Matthew S. Ross

Quantitative and Qualitative Analysis of Naphthenic Acids in Natural Waters Surrounding the Canadian Oil Sands Industry

The Canadian oil sands industry stores toxic oil sands process-affected water (OSPW) in large tailings ponds adjacent to the Athabasca River or its tributaries, raising concerns over potential seepage. Naphthenic acids (NAs; C(n)H(2n-Z)O(2)) are toxic components of OSPW, but are also natural components of bitumen and regional groundwaters, and may enter surface waters through anthropogenic or natural sources. This study used a selective high-resolution mass spectrometry method to examine total NA concentrations and NA profiles in OSPW (n = 2), Athabasca River pore water (n = 6, representing groundwater contributions) and surface waters (n = 58) from the Lower Athabasca Region. NA concentrations in surface water (< 2-80.8 μg/L) were 100-fold lower than previously estimated. Principal components analysis (PCA) distinguished sample types based on NA profile, and correlations to water quality variables identified two sources of NAs: natural fatty acids, and bitumen-derived NAs. Analysis of NA data with water quality variables highlighted two tributaries to the Athabasca River-Beaver River and McLean Creek-as possibly receiving OSPW seepage. This study is the first comprehensive analysis of NA profiles in surface waters of the region, and demonstrates the need for highly selective analytical methods for source identification and in monitoring for potential effects of development on ambient water quality.

Chemical fingerprinting of naphthenic acids and oil sands process waters—A review of analytical methods for environmental samples

This article provides a review of the routine methods currently utilized for total naphthenic acid analyses. There is a growing need to develop chemical methods that can selectively distinguish compounds found within industrially derived oil sands process affected waters (OSPW) from those derived from the natural weathering of oil sands deposits. Attention is thus given to the characterization of other OSPW components such as oil sands polar organic compounds, PAHs, and heavy metals along with characterization of chemical additives such as polyacrylamide polymers and trace levels of boron species. Environmental samples discussed cover the following matrices: OSPW containments, on-lease interceptor well systems, on- and off-lease groundwater, and river and lake surface waters. There are diverse ranges of methods available for analyses of total naphthenic acids. However, there is a need for inter-laboratory studies to compare their accuracy and precision for routine analyses. Recent advances in high- and medium-resolution mass spectrometry, concomitant with comprehensive mass spectrometry techniques following multi-dimensional chromatography or ion-mobility separations, have allowed for the speciation of monocarboxylic naphthenic acids along with a wide range of other species including humics. The distributions of oil sands polar organic compounds, particularly the sulphur containing species (i.e., OxS and OxS2) may allow for distinguishing sources of OSPW. The ratios of oxygen- (i.e., Ox) and nitrogen-containing species (i.e., NOx, and N2Ox) are useful for differentiating organic components derived from OSPW from natural components found within receiving waters. Synchronous fluorescence spectroscopy also provides a powerful screening technique capable of quickly detecting the presence of aromatic organic acids contained within oil sands naphthenic acid mixtures. Synchronous fluorescence spectroscopy provides diagnostic profiles for OSPW and potentially impacted groundwater that can be compared against reference groundwater and surface water samples. Novel applications of X-ray absorption near edge spectroscopy (XANES) are emerging for speciation of sulphur-containing species (both organic and inorganic components) as well as industrially derived boron-containing species. There is strong potential for an environmental forensics application of XANES for chemical fingerprinting of weathered sulphur-containing species and industrial additives in OSPW.

Isomer-Specific Biotransformation of Perfluorooctane Sulfonamide in Sprague–Dawley Rats

Great variability exists in perfluorooctane sulfonate (PFOS) isomer patterns in human and wildlife samples, including unexpectedly high percentages (e.g., >40%) of branched isomers in human sera. Previous in vitro tests showed that branched PFOS-precursors were biotransformed faster than the corresponding linear isomer. Thus, high percentages of branched PFOS may be a biomarker of PFOS-precursor exposure in humans. We evaluated this hypothesis by examining the isomer-specific fate of perfluorooctane sulfonamide (PFOSA), a known PFOS-precursor, in male Sprague-Dawley rats exposed to commercial PFOSA via food for 77 days (83.0 ± 20.4 ng kg(-1) day(-1)), followed by 27 days of depuration. Elimination half-lives of the two major branched PFOSA isomers (2.5 ± 1.0 days and 3.7 ± 1.2 days) were quicker than for linear PFOSA (5.9 ± 4.6 days), resulting in a depletion of branched PFOSA isomers in blood and tissues relative to the dose. A corresponding increase in the total branched isomer content of PFOS, the ultimate metabolite, in rat serum was not observed. However, a significant enrichment of 5m-PFOS and a significant depletion of 1m-PFOS were observed, relative to authentic electrochemical PFOS. The data cannot be directly extrapolated to humans, due to known differences in the toxicokinetics of PFOS in rodents and humans. However, the results confirm that in vivo exposure to commercially relevant PFOS-precursors can result in a distinct PFOS isomer profile that may be useful as a biomarker of exposure source.

Comparison of electrospray ionization, atmospheric pressure photoionization, and anion attachment atmospheric pressure photoionization for the analysis of hexabromocyclododecane enantiomers in environmental samples

Anion attachment atmospheric pressure photoionization (AA-APPI) has been suggested as a means of expanding the range of compounds that may be analyzed by LC-MS, and has been found to enhance the ionization of some macromolecules (e.g., peptides, polymers) that were unable to be ionized by other techniques. In this study, AA-APPI was compared to APPI, using hexabromocyclododecane (HBCD) enantiomers as a model compound, to provide proof of principle of the use of AA-APPI for small molecule analysis. The use of AA-APPI, with 1,4-dibromobutane in toluene as a bromide source, offered increased sensitivity and lower limits of detection than APPI. Minimal matrix effects were found with AA-APPI in sediment extracts spiked with HBCD post-extraction, with less than a 6% enhancement in the ion signal. Furthermore, enantiomer fractions of HBCD enantiomers were racemic in spiked sediment extracts, in contrast to the more commonly used technique of electrospray ionization, for which matrix effects caused ion signal modification to cause non-racemic measurement artifacts. The use of AA-APPI offers a simple means of further extending the range of compounds ionizable by AA-APPI while maintaining minimal matrix effects.

Potential for in situ chemical oxidation of acid extractable organics in oil sands process affected groundwater.

The process of bitumen extraction from oil sands in Alberta, Canada leads to an accumulation of toxic acid-extractable organics (AEOs) in oil sands process water (OSPW). Infiltration of OSPW from tailings ponds and from their retaining sand dykes and subsequent transport towards surface water has occurred. Given the apparent lack of significant natural attenuation of AEOs in groundwater, remediation may be required. This laboratory study evaluates the potential use of unactivated persulfate and permanganate as in situ oxidation agents for remediation of AEOs in groundwater. Naphthenic acids (NAs; CnH2n+zO2), which are a component of the acutely toxic AEOs, were degraded by both oxidants in OSPW samples. Permanganate oxidation yielded some residual dissolved organic carbon (DOC) whereas persulfate mineralized the AEO compounds with less residual DOC. Acid-extractable organics from oxidized OSPW had essentially no Microtox toxicity.

Enantioselectivity of polychlorinated biphenyl atropisomers in sediment and biota from the Turtle/Brunswick River estuary, Georgia, USA.

To investigate the potential for enantioselective transformation and accumulation, the enantiomer distributions of seven polychlorinated biphenyl (PCB) atropisomers were measured in the sediment and biota from a sub-tropical estuary heavily contaminated with Aroclor 1268, a technical mixture of highly chlorinated PCB congeners. Enantiomer fractions (EFs) of PCBs 91, 95, 136, 149, 174, 176, and 183 in marsh sediment, invertebrate, forage and predatory fish species, and bottlenose dolphins were determined. Non-racemic EFs greater than 0.75 were found in sediments for PCBs 136 and 174, likely the result of microbial dechlorination. Although enantiomer fractions in grass shrimp (Palaemonetes spp.) mirrored those of sediment, fish species had EFs that differed significantly from sediment or grass shrimp. Similarly, bottlenose dolphins were also found to contain non-racemic quantities of PCBs 91, 136, 174, 176, and 183. Non-racemic EFs in these biota were likely a result of both uptake of non-racemic proportions of PCBs from the diet and enantioselective biotransformation.

Tracking chiral polychlorinated biphenyl sources near a hazardous waste incinerator: fresh emissions or weathered revolatilization?

The Swan Hills Treatment Centre (SHTC), located in central Alberta, is the primary facility in Canada for incinerating polychlorinated biphenyls (PCBs). Past studies have shown significant contamination by PCBs and other pollutants of the immediate surrounding region. However, it is unclear whether the major source of contamination to the regions atmosphere is historical release incidents or long-term emissions. To answer this question, concentrations of PCBs and enantiomer fractions of several PCB congeners were determined in soil and air, via polyurethane foam passive samplers, over several seasons between 2005 and 2008. Concentrations in both media were highest for samples collected closest to the SHTC, demonstrating a concentration profile typical of a point source. Enantiomer analysis revealed racemic profiles in air for all congeners, while soil was significantly nonracemic for PCB 95, indicating significant microbial degradation of this congener. However, the primary source of this congener, and likely others, in the surrounding atmosphere is recent and continual releases from the SHTC, rather than the release of weathered PCBs previously deposited to local soils. In addition, enantiomer compositions for PCBs 95 and 149 yielded minimum biotransformation half-lives of 25 and 97 years, respectively, suggesting an expected gradual decline in the regions PCB load once fresh inputs cease.

Microchemical analysis of selenium in otoliths of two West Virginia fishes captured near mountaintop removal coal mining operations

Otoliths, calcified inner ear structures, were collected from creek chubs (Semotilus atromaculatus) and green sunfish (Lepomis cyanellus) living in mountaintop mining-impacted and reference streams and analyzed for selenium (Se) content using laser ablation-inductively coupled mass spectrometry. Significant differences in otolith Se were found between the 2 fish species. Results from the present study suggest that a retrospective reconstruction of Se concentrations in muscle can be derived from Se concentrations in otoliths in creek chub but not green sunfish, exemplifying the importance of species differences when determining partitioning of Se among specific tissues. Green sunfish otoliths from all sites contained background (<1 μg/g) or low (1-4 μg/g) average concentrations of whole-otolith Se. In contrast, creek chub otoliths from the historically mined site contained much higher (≥5 μg/g) concentrations of Se than for the same species in the unmined site or for the green sunfish. These data suggest that body burdens of Se in fish can vary considerably over time and that both the timing of sampling and species choice could heavily influence Se assessments.