Impact of the 2016 Fort McMurray wildfires on atmospheric deposition of polycyclic aromatic hydrocarbons and trace elements to surrounding ombrotrophic bogs.

Fort McMurray and the Athabasca oil sands region (AOSR) experienced major wildfires in 2016, but the impact of these on regional deposition of polycyclic aromatic hydrocarbons (PAHs) and trace elements has not been reported nor compared to industrial sources of these pollutants in the region. Living moss (Sphagnum fuscum) was collected in triplicate from five ombrotrophic bogs in the AOSR after the wildfires, and analyzed for PAHs and trace elements. These post-wildfire data were compared to data from previous years at the same sites, and also to remote reference bogs in Alberta and Ontario. Elevated post-wildfire concentrations and flux of naphthalene and fluorene were observed at all five bogs in the AOSR, but no consistent trend was evident for higher molecular weight PAHs or the sum of priority PAHs (∑13PAH). Trace elements at most AOSR bogs were not elevated post-wildfire, except at one bog in the burned area (MIL), but even here the elements that were increased (1.7-5.6 × ) were likely of bitumen-origin (i.e., V, Ni, Se, Mo and Re). Significant post-wildfire correlations between PAHs and most trace elements suggested a common source, and few significant correlations were observed with retene, suggesting that wildfires were not the dominant source of most contaminants detected. Mass balance receptor models were used to apportion sources, indicating that the major sources of trace elements among five AOSR bogs post-wildfire were oil sands ore (mean 42%), haul road dust (17%), and petcoke (11%), whereas wildfire was always a minor source (3-4%). For PAHs at the most contaminated site (MIL), delayed petcoke (27%) and wildfire (25%) were the major sources, but the contribution of wildfire to PAHs at other sites was less or not discernable. Impacts of the 2016 wildfires on regional atmospheric deposition of major pollutants was less than from ongoing deposition of anthropogenic dust from oil sands activities.

Contemporary and Historical Atmospheric Deposition of Arsenic and Selenium in the Athabasca Bituminous Sands Region.

Selenium (Se) is one of the trace elements that is enriched in bitumen. To assess the importance of atmospheric Se deposition from mining and upgrading of bituminous sands in northern Alberta, Canada, Sphagnum moss was obtained from 25 bogs near industrial operations. The average Se concentration in moss near industries (58 ± 13 µg/kg; n = 75) was greater than in remote sites in Alberta (29-50 µg/kg), but comparable to bogs in central regions of the province and lower than bogs in southern Ontario (121-244 µg/kg) or the west and east coasts (230-285 µg/kg). In bog vegetation and peat, arsenic (As) concentrations and accumulation rates are 10 times greater at the industrial site (MIL) compared to the control site (UTK), but this is proportional to the differences in scandium (a surrogate for mineral matter concentrations), which points to dust as the predominant As source. An age-dated peat core collected near industries revealed that both Se and As deposition have declined in recent years. A peat core from UTK provided a record of atmospheric deposition dating back over 2700 years, indicating that As and Se deposition in northern Alberta increased considerably in the early 19th century and then went into decline during ∼1950-1970.

Unravelled keratin-derived biopolymers as novel biosorbents for the simultaneous removal of multiple trace metals from industrial wastewater.

Biopolymers derived from modified poultry feathers (KB) were developed to target a broad range of potentially toxic trace elements for their removal from synthetic wastewater and industrial process affected water. The chemical modifications increased surface functionality of KBs for enhanced metal adsorption. Unmodified KB (SM-03) added to synthetic wastewater spiked with nine transition and redox sensitive elements (30-50 µg L-1 each) removed >82% of Pb, Ni, Co and Zn, whereas modified KBs (SM-01 and SM-06) removed 68-100% of SeIV, VV and CrVI. Similar results were observed when spiked process water was used. Experimental observation suggested chemical reduction of redox sensitive elements on the modified KB surfaces to their non-toxic/non-mobile redox states. Biopolymer SM-06 showed a maximum adsorption capacity of 17 mg g-1 for VV and 15 mg g-1 for CrVI at ~20 °C. Due to the abundance of raw material and simplicity of the modifications presented here, modified KBs may serve as a useful option for large-scale water treatment.

Selenium in surface waters of the lower Athabasca River watershed: Chemical speciation and implications for aquatic life.

Selenium in the lower Athabasca River (Alberta, Canada) is of concern due to potential inputs from the weathering of shallow bitumen deposits and emissions from nearby surface mines and upgraders. Understanding the source of this Se, however, is complicated by contributions from naturally saline groundwater and organic matter-rich tributaries. As part of a two-year multi-disciplinary study to assess natural and anthropogenic inputs, Se and its chemical speciation were determined in water samples collected along a ∼125 km transect of the Athabasca River and associated tributaries. Selenium was also determined in the muscle of Trout-perch (Percopsis omiscomaycus), a non-migratory fish species, that were sampled from selected locations. Dissolved (<0.45 µm) Se in the Athabasca River was consistently low in 2014 (0.11 ±â€¯0.02 µg L-1; n = 14) and 2015 (0.16 ±â€¯0.02 µg L-1; n = 21), with no observable increase from upstream to downstream. Selenate was the predominant inorganic form (∼60 ng L-1) and selenite was below detection limits at most locations. The average concentration of Se in Trout-perch muscle was 2.2 ±â€¯0.4 mg kg-1 (n = 34), and no significant difference (p > 0.05) was observed between upstream and midstream (industrial) or downstream reaches. Tributary waters contained very low concentrations of Se (typically < 0.1 µg L-1), which was most likely present in the form of dissolved organic colloids.

Characterization of Naphthenic Acids and Other Dissolved Organics in Natural Water from the Athabasca Oil Sands Region, Canada.

With growth of the Canadian oil sands industry, concerns have been raised about possible seepage of toxic oil sands process-affected water (OSPW) into the Athabasca River (AR). A sampling campaign in fall 2015 was undertaken to monitor for anthropogenic seepage while also considering natural sources. Naphthenic acids (NAs) and thousands of bitumen-derived organics were characterized in surface water, groundwater, and OSPW using a highly sensitive online solid phase extraction-HPLC-Orbitrap method. Elevated NA concentrations and bitumen-derived organics were detected in McLean Creek (30.1 µg/L) and Beaver Creek (190 µg/L), two tributaries that are physically impacted by tailings structures. This was suggestive of OSPW seepage, but conclusive differentiation of anthropogenic and natural sources remained difficult. High NA concentrations and bitumen-derived organics were also observed in natural water located far north of the industry, including exceedingly high concentrations in AR groundwater (A5w-GW, 2000 µg/L) and elevated concentration in a tributary river (Pierre River, 34.7 µg/L). Despite these evidence for both natural and anthropogenic seepage, no evidence of any bitumen-derived organics was detected at any location in AR mainstem surface water. The chemical significance of any bitumen-derived seepage to the AR was therefore minimal, and focused monitoring in tributaries will be valuable in the future.

Arsenic speciation in the lower Athabasca River watershed: A geochemical investigation of the dissolved and particulate phases.

Human and ecosystem health concerns for arsenic (As) in the lower Athabasca River downstream of Athabasca Bituminous Sands (ABS) mining (Alberta, Canada) prompted an investigation to determine its forms in surface and groundwater upstream and downstream of industry. Dissolved As species, together with total and particulate As, were used to evaluate the potential bioavailability of As in water as well as to decipher inputs from natural geological processes and ABS mining and upgrading activities. Water samples were collected from the river in October at 13 locations in 2014 and 19 locations in 2015, spanning up to 125 km. Additional samples were collected from groundwater, tributaries and springs. "Dissolved" (<0.45 µm) As was consistently low in the Athabasca River (average 0.37 ± 0.01 and 0.34 ± 0.01 µg L-1 in 2014 and 2015, respectively) as well as tributaries and springs (<1 µg L-1), with As(V) as the predominant form. The average total As concentration was higher in 2014 (12.7 ± 2.8 µg L-1) than 2015 (3.3 ± 0.65 µg L-1) with nearly all As associated with suspended solids (>0.45 µm). In 2014, when total As concentrations were greater, a significant correlation (p < 0.05) was observed with thorium in particles > 0.45 µm, suggesting that mineral material is an important source of As. Naturally saline groundwater contained low dissolved As (<2 µg L-1) and did not appear to be a significant source to the river. Arsenic in shallow groundwater near a tailings pond exceeded 50 µg L-1 predominantly as As(III) warranting further investigation.

Trace metals in the dissolved fraction (<0.45µm) of the lower Athabasca River: Analytical challenges and environmental implications.

Water samples were collected on the Athabasca River (AR), upstream and downstream from bitumen mines and upgrading facilities, to identify changes in water quality due to industrial activities in this region of northern Alberta, Canada. Starting upstream of Fort McMurray and proceeding downstream ca. 100km, waters were collected in duplicate at 13 locations on the main stem of the river, as well as 5 tributary streams, using ultraclean sampling protocols developed for polar snow and ice. To estimate potential bioaccessibility, trace elements of concern (Ag, Cd, Pb, Sb, Tl) were determined in the dissolved fraction (<0.45µm) along with metals known for their enrichments in bitumen (V, Ni, Mo, Re) and those found mainly in ionic (Li, Sr) or colloidal forms (Al, Co, Cr, Fe, Ga, Mn, Th, Y). Analyses were performed in the metal-free, ultraclean SWAMP lab using quadrupole and sector-field ICP-MS. Concentrations of Ag, Cd, Pb, Sb and Tl were extremely low, not significantly more abundant downstream of industry and probably reflect "background" values. In contrast, V, Ni, Mo and Re concentrations were all significantly (p<0.05) greater downstream of industry. However, chloride also increased downstream, due to natural inputs of saline groundwaters and it is unclear whether the increases in V, Ni, Mo and Re are due to natural or anthropogenic inputs to the river. Although it had been claimed that the industrial development of the Athabasca Bituminous Sands (ABS) is a significant source of Ag, Cd, Pb, Sb and Tl to the river, our study failed to find any evidence to support this. Here we provide a first, robust (accurate and precise) description of baseline values for these trace elements in the AR, and suggest that V, Ni, Mo and Re are more valuable tracers for environmental monitoring and source assessment.