Characterization of Oil Sands Process-Affected Waters by Liquid

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Characterization of Oil Sands Process-Affected Waters by Liquid Chromatography Orbitrap Mass Spectrometry Alberto S. Pereira,†,‡ Subir Bhattacharjee,‡ and Jonathan W. Martin*,† †

Division of Analytical and Environmental Toxicology, Department of Lab Medicine and Pathology, Faculty of Medicine and Dentistry, and ‡Department of Mechanical Engineering, Faculty of Engineering, University of Alberta, Edmonton, Alberta T6G 2G3, Canada S Supporting Information *

ABSTRACT: Recovery of bitumen from oil sands in northern Alberta, Canada, occurs by surface mining or in situ thermal recovery, and both methods produce toxic oil sands process-affected water (OSPW). A new characterization strategy for surface mining OSPW (sm-OSPW) and in situ OSPW (is-OSPW) was achieved by combining liquid chromatography with orbitrap mass spectrometry (MS). In electrospray positive and negative ionization modes (ESI+/ESI−), mass spectral data were acquired with high resolving power (RP > 100 000−190 000) and mass accuracy ( 100 000] have further demonstrated the absolute complexity of OSPW. For example, infusion of the organic fraction of sm-OSPW or is-OSPW to FT-ICR−MS, using electrospray ionization (ESI), allows for characterization of a much wider array of heteroatom-containing homologous series than other methods, including compounds with the general formula Ox, SOx, S2Ox, and NOx.22−25 Barrow et al. pushed the analytical boundaries for sm-OSPW characterization ahead by demonstrating the complementary analysis of the smOSPW organic fraction by FT-ICR−MS under four different ionization conditions: ESI and atmospheric pressure photoionization (APPI), in both positive- and negative-ion modes.22 Despite all previous infusion FT-ICR−MS studies of OSPW that had been conducted in ESI−, Barrow et al.22 showed that a greater number of distinct peaks were observed in ESI+. A natural question that emerges from the work by Barrow et al.22 is to what extent the OSPW analytes detected in ESI− are mutually exclusive of the peaks, with the same molecular formula, detected in ESI+. For example, are the NA species that are detected in ESI− the same or different from O2 species detected in ESI+? This in combination with knowledge that most compounds in OSPW will be present as multiple isomers,19 which are difficult or impossible to distinguish relying solely on mass spectrometry, encouraged us to combine liquid chromatography with orbitrap high-resolution mass spectrometry for the analysis of OSPW. There are no previous reports of high-performance liquid chromatography (HPLC) being combined with orbitrap or FT-ICR−MS for the analysis of OSPW. Orbitrap mass spectrometry has already proven effective for sm-OSPW analysis;26 however, we hypothesized that chromatographic separation, prior to orbitrap analysis, would resolve certain isomers that cannot be distinguished by mass spectrometry alone and that retention time information and MS/MS (or MSn) experiments could be used to further resolve and characterize the complex mixture of organics in

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EXPERIMENTAL SECTION Chemicals and Reagents. Acetic acid, sulfuric acid, methanol, dichloromethane, and acetone (all HPLC grade) were purchased from Fisher Scientific (Fair Lawn, NJ). Ultrapure water was prepared with a Milli-Q Gradient A10 System (Millipore, Billerica, MA). The various model compound standards (structures shown in the Supporting Information): (1) 1,2,3,4-tetrahydro-2-naphthoic acid (C11H12O2), (2) 1-adamantaneacetic acid (C12H18O2), (3) hexadecanedioic acid (C16H30O4), (4) ethyl 3-(1-adamantyl)-3oxoproprionate (C15H22O3), (5) progesterone (C21H30O2), and (6) 1-adamantyl methyl ketone (C12H18O) were purchased from Sigma-Aldrich (St. Louis, MO), while (7) 3-(1adamantyl)-1,3-butanediol (C14H24O2) was purchased from Maybridge (Leicestershire, U.K.). The sm-OSPW sample was collected on the site of Syncrude Canada, Ltd. (Fort McMurray, Alberta, Canada) from the West-in-Pit active settling basin in March 2011, and a sample of is-OSPW, from a SAGD surface treatment plant boiler (blowdown water), was obtained from an anonymous operator in Alberta, Canada. The SAGD sample was collected hot, sealed in a nitrogen blanket, cooled, and transported to the University of Alberta. Both samples were stored at 4 °C until analysis. Sample Preparation. A total of 1 L of sm-OSPW or isOSPW was filtered with a 0.45 μm filter (Millipore, Billerica, MA) to remove suspended solids, and the pH of the filtered water was reduced to 2 using 95% H2SO4. This was extracted 2 times with 200 mL of dichloromethane. The extract was than evaporated to near dryness with a rotary evaporator (model R210, Buchi, Toronto, Ontario, Canada). The remaining volume was transferred to a 10 mL glass vial and taken to full dryness under a gentle stream of nitrogen at 40 °C (Turbovap LV, Biotage, Charlotte, NC). A small portion of each residue (2 mg) was dissolved in 1 mL of acetone and transferred to a 2 mL vial for analysis. HPLC−LTQ-Orbitrap−MS. Reversed-phase liquid chromatography was paired with a linear ion trap-orbitrap mass spectrometer (Orbitrap XL, Thermo Fisher Scientific, San Jose, CA).27−30 The chromatographic separation was performed using a HPLC Accela System (Thermo Fisher Scientific, San Jose, CA), consisting of a degasser, a 600 bar quaternary pump, an autosampler, and a column oven. Separation was performed on a Cosmosil C18 MS-II column (100 × 3.0 mm, 2.5 μm particle size, Nacalai USA, San Diego, CA) at 40 °C. A flow rate of 0.5 mL/min and an injection volume of 3 μL were used in all analyses. The mobile phases consisted of (A) 0.1% acetic acid in water and (B) 100% methanol. The mobile phase composition was 5% B for 1 min, followed by a linear gradient ramp to 90% B at 9 min, to 99% B over 5 min, and returning to 5% B in 1 min, followed by a 4 min hold prior to the next injection. There was no carryover, as determined by injection of blanks after the analysis of samples. Mass spectrometer conditions are described in the Supporting Information. All reported species in the total ion mass spectrum had a peak threshold > 600, a mass spectral signal-to-noise ratio (S/N) > 3, and produced discernible extracted ion chromatographic peaks (i.e., chromatographic S/N > 3). Three-dimensional chromatograms were produced using MSight software (Swiss Institute of Bioinformatics, Lausanne, Switzerland).31 5505

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Figure 1. Total mass spectra of sm-OSPW and is-OSPW chromatograms acquired in positive and negative electrospray ionization modes. The resolving power of the orbitrap mass spectrometer was calculated across the range of detected analytes and is plotted on a secondary axis (in blue).

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RESULTS AND DISCUSSION Mass Spectrometry. Resolving power in mass spectrometry is the ability of an instrument to discriminate ions of similar m/z. It can be calculated as m/Δm, where m is the nominal mass of a given molecule and Δm is the width of the peak at half of its maximum height. For the Orbitrap XL mass spectrometer, the nominal resolving power was 100 000 at m/z 400, but for both OSPW samples, most detectable ions were between m/z 100 and 400, meaning that the method resolving power was between 100 000 (at m/z 400) and 190 000 (at m/z 100) (Figure 1). Although this resolving power was at least 5 times lower than what can be achieved by FT-ICR−MS instruments, for most ions (i.e., those below m/z 350), the resolving power was >120 000, which is sufficient to resolve the commonly encountered mass split of 3.4 Da (i.e., H4S versus C3).32 Assignment of empirical chemical formulas (i.e., CnOxSyNz) to each resolved peak was made when the difference between the theoretical and measured m/z was less than 2 ppm. Additional gains in specificity came from combining the orbitrap mass spectrometer with HPLC (see the next section). For comparison to the results by Barrow et al.,22 wherein infusion ESI−/ESI+ experiments were performed on a similar sm-OSPW organic acid fraction, Figure 1 shows the total ion mass spectra for the two modes of ionization from the current work (i.e., mass spectra in Figure 1 are summed across the entire chromatogram). The mass spectrum of sm-OSPW in ESI− was very similar to that published by Barrow et al.,22 but the results in ESI+ were visibly different. Specifically, the ESI+ spectrum in Barrow et al.22 showed the presence of ions between m/z 200 and 700, whereas the current spectra (for both sm-OSPW and is-OSPW) were restricted to the range of m/z 100−380. This may be because the samples were from different sources or were prepared differently, but it is possible that these differences could be attributed to the formation of adducts or dimers33,34 during the infusion experiments by Barrow et al. In the current work, the possibility of dimers or adducts was largely ruled out by a combination of elemental

compositions and retention time information. For example, in the ESI+ spectrum of is-OSPW (Figure 1), the majority of ions above m/z 260 eluted after 8 min, whereas all smaller ions eluted before 8 min. Figure 2 shows that the relative distribution of major compounds in sm-OSPW and is-OSPW contrasted between ESI+ and ESI−. With the acknowledgment that the underlying complex mixture that is present within each elemental composition and the fact that no quantitative calibration was attempted, these data are primarily qualitative. The main classes of compounds were O, O2, O3, O4, O5, O6, N, NO, NO2, NO3, NO4, S, SO, SO2, SO3, SO4, and NO2S. In both OSPWs, the empirical formula class distributions were similar, but in general, the sm-OSPW had relatively more Ox species, while the is-OSPW had relatively more N, NOx, SOx, and NO2S species; albeit, there were exceptions between ESI+ and ESI− modes. HPLC−MS. The high diversity of analytes in OSPW, with varying physical properties and structures, makes it challenging to develop a HPLC method that is ideal for all compounds. Nevertheless, the method here displayed good peak shapes and highly reproducible retention times (see Figure S1 of the Supporting Information). The HPLC−MS total ion chromatograms (TICs) obtained for the OSPW extracts, from both ionization conditions (ESI− and ESI+), are shown in Figure 3. In ESI+ (panels B and D of Figure 3) the TICs showed few distinguishable features between the two OSPW samples, but in ESI− (panels A and C of Figure 3), the sm-OSPW and is-OSPW TICs were distinct, whereby the is-OSPW species were generally eluted earlier, suggesting a higher proportion of more hydrophilic analytes. In fact, between 4 and 6 min, several peaks were observed in is-OSPW that were absent in smOSPW. The overall advantage of combining HPLC with orbitrap mass spectrometry can be visualized in a three-dimensional plot of m/z, retention time, and intensity (Figure 4). The chromatographic separation was added to the overall method 5506

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resolving power for many OSPW organic compounds, particularly for compounds in the major oxygenated homologue classes from O2 to O5, whereby isomers could be partially resolved (Figure 5). Such separations were particularly evident in ESI− for compounds with lower hydrogen deficiency (i.e., DBE of 1−4) and for molecules with fewer than 12 carbons, although even some C15 compounds showed evidence for partial isomer separation (Figure 5). In contrast to the isomer distribution of the is-OSPW and sm-OSPW samples (Figure 5), it was evident that the isomer distributions were very different for the same empirical formula class. Thus, from the introduction of a chromatographic separation, an additional layer of data became available that could be useful for improving the fingerprinting of different OSPW samples, as was previously demonstrated by infusion orbitrap analysis.26 The identity of the isomers or isomer groups could be probed by MSn experiments in future work. Further MSn experiments and model compound work is also required to elucidate the purity of any isomer(s) in these peaks. Only single chromatographic peaks were observed for larger O2 and O3 compounds with higher DBEs; albeit, it is recognized that these single peaks likely contain many isomers. Characterization of O2 Species. Owing to the historical focus on NAs (CnH2n + ZO2) in OSPW and the fact that O2 species were among the three most abundant empirical formula classes in both ionization modes (Figure 2), here, we focused on further characterization of the O2 species. Of particular interest was that the retention times were different when comparing ESI+ and ESI− extracted ion chromatograms for the same empirical formula. More specifically, for analysis of either is-OSPW or sm-OSPW, distinct groups of compounds were observed when comparing the retention time for a particular O2 species (CnH2n + ZO2) detected in ESI− as [CnH2n + ZO2 − H]−,

Figure 2. Comparison of total species abundance by heteroatom class based in the sum of the peak areas in the chromatograms of sm-OSPW and is-OSPW acquired in (A) ESI− and (B) ESI+.

Figure 3. TICs of the OSPW samples acquired in positive and negative electrospray ionization mode. 5507

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Figure 4. Three-dimensional view of the TIC of (A) sm-OSPW and (B) is-OSPW acquired in negative electrospray ionization mode over the range of m/z 100−400.

homologous series [C12−C14 (DBE = 5)] are shown in Figure S3 of the Supporting Information. Each O2+ MS/MS spectrum (e.g., Figure 8 and panels A, B and C of Figure S4 of the Supporting Information) most certainly represents a composite spectrum of several isomers. In the current work, no attempt was made to identify specific isomers; rather, we concentrated on confirming that these compounds include dihydroxy, diketo, or ketohydroxy functionalities by comparison to model compounds. Progesterone (5, C21H30O2) is a diketo compound, and it eluted within the retention time window of the unknown OSPW C21H30O2 analytes in ESI+ (see Figure S5 of the Supporting Information). Furthermore, its MS/MS spectrum included [M − H2O]+ and [M − 2H2O]+, as observed in Figure 8 for the unknown species. Similarly, a model dihydroxy compound, 3-(1adamantyl)-1,3-butanediol (6, C24H24O2), eluted within the retention time window of the unknown OSPW C24H24O2 species in ESI+ (see Figure S5 of the Supporting Information). Upon MS/MS analysis, this diol also lost two molecules of water (see Figure S6 of the Supporting Information) and generated product ions, including m/z 149.1 (C11H17) and m/z 135.1 (C10H15), which were also present in the MS/MS spectrum of the unknown O2+ compounds in OSPW (e.g., Figure 8). Two other model compounds (4 and 7) containing ketone moieties showed neutral losses of CO (see Figure S6 of the Supporting Information), consistent with what was observed in Figure 8. It is also important to note that the four non-acidic model compounds (4, 5, and 7) produced no detectable signal in ESI− (see Figure S5C of the Supporting Information), identical to the behavior of the unknown O2+ species in both OSPW samples. The collective evidence confirms that the unknown O2+ species could indeed be dihydroxy, diketo, or ketohydroxy compounds, but further purifications and research would be required to identify the exact structure for any of these novel OSPW species. It is only germane to note that (i) some sex steroids are also dihydroxy (e.g., 5-adrostenediol), ketohydroxy (e.g., testosterone) or diketo (e.g., adrostenedione) compounds and (ii) OSPW is known to have steroidogenic and endocrinedisrupting effects in vitro and in whole organisms. For example, OSPW alters the concentrations of testosterone and 17βestradiol in goldfish (Carassius auratus), yellow perch (Perca

versus the corresponding O2 species detected in ESI+ as [CnH2n + ZO2 + H]+ (Figure 6). On the basis of their different retention times, it is clear that the O2 species detected in ESI+ are chemically distinct from the corresponding O2 species detected in ESI−. Therefore, in addition to the NA species observed in sm-OSPW (Figure 7A, 145 species) and is-OSPW (Figure 7C, 153 species) by ESI−, it was possible to confirm the presence of 162 and 85 new and distinct O2 species in smOSPW (Figure 7B) and is-OSPW (Figure 7D), respectively, in ESI+. In subsequent discussion, we adopt a simple convention to distinguish the new group of “non-naphthenic acid” compounds detected in positive-ion mode (O2+) from NAs detected in negative-ion mode (O2−). It is reasonable and accepted that the O2− species correspond to NAs; however, the nature of the prominent O2+ species, reported here and previously by Barrow et al.,22 has never been discussed. The O2+ species are unlikely carboxylic acids, not only because their retention times are different from the O2− species, which are indeed carboxylic acids (Figure 6), but also because authentic carboxylic acid standards had no measurable response under ESI+ conditions (see Figure S2B of the Supporting Information). The O2+ species are also apparently not phenolic compounds35 (i.e., weak proton donors) based on the absence of any signal in ESI− at the same retention time (Figure 6). Alternatively, we hypothesized that the O2+ species are composed of dihydroxy, diketo, or ketohydroxy compounds. This hypothesis was supported by the MS/MS spectrum of an example O2+ species [C13H20O2 + H]+, showing that the main product ion was C13H19O+, resulting from neutral loss of H2O and subsequent loss of CO (yielding m/z 163.1483) or another H2O (yielding m/z 173.1326) (Figure 8B). After the first loss of H2O, the secondary loss of H2O and CO was confirmed by MS3 (Figure 8C) of m/z C13H19O+, isolated with a mass error of 10 ppm from the MS/MS experiment (Figure 8B). At a lower m/z range of the MS/MS and MS3 spectra was a homocyclic homologous series of product ions with a repeating difference of CH2: m/z 149.1328 (C11H17+), m/z 135.1171 (C10H15+), m/z 121.1012 (C9H13+), m/z 107.0855 (C8H11+), and m/z 95.0855 (C7H9+), confirming that oxygen is not incorporated anywhere in the rings of the molecules (Figure 8). Analogous spectra were recorded for many other O2+ species, and examples of three others in a 5508

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Figure 5. Extracted ion chromatograms (m/z ±0.003) showing isomers of some representative O2−O5 species in sm-OSPW and is-OSPW in negative electrospray ionization mode.

flavescens), and human H295R cells.36−38 The compounds responsible for such effects may include classical NAs or the polycyclic monoaromatic acids and pentacyclic acids, as recently proposed by Scarlett et al.,39 but the new O2+ species

described here should also be considered as candidate molecules for these adverse effects. Characterization of Other Oxygenated Species (Ox). Despite the chromatography, the need for the high resolving 5509

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Figure 6. Representative extracted ion chromatograms (m/z ±0.002) of O2 species detected in negative electrospray ionization mode (red chromatograms) compared to the corresponding O2 species (i.e., with the same molecular formula) detected in positive electrospray ionization mode (blue chromatograms).

Figure 7. Plots showing the distribution of O2 species under positive and negative electrospray ionization conditions for sm-OSPW and is-OSPW. On the basis of their chromatographic separation (see Figure 6), all species shown in panels A and C are confirmed to be chemically distinct from those shown in panels B and D, respectively.

species, which have overlapping retention times and have a difference in molecular mass of less than 3 mDa. Monooxygenated species were detected primarily in ESI+ (Figure 2).

power of the orbitrap was still necessary to fully resolve certain coeluting compounds. This was especially true in the case of resolving the respective homologous series of O and SO 5510

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Figure 8. (A) Extracted ion chromatogram of the unknown O2+ species, C13H20O2, in ESI+ ([M + H]+; m/z 209.1556 ± 0.0020) for sm-OSPW, (B) associated MS/MS spectrum, and (C) MS3 spectrum of m/z 191.1431. The initial loss of H2O, forming m/z 191.1431, and subsequent MS3 fragementation, showing subsequent loss of H2O (m/z 173.1326) or CO (m/z 163.1483), suggests a mix of dihydroxy, diketo, or ketohydroxy isomers. The absence of any oxygen in the small m/z fragment ions suggests that no oxygen atoms are incorporated into the rings of the compounds.

have previously been confirmed in OSPW.21 In general, in both ionization modes, the majority of the polyoxygenated compounds for both samples were in the DBE range of 2− 16 with between 10 and 25 carbons. As a general trend, species with higher numbers of oxygen atoms were detected at lower abundance and with fewer total species detected (i.e., by carbon number and DBE). Nitrogenated and Sulfurated Compounds. In other smOSPW and is-OSPW samples, the presence of N, NOx, and NOxS compounds has previously been reported.9,10 The retention time of peaks corresponding to mono-nitrogenated compounds were very similar between ESI− and ESI+ in either OSPW sample; thus, no new information was revealed by chromatography. Interestingly, for the is-OSPW sample, the

For sm-OSPW, the O species ranged in carbon number from 10 to 25 and DBE ranged from 2 to 14, while for is-OSPW, the carbon number ranged from 7 to 26 and DBE ranged from 3 to 13. For polyoxygenated compounds (Ox, where x ≥ 3), as discussed above for O2 species, extracted ion chromatograms of analogous molecules were compared in both ESI+ and ESI− (Figure 2). However, no significant differences in retention times were observed, thereby providing no clues as to whether the analyte peaks detected in each mode are chemically distinct or rather represent the same group of chemicals that can form both positive and negative ions in ESI+ and ESI−, respectively. The latter possibility is consistent with the expected ionization behavior of hydroxy-NAs (O3 compounds), some of which 5511

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homologue group having the formula C12H28N [M + H]+ accounted for more than 80% of the total signal of mononitrogenated compounds in ESI+ and is compatible with small amines, such as tributylamine, which could be relevant to in situ bitumen recovery because low-molecular-weight basic aliphatic amines can form salts with low-molecular-weight organic acids, thereby producing powerful surfactants.40 The NOx (x = 1−4) species were detected under both ionization conditions (Figure 2). Among the NO species, the most intense peaks were related to non-aromatic small species with 6 and 7 carbons, corresponding to 14% (ESI−) and 41% (ESI+) of the total NO response in sm-OSPW and 26% (ESI−) and 48% (ESI+) of the total NO response in is-OSPW. For the majority of NO2−NO4 species, these were in the carbon number range of 8−24 and DBE range of 2−10 for both OSPW samples. Approximately 20 mono-sulfur-containing species were detected with carbon numbers between 8 and 27, with DBEs ranging from 2 to 15, in both OSPW samples in both ionization modes. The presence of the mono-sulfur-containing species was confirmed by analysis with atmospheric pressure photoionization (data not shown). For each SOx empirical formula class, more than 100 unique species were detected in each ionization mode for each sample. Neither ESI− nor ESI+ modes were clearly favorable for their ionization (Figure 2), suggesting that these may be a complex mixture of compounds with different functionalities, such as sulfoxides and acidic sulfur compounds. In both OSPW samples and in both ionization modes, NO2S was the main NOxS species detected, validated by observation of the 34S isotope. Although some NOS and NO3S species were present slightly above detection limits, they are not reported here because of the possibility of misassignment. The detected NO2S species had carbon numbers between 7 and 19, with DBE ranging from 2 to 8. For all of the above sulfur-containing species, the retention times were similar for analogous ions in both ESI− and ESI+ chromatograms; thus, further MS n experiments will be needed to confirm the nature of these species in both ionization modes. Environmental Relevance. The overall results indicate that several distinguishable features exist between the libraries of organic compounds identified in sm-OSPW and is-OSPW and the level of new detail from application of the current method can only help to distinguish anthropogenic and natural sources of chemicals in the Athabasca River watershed. A larger and more systematic survey of various OSPW and natural waters by this new method is warranted. For the first time, the combined use of liquid chromatography, two ionization modes (ESI−/ESI+), and high-resolution mass spectrometry (i.e., RP > 100 000) revealed distributions of isomers for Ox species and, in particular, revealed more than 100 distinct non-naphthenic acid O2 species containing hydroxy and/or keto functional groups, as determined by MS/MS and MS3. Further MSn experiments on the various peaks, with either the current chromatographic method or alternate stationary phase chemistries, are likely to reveal new information that may help to explain the toxicology of various OSPW samples or that might inform better extraction and water management strategies.

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ASSOCIATED CONTENT

S Supporting Information *

MS, MS/MS, and MS3 operating conditions described, along with additional chromatograms, mass spectra, and structures of the model compounds. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Telephone: 780-492-1190. Fax: 780-492-7800. E-mail: jon. [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank Professor Richard Fahlman (Department of Biochemistry, Faculty of Medicine, University of Alberta) for the access and his support with the Orbitrap XL and Pengxiang Yang and Stephen Hassan from Thermo Fisher Scientific for the support with the Orbitrap Elite. Funding for this research was provided from the Helmholtz Alberta Initiative, Theme 5 (University of Alberta, Project Lead: Mohamed Gamal El-Din), a Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant, and a NSERC Industrial Research Chair Program in Water Quality Management for Oil Sands Extraction. Alberta Health and Wellness is also thanked for supporting laboratory activities through an operating grant.

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REFERENCES

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dx.doi.org/10.1021/es401335t | Environ. Sci. Technol. 2013, 47, 5504−5513