A risk-based approach for identifying constituents of concern in oil sands process-affected water from the Athabasca Oil Sands region.

Mining leases in the Athabasca Oil Sands (AOS) region produce large volumes of oil sands process-affected water (OSPW) containing constituents that limit beneficial uses and discharge into receiving systems. The aim of this research is to identify constituents of concern (COCs) in OSPW sourced from an active settling basin with the goal of providing a sound rational for developing mitigation strategies for using constructed treatment wetlands for COCs contained in OSPW. COCs were identified through several lines of evidence: 1) chemical and physical characterization of OSPW and comparisons with numeric water quality guidelines and toxicity endpoints, 2) measuring toxicity of OSPW using a taxonomic range of sentinel organisms (i.e. fish, aquatic invertebrates, and a macrophyte), 3) conducting process-based manipulations (PBMs) of OSPW to alter toxicity and inform treatment processes, and 4) discerning potential treatment pathways to mitigate ecological risks of OSPW based on identification of COCs, toxicological analyses, and PBM results. COCs identified in OSPW included organics (naphthenic acids [NAs], oil and grease [O/G]), metals/metalloids, and suspended solids. In terms of species sensitivities to undiluted OSPW, fish ≥ aquatic invertebrates > macrophytes. Bench-scale manipulations of the organic fractions of OSPW via PBMs (i.e. H2O2+UV254 and granular activated charcoal treatments) eliminated toxicity to Ceriodaphnia dubia (7-8 d), in terms of mortality and reproduction. Results from this study provide critical information to inform mitigation strategies using passive or semi-passive treatment processes (e.g., constructed treatment wetlands) to mitigate ecological risks of OSPW to aquatic organisms.

Effects of environmental conditions on aerobic degradation of a commercial naphthenic acid.

Naphthenic acids (NAs) are problematic constituents in energy-derived waters, and aerobic degradation may provide a strategy for mitigating risks to aquatic organisms. The overall objective of this study was to determine the influence of concentrations of N (as ammonia) and P (as phosphate), and DO, as well as pH and temperatures on degradation of a commercial NA in bench-scale reactors. Commercial NAs provided replicable compounds necessary to compare influences of environmental conditions on degradation. NAs were quantified using high performance liquid chromatography. Microbial diversity and relative abundance were measured in treatments as explanatory parameters for potential effects of environmental conditions on microbial populations to support analytically measured NA degradation. Environmental conditions that positively influenced degradation rates of Fluka NAs included nutrients (C:N 10:1-500:1, C:P 100:1-5000:1), DO (4.76-8.43 mg L(-1)), pH (6-8), and temperature (5-25 °C). Approximately 50% removal of 61 ± 8 mg L(-1) was achieved in less than 2 d after NA introduction, achieving the method detection limit (5 mg L(-1)) by day 6 of the experiment in treatments with a C:N:P ratio of 100:10:1, DO > 8 mg L(-1), pH ∼8-9, and temperatures >23 °C. Microbial diversity was lowest in lower temperature treatments (6-16 °C), which may have resulted in observed slower NA degradation. Based on results from this study, when macro- and micronutrients were available, DO, pH, and temperature (within environmentally relevant ranges) influenced rates of aerobic degradation of Fluka NAs. This study could serve as a model for systematically evaluating environmental factors that influence NA degradation in field scenarios.

Effects of simulated oilfield produced water on early seedling growth after treatment in a pilot-scale constructed wetland system.

Seed germination and early seedling growth bioassays were used to evaluate phytotoxicity of simulated oilfield produced water (OPW) before and after treatment in a subsurface-flow, pilot-scale constructed wetland treatment system (CWTS). Responses to untreated and treated OPW were compared among seven plant species, including three monocotyledons: corn (Zea mays), millet (Panicum miliaceum), and sorghum (Sorghum bicolor); and four dicotyledons: lettuce (Lactuca sativa), okra (Abelmoschus esculents), watermelon (Citrullus lanatus), and soybean (Glycine max). Phytotoxicity was greater in untreated OPW than in treated OPW. Exposures to untreated and treated OPW enhanced growth in some plant species (sorghum, millet, okra, and corn) relative to a negative control and reduced growth in other plant species (lettuce, soybean, and watermelon). Early seedling growth parameters indicated that dicotyledons were more sensitive to test waters compared to monocotyledons, suggesting that morphological differences between plant species affected phytotoxicity. Results indicated the following sensitivity scale for plant species: lettuce>soybean>watermelon>corn>okra≈millet>sorghum. Phytotoxicity of the treated OPW to lettuce and soybean, although concentrations of COCs were less than irrigation guideline concentrations, suggests that chemical characterization and comparison to guideline concentrations alone may not be sufficient to evaluate water for use in growing crops.

Treatment of oil and grease in produced water by a pilot-scale constructed wetland system using biogeochemical processes.

Constructed wetland treatment systems (CWTSs) can effectively remove many constituents that limit beneficial use of oilfield produced water. The objectives of this investigation were: (1) to assess the effect of mass loadings of oil and grease (O & G) on treatment performance in pilot-scale subsurface flow and free water surface CWTS series having sequential reducing and oxidizing cells, and (2) to evaluate effects on treatment performance of adding a pilot-scale oil-water separator. Increase in O & G mass loading from 5 to 20 mg min(-1) caused decreases in both dissolved oxygen concentration and sediment redox potential, which affected treatment performance. Biogeochemical pathways for removal of O & G, iron, and manganese operate under oxidizing conditions, and removal rate coefficients for these constituents decreased (0.905-0.514 d(-1) for O & G, 0.773-0.452 d(-1) for iron, and 0.970-0.518 d(-1) for manganese) because greater mass loading of O & G promoted reducing conditions. With increased mass loading, removal rate coefficients for nickel and zinc increased from 0.074 to 0.565 d(-1) and from 0.196 to 1.08 d(-1), respectively. Although the sequential reducing and oxidizing cells in the CWTS were very effective in treating the targeted constituents, an oil-water separator was added prior to wetland cells to enhance O & G removal at high inflow concentration (100 mg L(-1)). The oil-water separator removed approximately 50% of the O & G, and removal extents and efficiencies approximated those observed at 50 mg L(-1) inflow concentration during treatment without an oil-water separator.

Chemical and physical characterization of produced waters from conventional and unconventional fossil fuel resources.

Characterization of produced waters (PWs) is an initial step for determining potential beneficial uses such as irrigation and surface water discharge at some sites. A meta-analysis of characteristics of five PW sources [i.e. shale gas (SGPWs), conventional natural gas (NGPWs), conventional oil (OPWs), coal-bed methane (CBMPWs), tight gas sands (TGSPWs)] was conducted from peer-reviewed literature, government or industry documents, book chapters, internet sources, analytical records from industry, and analyses of PW samples. This meta-analysis assembled a large dataset to extract information of interest such as differences and similarities in constituent and constituent concentrations across these sources of PWs. The PW data analyzed were comprised of 377 coal-bed methane, 165 oilfield, 137 tight gas sand, 4000 natural gas, and 541 shale gas records. Majority of SGPWs, NGPWs, OPWs, and TGSPWs contain chloride concentrations ranging from saline (>30000 mg L(-1)) to hypersaline (>40000 mg L(-1)), while most CBMPWs were fresh (<5000 mg L(-1)). For inorganic constituents, most SGPW and NGPW iron concentrations exceeded the numeric criterion for irrigation and surface water discharge, while OPW and CBMPW iron concentrations were less than the criterion. Approximately one-fourth of the PW samples in this database are fresh and likely need minimal treatment for metal and metalloid constituents prior to use, while some PWs are brackish (5000-30000 mg Cl(-) L(-1)) to saline containing metals and metalloids that may require considerable treatment. Other PWs are hypersaline and produce a considerable waste stream from reverse osmosis; remediation of these waters may not be feasible. After renovation, fresh to saline PWs may be used for irrigation and replenishing surface waters.

A risk assessment approach to identifying constituents in oilfield produced water for treatment prior to beneficial use.

A risk assessment approach incorporating exposure pathways and calculated risk quotients was applied to identifying constituents requiring treatment prior to beneficial use of oilfield produced water (OPW). In this study, risk quotients are ratios of constituent concentrations in soil or water to guideline concentrations for no adverse effects to receptors. The risk assessment approach is illustrated by an example of an oilfield water produced from non-marine geologic strata of a rift basin in sub-Saharan Africa. The OPW studied has the following characteristics: 704-1370 mg L(-1) total dissolved solids (TDS), 45-48 mg L(-1) chloride, and 103.8 mg L(-1) oil and grease. Exposure pathways of constituents in OPW used for irrigation include: ingestion of plant tissue, ingestion and direct contact of irrigated soil by livestock, inhalation of aerosols or volatilized constituents, and ingestion of OPW directly by livestock. Applying risk quotient methods for constituents in soil and water, constituents of concern (COCs) identified for irrigation and livestock watering using the OPW studied include: iron (Fe), manganese (Mn), nickel (Ni), zinc (Zn), and oil and grease. Approximately 165,000 barrels d(-1) (26,233 m(3) d(-1)) of OPW from the study site are available for use. Identification of COCs and consideration of water quantity allows for development of reliable treatment design criteria to ensure effective and consistent treatment is achieved to meet guideline levels required for irrigation, livestock watering, or other uses. This study illustrates the utility of risk assessment for identifying the COCs in OPW for treatment, the level of treatment required, and viable options for use of the treated water.

Performance of a pilot-scale constructed wetland system for treating simulated ash basin water.

A pilot-scale constructed wetland treatment system (CWTS) was designed and built to decrease the concentration and toxicity of constituents of concern in ash basin water from coal-burning power plants. The CWTS was designed to promote the following treatment processes for metals and metalloids: precipitation as non-bioavailable sulfides, co-precipitation with iron oxyhydroxides, and adsorption onto iron oxides. Concentrations of Zn, Cr, Hg, As, and Se in simulated ash basin water were reduced by the CWTS to less than USEPA-recommended water quality criteria. The removal efficiency (defined as the percent concentration decrease from influent to effluent) was dependent on the influent concentration of the constituent, while the extent of removal (defined as the concentration of a constituent of concern in the CWTS effluent) was independent of the influent concentration. Results from toxicity experiments illustrated that the CWTS eliminated influent toxicity with regard to survival and reduced influent toxicity with regard to reproduction. Reduction in potential for scale formation and biofouling was achieved through treatment of the simulated ash basin water by the pilot-scale CWTS.

Design and performance of a pilot-scale constructed wetland treatment system for natural gas storage produced water.

To test the hypothesis that water produced from natural gas storage wells could be treated effectively by constructed wetland treatment systems, a modular pilot-scale system was designed, built, and used for treating gas storage produced waters. Four simulated waters representing the range of contaminant concentrations typical of actual produced waters were treated, and the system's performance was monitored. Freshwater wetland cells planted with Schoenoplectus californicus and Typha latifolia were used to treat fresh and brackish waters. Saline and hypersaline waters were treated by saltwater wetland cells planted with Spartina alterniflora and by reverse osmosis. Effective removal of cadmium, copper, lead, and zinc was achieved by the pilot-scale system. Results suggest that use of specifically designed constructed wetland treatment systems provides a flexible and effective approach for treating gas storage produced waters over a wide range of compositions.