A Light Touch: Solar Photocatalysis Detoxifies Oil Sands Process-Affected Waters Prior to Significant Treatment of Naphthenic Acids.

Environmental reclamation of Canada's oil sands tailings ponds is among the single largest water treatment challenges globally. The toxicity of oil sands process-affected water (OSPW) has been associated with its dissolved organics, a complex mixture of naphthenic acid fraction components (NAFCs). Here, we evaluated solar treatment with buoyant photocatalysts (BPCs) as a passive advanced oxidation process (P-AOP) for OSPW remediation. Photocatalysis fully degraded naphthenic acids (NAs) and acid extractable organics (AEO) in 3 different OSPW samples. However, classical NAs and AEO, traditionally considered among the principal toxicants in OSPW, were not correlated with OSPW toxicity herein. Instead, nontarget petroleomic analysis revealed that low-polarity organosulfur compounds, composing <10% of the total AEO, apparently accounted for the majority of waters' toxicity to fish, as described by a model of tissue partitioning. These findings have implications for OSPW release, for which a less extensive but more selective treatment may be required than previously expected.

Treatment of oil sands process water using petroleum coke: Field pilot.

This is the first large-scale field pilot study that examined the feasibility and effectiveness of petroleum coke (PC), produced by a Fluid Coking Process, as an adsorbent for oil sands process water (OSPW) treatment. The pilot program consisted of an inline series of two reactors (pipeline reactor 1, and batch reactor 2) and lasted for approximately 4 months. The quality of treated OSPW as a function of residence time in the PC deposit under natural climatic conditions was assessed by looking at changes in organic compounds (acid extractable fraction (AEF), dissolved organic carbon (DOC), etc.), vanadium, and other trace element concentrations, major ions, conductivity, total suspended solids (TSS), pH and toxicity. The results indicated that the AEF adsorption by PC followed pseudo-second order kinetics and the overall combined removal efficiency of AEF was greater than 80%. Reactor 1 showed higher AEF removal than Reactor 2. DOC decreased about 50% after 4 weeks of retention in the PC deposit. An increase of vanadium concentration after PC contact indicated that vanadium leaching occurred. However, with increased residence time in the PC deposit, vanadium concentration decreased in the cells and tanks by 42% and 98%, respectively. Filtration through the PC deposit reduced the TSS in OSPW to less than laboratory detectable limits. Unlike untreated OSPW, treated OSPW did not show an acute toxic response based on whole effluent toxicity testing using trout, zooplankton, and bacteria. This study demonstrated that PC adsorption is a potentially commercially viable technology for highly efficient treatment of OSPW.

Bioaccumulation potential of naphthenic acids and other ionizable dissolved organics in oil sands process water (OSPW) - A review.

Bitumen recovery via mining in Alberta's Athabasca region generates large quantities of oil sands process water (OSPW). Aquatic toxicity of OSPW has been well-studied and the class of organic compounds referred to as naphthenic acids (NAs) are consistently implicated as the primary driver. Proposed lease closure options include treated produced waters in reclaimed landscapes such as pit lakes and wetlands. Consequently, it is crucial to understand the bioaccumulation potential of NAs and other OSPW dissolved organics in these environments. Early studies were focussed only on NAs due to analytical limitations, however, later studies investigated additional classes of dissolved organics in OSPW. Reported bioconcentration factors (BCFs) for NAs in fish and amphibians range from 0.24 to 53 L/kg wet-weight. Most quantitative assessments of NAs bioaccumulation potential evaluated commercial NAs mixtures as a surrogate for OSPW and used using single-ion monitoring for measuring NAs concentrations. The resulting BCF values are based on the NA isomers that conform to the formula, C13H22O2. More recently, an advanced analytical technique capable of determining the profile of different isomer classes in OSPW showed that NAs and other OSPW ionizable dissolved organics (OSPW-IDO) have low partitioning to simulated biological storage lipids, suggesting low bioaccumulation potential. Using the same analytical technique to assess in vivo fish exposures, a subsequent study reported a range of BCFs for OSPW NAs between 0.7 and 53 L/kg wet-weight and heteroatomic isomer classes containing S or N heteroatoms had BCFs between 0.6 and 28 L/kg wet-weight. Reported BCFs for all isomer classes of the OSPW-IDO fraction were less than the Canadian standard for bioaccumulative designation (i.e., BCF ≥ 5000).

Overview of Existing Science to Inform Oil Sands Process Water Release: A Technical Workshop Summary.

The extraction of oil sands from mining operations in the Athabasca Oil Sands Region uses an alkaline hot water extraction process. The oil sands process water (OSPW) is recycled to facilitate material transport (e.g., ore and tailings), process cooling, and is also reused in the extraction process. The industry has expanded since commercial mining began in 1967 and companies have been accumulating increasing inventories of OSPW. Short- and long-term sustainable water management practices require the ability to return treated water to the environment. The safe release of OSPW needs to be based on sound science and engineering practices to ensure downstream protection of ecological and human health. A significant body of research has contributed to the understanding of the chemistry and toxicity of OSPW. A multistakeholder science workshop was held in September 2017 to summarize the state of science on the toxicity and chemistry of OSPW. The goal of the workshop was to review completed research in the areas of toxicology, chemical analysis, and monitoring to support the release of treated oil sands water. A key outcome from the workshop was identifying research needs to inform future water management practices required to support OSPW return. Another key outcome of the workshop was the recognition that methods are sufficiently developed to characterize chemical and toxicological characteristics of OSPW to address and close knowledge gaps. Industry, government, and local indigenous stakeholders have proceeded to utilize these insights in reviewing policy and regulations. Integr Environ Assess Manag 2019;15:519-527. © 2019 SETAC.

Petroleum coke adsorption as a water management option for oil sands process-affected water.

Water is integral to both operational and environmental aspects of the oil sands industry. A water treatment option based on the use of petroleum coke (PC), a by-product of bitumen upgrading, was examined as an opportunity to reduce site oil sands process-affected water (OSPW) inventories and net raw water demand. Changes in OSPW quality when treated with PC included increments in pH levels and concentrations of vanadium, molybdenum, and sulphate. Constituents that decreased in concentration after PC adsorption included total acid-extractable organics (TAO), bicarbonate, calcium, barium, magnesium, and strontium. Changes in naphthenic acids (NAs) speciation were observed after PC adsorption. A battery of bioassays was used to measure the OSPW toxicity. The results indicated that untreated OSPW was toxic towards Vibrio fischeri and rainbow trout. However, OSPW treated with PC at appropriate dosages was not acutely toxic towards these test organisms. Removal of TAO was found to be an adsorption process, fitting the Langmuir and Langmuir-Freundlich isotherm models. For TAO concentrations of 60 mg/L, adsorption capacities ranged between 0.1 and 0.46 mg/g. This study demonstrates that freshly produced PC from fluid cokers provides an effective treatment of OSPW in terms of key constituents' removal and toxicity reduction.

Naphthenic acids speciation and removal during petroleum-coke adsorption and ozonation of oil sands process-affected water.

The Athabasca Oil Sands industry produces large volumes of oil sands process-affected water (OSPW) as a result of bitumen extraction and upgrading processes. Constituents of OSPW include chloride, naphthenic acids (NAs), aromatic hydrocarbons, and trace heavy metals, among other inorganic and organic compounds. To address the environmental issues associated with the recycling and/or safe return of OSPW into the environment, water treatment technologies are required. This study examined, for the first time, the impacts of pretreatment steps, including filtration and petroleum-coke adsorption, on ozonation requirements and performance. The effect of the initial OSPW pH on treatment performance, and the evolution of ozonation and its impact on OSPW toxicity and biodegradability were also examined. The degradation of more than 76% of total acid-extractable organics was achieved using a semi-batch ozonation system at a utilized ozone dose of 150 mg/L. With a utilized ozone dose of 100 mg/L, the treated OSPW became more biodegradable and showed no toxicity towards Vibrio fischeri. Changes in the NA profiles in terms of carbon number and number of rings were observed after ozonation. The filtration of the OSPW did not improve the ozonation performance. Petroleum-coke adsorption was found to be effective in reducing total acid-extractable organics by a 91%, NA content by an 84%, and OSPW toxicity from 4.3 to 1.1 toxicity units. The results of this study indicate that the combination of petroleum-coke adsorption and ozonation is a promising treatment approach to treat OSPW.

Ozonation of oil sands process water removes naphthenic acids and toxicity.

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).