.04 0.04 0.39 2.16 0.06 0.37
Al 0.25 0.06 0.25 0.02 2.38 0.04 0.10 1.40 0.07 0.21 0.17
Fe 0.08 0.22 0.66 0.20 1.72 0.17 0.07 0.93 2.67 0.16 2.59
Zn 0.18 0.15 0.02 0.16 0.09 0.04 0.07 0.05 0.12 0.13 0.13
Mn 0.01 0.00 0.02 0.01 0.04 0.01 0.00 0.02 0.06 0.00 0.10
Si 98.25 36.94 256.68 72.55 134.98 84.01 16.44 150.11 87.39 14.64 114.47
P 0.35 0.13 0.51 <DL 0.10 0.33 0.16 0.75 <DL 0.11 0.94
B 20.05 20.61 99.73 18.08 84.30 31.20 34.99 193.49 15.61 30.91 184.66

water (2 mL of BBD water) was extracted using 10 mL of CH2Cl2.

The CH2Cl2 extracts were then diluted 100 times in 3:1 MeOH/
Toluene with 0.1% NH4OH added.
Gas Chromatography−Mass Spectrometry (GC-MS). GC-MS
analysis was performed with a TRACE Ultra (Thermo Fisher
Scientific) gas chromatograph equipped with a 30 m × 0.25 mm ID
capillary column (TR-5MS) coupled with a DSQ II mass spectrometer
(Thermo-Fisher Scientific). Helium, with 1.0 mL/min flow rate, was
used as a carrier gas.The temperature of the injector, GC-transfer line,
and the ion source was adjusted at 150 °C, 300 °C and 200 °C,
respectively. The sample injections were done in the splitless mode.
The oven temperature program maintained at 80 °C for 3 min and
then increased to 300 °C with the rate of 8 °C/min. The samples were
analyzed by electron ionization (EI) at 70 eV in the full scan mode,
and the scanned mass range was 50−500 m/z. The acceleration
voltage was turned on after a solvent delay of 400 s.
In this study, the pH of SAGD water was adjusted to 2.0, and
dichloromethane was used to extract organics from the process water.
Ten millilters of SAGD water (2 mL for the BBD water) was extracted
three times with 5 mL portions of CH2Cl2. The extracted organic
phase was dried under house vacuum. The resulting residue was
resuspended in 1 mL of CH2Cl2. Prior to the GC-MS measurement,
100 μL of the solution was mixed with 100 μL of the derivatizing agent
in a 2 mL glass vial. N-tert-Butyldimethylsilyl-N-methyl trifluoroace-
tamide (MTBSTFA) was used as the derivatizing agent for the
carboxyl and phenol group. The glass vial was sealed with Teflon-lined
caps and heated at 60 °C for 30 min. The derived samples were
analyzed by GC-MS employing a mass spectral standard reference
database (NIST Mass Spectral Library, Thermo Fisher Scientific
Xcalibur software). The matching factors in this search program are
1000, 900, 800−900, and 700−800 for perfect, excellent, good, and fair
matches, respectively. In the present study, unknown spectra with a
matching factor above 700 were included in the list of identified
organics.
8367
■ RESULTS AND DISCUSSION
General Chemistry. All process water samples were highly
colored, due to the high amounts of DOM, as shown in Figure
S3. The summary of the general analysis for all of the SAGD
water samples is presented in Table 2. The general inorganic
analysis is presented in Table 3. The data in Table 2 illustrate
the chemical changes in the process water through the SAGD
water treatment plant. Because minimal processing occurs
through the oil removal steps other than free and emulsified oil
removal, DOW is chemically representative of the produced
water. DOW pH ranged from 7 to 9, with TDS between 1800
and 5500 mg/L. TOC ranged from 280 to 550 mg/L. BFW pH
increased to 9−10, reflecting the influence of the lime softening
process, and the concentration of all components increased due
to the addition of recycled BBD upstream of the WLS. BBD
samples were highly concentrated, corresponding to the 70−
80% steam quality produced in the OTSGs. BBD pH was also
elevated due to the addition of OH− generated in the boiler due
to the decomposition of carbonate. The operation of the SAGD
water treatment plant is highly variable; with blowdown recycle
amounts, WLS chemical doses, and steam qualities frequently
changed in response to operating requirements, so the data in
Table 2 should be considered as an operational snapshot at a
single sampling time. The inorganic ions in these process water
samples were analyzed using ICP-MS (Table 3).
GC-MS Analysis of DOM. SAGD water contains hundreds
of individual organic compounds with different chemical
characteristics. Therefore, more than one analytical technique
is required to characterize water samples with such a high level
of complexity. GC-MS is appropriate for identifying and
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Energy & Fuels
Figure 2. GC-MS relative intensity distribution of organic acids and phenols extracted and derived from SAGD process water.
quantifying DOM with low molecular weight (less than 500 g/
mol) and low boiling point (less than 250 °C). MTBSTFA
derivatization was used to facilitate the detection of DOM that
contained polar groups.
The relative abundance of phenols and organic acids, which
were identified as silylated derivatives in the GC-MS analysis,
are summarized in Figure 2 and Table S1. The relative
abundance values were calculated by dividing the peak area of
each identified chemical by the total peak area of all chemicals.
The isomer peaks related to the organic acids were combined
into one compound.
As shown in Table S1, all process water samples have a
significant amount of phenols, aliphatic acids, and aromatic
acids. The relative abundance of phenols was found to decrease
8368
Article
through the SAGD process (from DOW, BFW, to BBD), while
the relative abundance of aliphatic acids increased. Plant B BBD
has a significantly higher amount of phenols and lower amounts
of organic acids than the other three BBDs. For all process
waters, aliphatic acids with carbon number 5−8 were most
prevalent. No aliphatic acids with carbon number above 10
were identified using GC-MS. In this study, we identified
around 14 organic compounds from SAGD water using GC-
MS.
High-Resolution ESI-FT-ICR-MS Analysis. The ultrahigh
resolution ESI-FT-ICR method can measure molecular weight
with 2 ppm mass accuracy and can provide molecular weight
distribution as well as molecule formula of the dissolved
organics. Since this technique measures large molecules from
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Energy & Fuels
Figure 3. 3D distribution of the relative peak intensities obtained from ESI-FT-ICR-MS spectra of SAGD process water samples corresponding to
formula CnH2n‑ZO2.
150 to 2000 m/z, it can be used as a complement to the GC-
MS method to determine the content of organic acids in SAGD
water samples. Therefore, the mass spectra of SAGD process
water samples from Plant A and B were collected under
negative ESI mode.27
As shown in Figure S4, the molecular weight distribution of
organics in Plant A process waters is entirely different from
Plant B process waters. Plant A waters have a broad molecular
weight distribution from 200 to 360 m/z with a number of
detected peaks from 700 to 1000 (Table S2). Plant B waters
have molecular weight distribution from 200 to 290 m/z with
some of the detected peaks only around 600. The DOW of
Plant A has the strongest signal at 269.1217 m/z compared to
the others, which matches the formula of C14H21O3S.
The molecular formulas of the detected peak were
summarized as nine groups such as CxHyO, CxHyO2, CxHyO3,
CxHyO4, CxHyS, CxHySO3, CxHyNO2, CxHyNO3, etc. The
relative intensities of each group of molecules were calculated
against the total peak intensities and expressed as percentages
shown in Table S2. Process waters from Plant B have a higher
relative intensity of CxHyO2 group (>60%) than Plant A’s
water. Plant A process streams have higher percentages of
CxHyO4 and CxHySO3 than Plant B’s water. Plant A process
waters also have a larger amount of other detected molecules
than Plant B water.
SAGD produced water contains a significant amount of
organic acids which may be found in CxHyO2, CxHyO3, CxHyO4
and other groups with two or more oxygens. The materials with
different chemical properties have a distinct ionization
efficiency that makes their comparison challenging. However,
it is possible to compare within a group that has similar
chemical properties. In the present study, CxHyO2 is considered
as the major group of dissolved organic acids to investigate the
8369
Article
molecular distributions of SAGD produced water. Then the
formula of CnH2n+ZO2 is used to describe these organic acids.
The relative intensity value of each organic acid was calculated
against the sum of all organic acids (with CnH2n+ZO2 formula).
The three-dimensional (3D) distribution of the relative
intensity of the organic acids in the SAGD produced water is
shown in Figure 3.
Process water samples from Plant A and Plant B have
distinctively different distributions. The highest portion of z = 0
acids (especially the peak with C = 16 and C = 18) is found in
Plant A SAGD waters with a decreasing trend from its DOW,
BFW, to BBD water. This observation may indicate that Plant
A water has relatively more saturated monocarboxylic acids
than Plant B water. Plant B waters have a significantly large
portion of Z = 4 and 6 acids with C = 13, 14, 15, and 16. Plant
A SAGD water streams have a higher relative amount of Z = 12
and 14 acids than Plant B waters which may indicate higher
aromatic portions
Resin Fractionation of DOM. For the estimation of
relative amounts of hydrophobic and hydrophilic fractions in
the SAGD water samples, a resin based fractionation method
was applied. The percentage distribution of hydrophilic and
hydrophobic fractions was calculated from the corresponding
TOC values as given in Figure 4 and Table S3. It compares
between different types of process water samples and those
received from various SAGD sites. These results show that the
primary DOM constituents in these fractions are HPoA, HPoN,
and HPiN. In all these samples, the relative amount of
hydrophobic fractions was in the range of 50−90%. The HPoA
and HPoN fractions of respective water samples from Plant C
and Plant D sites indicated similar quantities. An earlier analysis
of SAGD BBD water showed HPoA and HPiN as the dominant
fractions (38.7 and 28.4%, respectively).20 However, in the
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Energy & Fuels Article

For example, SUVA values increased through the plant for

Figure 4. Distribution of DOM fractions in DOW, BFW, and BBD
water samples from different SAGD plants.
current analysis of BBD water samples, HPoA and HPoN
fractions were found to dominate with less than 10% of HPiN
fractions. Furthermore, in all these samples, the hydrophilic
base fraction (HPiB) was found to be very low (<2%)
compared to 5% reported for the SAGD BBD water.20 As
expected, the BBD samples show slightly higher acidification
loss (Table S3) due to precipitate formation when adjusting the
solution pH to 2. Here the BBD samples from Plant C and
Plant B show high percentages of acidification loss. This result
Plants A, B and D, whereas SUVA decreased for Plant C.
Similarly, no consistent trends were observed when comparing
the SUVA of the various resin fractions between the different
plants.
FEEMS Analysis. Fluorescence excitation−emission matrix
spectroscopy can be used a “fingerprint” technique for mapping
DOM components in the SAGD water samples.29 Since the
fluorescence data are influenced by several factors including pH
and concentration, it is always desirable to collect the spectra
under identical conditions. The processed FEEM spectra
represent two-dimensional contour plots of excitation−
emission fluorescence matrices (Figure S6, Supporting
Information). For comparing this relatively large data set of
DOM fractions from different SAGD plants, the major peaks in
the FEEMS contour plots have been selected and plotted as
shown in Figure 5. As expected, HPoA and HPiA fractions from
all plants fall in region V (humics), and the HPoN fractions are
distributed between region III (fulvics) and V (humics). The
FEEMS results agree with the TOC fractionation data (Figure
4) in that HPoA and HPoN are the two dominant fractions in
the process water from all the plants. However, the FEEMS
data do not show any significant signature for HPiN fractions,
even though the fractionation data demonstrate that HPiN is
one of the major components. One plausible explanation is the
hydrophilic neutral fractions may consist of high amounts of
fluorescent-inactive, hydrocarbon molecules. This explanation
is further supported by the relatively low SUVA values of these
fractions (Table 4) implying the presence of relatively smaller
amounts of aromatic hydrocarbons. The FEEMS results of
BBD samples in the present work show some agreement with
those of SAGD BBD water reported in the previous study.20
However, no significant FEEMS signals for HPiN fractions
were observed with the current BBD samples. The reasons for
these differences are presently unknown but assumed to be due
to variability in the plant operation or the source bitumen.

is possibly due to the precipitation of acidic DOM components
or silica-organic coprecipitation in the presence of high
amounts of silica in the SAGD BBD water.28
Specific UV absorbance values have been shown to correlate
with the percent aromaticity of DOM in aqueous environ-
ments.24 A summary of the SUVA values for the raw water
samples and their corresponding resin fractions are given in
Table 4. For SUVA analysis, the water samples were diluted
with deionized water to get a TOC concentration of 20 mg/L
to match the TOC concentration of the resin fractions. The
SUVA values for the unfractionated samples showed significant
variation between sites, as expected since each plant is
extracting bitumen from a different geographical location.
Plant D SUVA values were also seen to vary between sample
sites for the same plant, although no clear trends were evident.
■
DISCUSSION
One of the main objectives of this research was to compare the
nature of the dissolved organics between several SAGD plants
to get a better understanding of the variation in the types and
quantities of dissolved organic species between plants located in
different geographies, extracting bitumen from different geo-
logical formations, and using different bitumen separation
techniques. The GC-MS, resin fractionation, and FEEMs
results presented above show that the same major classes of
organic species were present in the process waters from all four
sites. However, the results do indicate that differences do exist
between the different plants. This is an important finding, as a
detailed comparison of the nature of the dissolved organics

Table 4. Specific UV Absorbance (SUVA254) Values of SAGD Produced Water Samples and Their Fractions

Plant A Plant B Plant C Plant D

no. fractions DOW BFW BBD DOW BBD DOW BFW BBD DOW BFW BBD
Raw Sample 3.34 4.37 5.21 2.98 3.05 3.85 4.20 3.10 2.55 2.80 2.75
1 HPoA 2.22 2.37 2.82 2.13 1.60 4.57 3.25 4.88 3.98 3.03 2.66
2 HPoB 2.34 1.46 2.15 2.08 1.94 3.19 1.46 6.78 0.93 1.00 0.18
3 HPoN 3.20 1.15 2.61 2.70 2.45 3.07 3.07 3.07 4.04 2.75 2.36
4 HPiA 1.06 0.62 1.46 1.72 1.06 2.18 2.18 3.98 2.29 1.91 0.63
5 HPiB 0.71 2.70 0.70 0.29 0.06 1.09 0.77 1.50 2.25 2.21 1.69
6 HPiN 0.03 0.13 0.52 0.28 0.30 2.95 1.65 2.81 0.21 0.28 0.12

8370 DOI: 10.1021/acs.energyfuels.7b00483

Energy Fuels 2017, 31, 8363−8373
Energy & Fuels Article

Figure 5. Summary of the FEEMS analysis of resin fractionated SAGD DOW, BFW and BBD water samples. Symbol key: Plant A (circles), Plant B
(squares), Plant C (triangles), Plant D (diamonds). The resin fractions are represented as HPoA (solid black fill), HPoN (solid gray fill), HPoB
(solid white fill), HPiA (vertical black line fill), HPiN (horizontal black line fill), HPiB (diagonal black line fill).

from multiple SAGD plants using the same methodology has
not been reported prior to this study.
The high-resolution ESI-FT-ICR-MS analysis performed on
water samples from Plants A and B did show significant
differences between the organic speciation between these two
plants. What cannot be concluded from the limited sample size
examined in this study is whether these differences are due to
8371
inherent differences in the organics originating from the
subsurface bitumen deposits or were influenced by the absence
of diluent in the high-temperature separation process. Differ-
ences in the source bitumen are likely. However, it is also
possible that the addition of diluent during the bitumen
separation step also influences the partitioning of dissolved
organics into the water phase. The organic species present in
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Energy & Fuels
the produced emulsion exhibit a spectrum of molecular weights,
polarities, and hydro- and oleo-philicities. Analogous to the
precipitation behavior of some asphaltenes upon diluent
addition, some of these dissolved organics may precipitate as
solids or partition into the diluent phase, changing the
distribution of species remaining in the produced water
phase. Organics characterization experiments performed on
emulsion samples obtained before and after diluent addition
and using different diluents would be valuable in this regard.
One of the long-term objectives of the overall research
program that this study was a part of was to assess whether
there are specific dissolved organic compounds that may be
present in the produced water that could be responsible for
OTSG fouling. On the basis of the heterogeneous nature of the
organic compounds identified in this study, and the similarities
between the water samples, no clear class of fouling compounds
can be discerned. Of the four plants sampled, the reported
frequency of OTSG fouling incidents ranged as follows: Plant B
< D < A < C. It is tempting to correlate the low fouling rates
seen for Plant B with its organic speciation and further associate
that with the high-temperature separation process employed,
but our limited data set is insufficient to support that claim.
Ongoing research into OTSG fouling mechanisms suggests that
fouling is dependent upon many factors other than the
composition of dissolved organics, including boiler tube
materials, tube temperatures and heat flux rates, fluid
turbulence, and pigging practices. Although the data from this
study will be useful in subsequent fouling investigation, no clear
linkages between organic speciation and the degree of OTSG
fouling seen in the field can be made at this time.
■
CONCLUSIONS
A comprehensive analysis has been conducted on the SAGD
produced water samples received from four sites in the
Athabasca Oil Sands regions in northern Alberta. The analysis
of raw water samples and their fractions was performed using
various analytical techniques including ICP-MS, GC-MS,
FEEMS, SUVA, and ultrahigh resolution ESI-FT-ICR-MS.
The results from the conventional analysis of the SAGD
produced waters agreed with the results of previous work
discussed in the literature review.
More than 14 different organic materials were identified
using GC-MS, which included three groups of chemicals:
phenols, aromatic acids, and aliphatic acids. The relative
amount of phenols was found to decrease through the water
treatment process, while the relative amount of aliphatic acids
increased. Using ultrahigh resolution ESI-FT-ICR-MS, we
found 500−1000 different molecular ions in Plant A and
Plant B process waters. Naphthenic acids and larger carboxylic
acids were found in all samples. The relative amounts of acidic
compounds increased from BFW to BBD. Organic acids with
2−3 oxygen atoms represented the majority of acid species.
Distinctively different distributions of molecular composition
were found between Plant A and Plant B water treatment
processes. Plant A process waters contained a significantly
higher portion of saturated monocarboxylic acids with carbon
number = 16 and 18. Plant B process waters contain a higher
portion of unsaturated monocarboxylic acids (z = 4 and 6) with
carbon number from 13 to 16. Overall, Plant B, the high-
temperature separation process, showed distinctly different
organic speciation compared to process waters from the other
diluted bitumen process sites. Specifically, Plant B acids tended
to be less aromatic and of lower molecular weight.
8372
Article
The present results discussed herein show that SAGD water
samples received from various processing sites have some
common chemical signatures and some significant differences.
On the basis of this research alone, it is not possible to
conclude whether the unique nature of the chemical
composition of the samples from Plant B was due to inherent
differences in the organics originating from the subsurface
bitumen deposit or were influenced by the absence of diluent in
the high-temperature separation process; further work is
required in this area. Similarly, no clear linkages between
organic speciation and the degree of OTSG fouling seen in the
field can be made based on this data. More detailed information
about the components of DOM fractions and the acid
precipitates will be beneficial to acquire further knowledge
about the DOM composition in the SAGD process water.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.energy-
fuels.7b00483.
SAGD plant diagram, details of resin fractionation,
images of SAGD water samples, the relative abundance
of components from GC-MS and FT-ICR-MS analysis,
representative data of 2D FT-ICR-MS and FEEMS
contour plots (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*(R.G.P.) E-mail: Rajesh.Pillai@nrc-cnrc.gc.ca. Fax: +1 (780)
641-1601. Present address: National Institute for Nano-
technology, National Research Council Canada, Edmonton,
Alberta, T6G 2M9 Canada.
*(D.P.) E-mail: David.Pernitsky@stantec.com. Present address:
Stantec, 200-325 25 Street SE, Calgary, Alberta, T2A 7H8
Canada.
ORCID
Rajesh G. Pillai: 0000-0003-2106-7477
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the funding from the Canadian Oil
Sands Innovation Alliance (COSIA). We thank Jiacheng Yao
and Lauren Mullen (WISEST Summer Research Program) for
assistance with the resin fractionation and spectrofluorescence
experiments. We acknowledge Randy Whittal from the
Department of Chemistry, University of Alberta, for ESI-FT-
ICR-MS analysis, and Dr. Basil Perdicakis from Suncor Energy
for assistance throughout the project.
■
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8373 DOI: 10.1021/acs.energyfuels.7b00483

Energy Fuels 2017, 31, 8363−8373