Toxicity of oil sands acid-extractable organic fractions to freshwater fish: Pimephales promelas (fathead minnow) and Oryzias latipes (Japanese medaka).

The Alberta oil sands are one of the largest global petroleum deposits and, due to non-release practices for oil sands process-affected waters, produced tailings are stored in large ponds. The acid extractable organic (AEO) compounds in oil sands process-affected water are of greatest concern due to their persistence and toxicity to a variety of aquatic biota. The present study evaluated the toxicity of the five AEO fractions to two fish species: Oryzias latipes (Japanese medaka) and Pimephales promelas (fathead minnow). The fractions (F1-F5) were comprised of AEO with increasing mean molecular weight and subsequent increases in cyclicity, aromaticity, degree of oxygenation, and heteroatom content. The lowest molecular weight fraction, F1, displayed the lowest acute toxicity to both fish species. For fathead minnow, F5 displayed the greatest toxic potency, while F2 to F4 displayed intermediate toxicities. For Japanese medaka, F2 and F3 displayed the greatest acute toxicities and F1, F4 and F5 were significantly less potent. Overall, fathead minnow were more acutely sensitive to AEO than Japanese medaka. The present study indicates that AEO toxicity may not be solely driven by a narcotic mode of action, but chemical composition such as aromaticity and heteroatom content and their relation to toxicity suggest other drivers indicative of additional modes of toxic action.

Assessing the bioremediation potential of algal species indigenous to oil sands process-affected waters on mixtures of oil sands acid extractable organics.

Surface mining extraction of bitumen from oil sand in Alberta, Canada results in the accumulation of oil sands process-affected water (OSPW). In attempts to maximize water recycling, and because its constituents are recognized as being toxic, OSPW is retained in settling basins. Consequently, research efforts are currently focused on developing remediation strategies capable of detoxifying OSPW to allow for eventual release. One potential bioremediation strategy proposes to utilize phytoplankton native to the Alberta oil sand region to sequester, break down, or modify the complex oil sands acid extractable organic (AEO) mixtures in OSPW. Preliminary attempts to quantify changes in total oil sands AEO concentration in test solutions by ESI-MS following a 14-day algal remediation period revealed the presence of unknown organic acids in control samples, likely released by the phytoplankton strains and often of the same atomic mass range as the oil sands AEO under investigation. To address the presence of these "biogenic" organic acids in test samples, ESI-MS in MRM mode was utilized to identify oil sands AEO "marker ions" that were a) present within the tested oil sands AEO extract and b) unique to the oil sands AEO extract only (e.g. atomic masses different from biogenic organic acids). Using this approach, one of the 21 tested algal strains, Stichococcus sp. 1, proved capable of significantly reducing the AEO marker ion concentration at test concentrations of 10, 30, and 100mgL(-1). This result, along with the accelerated growth rate and recalcitrance of this algal strain with exposure to oil sands AEO, suggests the strong potential for the use of the isolated Stichococcus sp. 1 as a candidate for bioremediation strategies.

Factors influencing stable isotopes and growth of algae in oil sands aquatic reclamation.

Previous studies reported (15)N enrichment of biota in reclamation wetlands that contain oil sands processed material (e.g., processed water and tailings); however, there is little information on the factors controlling (15)N enrichment in these systems. In this microcosm study, the aim was to examine stable C and N isotopes and growth (chlorophyll a [chl a] and dry weight) of algae as a function of exposure to different sources and concentrations of water-soluble fractions (WSF) derived from tailings. Two sources of tailings including mature fine tailings (MFT) and consolidated tailings (CT) and peat-mineral overburden were utilized to generate separate WSF that differed in water quality. In general, there was (15)N enrichment of filamentous algae along the increasing gradient of WSF/nutrient concentrations in both CT and peat microcosms, and among the different sources, algae were more (15)N enriched in CT WSF than in peat WSF. Growth of filamentous algae was inhibited at higher WSF concentrations, possibly due to reduced light availability at elevated levels of fine clay particles in MFT microcosms and colored dissolved organic carbon (DOC) in peat microcosms. Filamentous algae displayed lower biomass and (15)N depletion in 100% peat WSF. This study indicated that both the quality (source) and quantity of WSF affected algal growth and directly and/or indirectly influenced δ(15)N of algae. The distinct (15)N enrichment of primary producers derived from tailings suggest that stable N isotopes might be useful to trace exposure to oil sands processed material in biota that utilize these resources in reclaimed systems constructed with tailings or natural systems that receive tailings dyke seepage.

Field survey of Canadian background soils: Implications for a new mathematical gas chromatography-flame ionization detection approach for resolving false detections of petroleum hydrocarbons in clean soils.

The reference method for the Canada-wide standard (CWS) for petroleum hydrocarbons (PHCs) in soil provides laboratories with methods for generating accurate and reproducible soil analysis results. The CWS PHC tier 1 generic soil-quality guidelines apply to 4 carbon ranges/fractions: F1 (C6-C10), F2 (C10-C16), F3 (C16-C34), and F4 (>C34). The methods and guidelines were developed and validated for soils with approximately 5% total organic carbon (TOC). However, organic soils have much higher TOC levels because of biogenic organic compounds (BOCs) originating from sources such as plant waxes and fatty acids. Coextracted BOCs can have elevated F2-F4 concentrations, which can cause false exceedances of PHC soil guidelines. The present study evaluated false PHC detections in soil samples collected from 34 background sites. The list of analytes included soil type, TOC, polycyclic aromatic hydrocarbons (PAHs), F2, F3, F4, F3a (C16-C22), and F3b (C22-C34). Soils with 3% to 41% TOC falsely exceeded the CWS PHC 300 mg/kg F3 coarse soil guideline. It was previously demonstrated that clean peat had F2:F3b ratios of less than 0.10, while crude oil spiked peat and spiked sand had higher ratios of greater than 0.10. In the present background study, all of the clean organic soils with at least 300 mg/kg F3 had F2:F3b ratios of less than 0.10, which indicated false guideline exceedances. Clean inorganic soils had low F3 concentrations, resulting in high F2:F3b ratios of greater than 0.10. Validation field studies are required to determine if the F2:F3b 0.10 PHC presence versus absence threshold value is applicable to crude oil- and diesel-contaminated sites.

Is it clean or contaminated soil? Using petrogenic versus biogenic GC-FID chromatogram patterns to mathematically resolve false petroleum hydrocarbon detections in clean organic soils: a crude oil-spiked peat microcosm experiment.

The Canadian Council of Ministers of the Environment (CCME) reference method for the Canada-wide standard (CWS) for petroleum hydrocarbon (PHC) in soil provides chemistry analysis standards and guidelines for the management of contaminated sites. However, these methods can coextract natural biogenic organic compounds (BOCs) from organic soils, causing false exceedences of toxicity guidelines. The present 300-d microcosm experiment used CWS PHC tier 1 soil extraction and gas chromatography-flame ionization detector (GC-FID) analysis to develop a new tier 2 mathematical approach to resolving this problem. Carbon fractions F2 (C10-C16), F3 (C16-C34), and F4 (>C34) as well as subfractions F3a (C16-C22) and F3b (C22-C34) were studied in peat and sand spiked once with Federated crude oil. These carbon ranges were also studied in 14 light to heavy crude oils. The F3 range in the clean peat was dominated by F3b, whereas the crude oils had approximately equal F3a and F3b distributions. The F2 was nondetectable in the clean peat but was a significant component in crude oil. The crude oil­spiked peat had elevated F2 and F3a distributions. The BOC-adjusted PHC F3 calculation estimated the true PHC concentrations in the spiked peat. The F2:F3b ratio of less than 0.10 indicated PHC absence in the clean peat, and the ratio of greater than or equal to 0.10 indicated PHC presence in the spiked peat and sand. Validation studies are required to confirm whether this new tier 2 approach is applicable to real-case scenarios. Potential adoption of this approach could minimize unnecessary ecological disruptions of thousands of peatlands throughout Canada while also saving millions of dollars in management costs.

Has Alberta oil sands development altered delivery of polycyclic aromatic compounds to the Peace-Athabasca Delta?

BACKGROUND: The extent to which Alberta oil sands mining and upgrading operations have enhanced delivery of bitumen-derived contaminants via the Athabasca River and atmosphere to the Peace-Athabasca Delta (200 km to the north) is a pivotal question that has generated national and international concern. Accounts of rare health disorders in residents of Fort Chipewyan and deformed fish in downstream ecosystems provided impetus for several recent expert-panel assessments regarding the societal and environmental consequences of this multi-billion-dollar industry. Deciphering relative contributions of natural versus industrial processes on downstream supply of polycyclic aromatic compounds (PACs) has been identified as a critical knowledge gap. But, this remains a formidable scientific challenge because loading from natural processes remains unknown. And, industrial activity occurs in the same locations as the natural bitumen deposits, which potentially confounds contemporary upstream-downstream comparisons of contaminant levels. METHODS/PRINCIPAL FINDINGS: Based on analyses of lake sediment cores, we provide evidence that the Athabasca Delta has been a natural repository of PACs carried by the Athabasca River for at least the past two centuries. We detect no measureable increase in the concentration and proportion of river-transported bitumen-associated indicator PACs in sediments deposited in a flood-prone lake since onset of oil sands development. Results also reveal no evidence that industrial activity has contributed measurably to sedimentary concentration of PACs supplied by atmospheric transport. CONCLUSIONS/SIGNIFICANCE: Findings suggest that natural erosion of exposed bitumen in banks of the Athabasca River and its tributaries is a major process delivering PACs to the Athabasca Delta, and the spring freshet is a key period for contaminant mobilization and transport. This baseline environmental information is essential for informed management of natural resources and human-health concerns by provincial and federal regulatory agencies and industry, and for designing effective long-term monitoring programs for the lower Athabasca River watershed.

Has Alberta oil sands development increased far-field delivery of airborne contaminants to the Peace-Athabasca Delta?

Identifying potential regional contamination by Alberta oil sands industrial emissions on sensitive ecosystems like the Peace-Athabasca Delta, ~200 km to the north, requires knowledge of historical contaminant levels and trends. Here we provide some of these critically-needed data, based on analysis of metals in a sediment core from an upland precipitation-fed lake in the delta. The lake is well-situated to record the anthropogenic history of airborne contaminant deposition for this region. Sediment records of metals of concern (Pb, Sb, As, Hg) reflect early to mid-20th century increases in North American industrial emissions, followed by reduced emissions due to improved industrial practices after 1950-70. Notably, Pb, Sb, As and Hg have declined since the onset of Alberta oil sands production, belying concerns that this activity has enhanced far-field atmospheric delivery of these contaminants to the delta.

Tolerance of transgenic canola plants (Brassica napus) amended with plant growth-promoting bacteria to flooding stress at a metal-contaminated field site.

The growth of transgenic canola (Brassica napus) expressing a gene for the enzyme 1-aminocyclopropane-1-carboxylate (ACC) deaminase was compared to non-transformed canola exposed to flooding and elevated soil Ni concentration, in situ. In addition, the ability of the plant growth-promoting bacterium Pseudomonas putida UW4, which also expresses ACC deaminase, to facilitate the growth of non-transformed and transgenic canola under the above mentioned conditions was examined. Transgenic canola and/or canola treated with P. putida UW4 had greater shoot biomass compared to non-transformed canola under low flood-stress conditions. Under high flood-stress conditions, shoot biomass was reduced and Ni accumulation was increased in all instances relative to low flood-stress conditions. This is the first field study to document the increase in plant tolerance utilizing transgenic plants and plant growth-promoting bacteria exposed to multiple stressors.

Phototoxicity of oil sands-derived polycyclic aromatic compounds to Japanese medaka (Oryzias latipes) embryos.

Alkylated polycyclic aromatic compounds (PACs), which are rich in dibenzothiophenes, are present in natural and reclaimed aquatic environments in the oil sands region of northern Alberta (Canada). An oil sands-derived PAC extract has been shown to induce signs of blue sac disease in Japanese medaka (Oryzias latipes) embryos. Information regarding exposure to and effects of oil sands PACs is available, but little of this information concerns the impact of modifying factors. The present study focuses on the effect of simulated solar radiation on oil sands-derived PAC toxicity to Japanese medaka embryos. Photomodification of the oil sands PAC extract caused reduced toxicity with an increase in the duration of ultraviolet (UV) exposure. Generally, mortality and developmental endpoints and, to a lesser extent, growth were affected by photomodification. Coexposures of the PAC mixture and UV caused slight increases in toxicity for mortality and embryonic developmental endpoints at the longest duration of UV exposure tested (16 h). Based on the modest phototoxicity of the oil sands PAC extract to Japanese medaka embryos, enhanced toxicity associated with UV irradiation may not be a concern for embryos of fish species that are common to the oil sands region. However, testing the effects of differing levels of UV irradiation on larval fish and invertebrates that may differ in their PAC bioaccumulation would improve our understanding concerning the importance of UV irradiation as a modifying factor in oil sands environmental risk assessment.