Ania C. Ulrich

Oil sands naphthenic acids: a review of properties, measurement, and treatment.

The Alberta oil sands contain one of the worlds largest reserves of oil - over 169 billion barrels of bitumen are economically recoverable with current extraction technologies. Surface mining and subsequent hot water extraction of bitumen from the ore generates about nine cubic meters of raw tailings per cubic meter of oil. Oil sands facilities are required to operate under a policy of zero water discharge, resulting in ponds containing more than one billion cubic meters of tailings, a mixture of sand, fines and process-affected water. Process-affected water contains numerous organic compounds, including naphthenic acids (NAs), which have been identified as the primary source of acute toxicity of process-affected water. Developments in analytical techniques, aerobic biodegradability, and treatment via chemical oxidation (ozone) of NAs are reviewed. The field continues to be challenged by the lack of a cost-effective, accurate analytical technique for NAs or an understanding of all the organic constituents in process-affected water that may be contributing to observed toxicity and thus requiring treatment.

In situ biodegradation of naphthenic acids in oil sands tailings pond water using indigenous algae-bacteria consortium.

In this study, the biodegradation of total acid-extractable organics (TAOs), commonly called naphthenic acids (NAs), was investigated. An indigenous microbial culture containing algae and bacteria was taken from the surface of a tailings pond and incubated over the course of 120days. The influence of light, oxygen and the presence of indigenous algae and bacteria, and a diatom (Navicula pelliculosa) on the TAO removal rate were elucidated. The highest biodegradation rate was observed with bacteria growth only (without light exposure) with a half-life (t(1/2)) of 203days. The algae-bacteria consortium enhanced the detoxification process, however, bacterial biomass played the main role in toxicity reduction. Principal component analysis (PCA) conducted on FT-IR spectra, identified functional groups and bonds (representing potential markers for biotransformation of TAOs) as follows: hydroxyl, carboxyl and amide groups along with CH, arylH, arylOH and NH bonds.

Metal removal from oil sands tailings pond water by indigenous micro-alga.

This paper reports the removal of ten target metals of environmental concern ((53)Cr, Mn, Co, (60)Ni, (65)Cu, (66)Zn, As, (88)Sr, (95)Mo, and Ba) from oil sands tailings pond water. The organism responsible for removal was found to be an indigenous green micro-alga identified as Parachlorella kessleri by sequencing of the 23S rRNA gene. P. kessleri grew in tailings pond water samples taken from two oil sands operators (Syncrude Canada Ltd. and Albian Sands Energy Inc.), and enriched with low (0.24 mM NO(3)(-) and 0.016 mM PO(4)(-3)) and high (1.98 mM NO(3)(-) and 0.20mM PO(4)(-3)) concentrations of nutrient supplements (the most realistic scenario). The removal of (60)Ni, (65)Cu, As, (88)Sr, (95)Mo, and Ba from Syncrude tailings pond water was significantly enhanced by high concentrations of nitrogen and phosphorus, whereas the high nutrient concentrations adversely affected the removal of Co, (60)Ni, As, (88)Sr, and Mo in samples of Albian tailings pond water. Based on ANOVA two-factor analysis, higher nutrient concentration does not always result in higher metal removal, and TPW source must also be considered.

Adsorption of Acid Extractable Oil Sands Tailings Organics onto Raw and Activated Oil Sands Coke

AbstractThe accumulation of organic contaminants in process-affected (PA) water represents an environmental liability for oil sands operators. Oil sands coke is a promising adsorbent for removing dissolved organic carbon (DOC), which includes toxic acid-extractable oil sands tailings organics (AEOSTO) found in PA water. The ability of raw and activated delayed and fluid coke to remove DOC and AEOSTO from PA water was assessed. Treatment with 5  g/L of activated delayed and fluid coke removed 91% of DOC and 92% of AEOSTO at levels of 36  mg/L and 60  mg/L, respectively. Heavy metal leaching of vanadium at 5.9  mg/L was observed for a 5  g/L application of activated delayed coke, representing a challenge to the approach. Microtox testing indicated that higher carbon doses of activated cokes were effective in reducing toxic the biological response caused by organic compounds; however, exposure to heavy metals increased the toxic effect with time. The proposed methodology should be coupled with an inorganic t...

Coupling bioelectricity generation and oil sands tailings treatment using microbial fuel cells.

In this study, four dual-chambered microbial fuel cells (MFC1-4) were constructed and filled with different ratios of mature fine tailings and oil sands process-affected water to test the feasibility of MFCs to simultaneously generate electricity and treat oil sands tailings. After 800 h of operation, the maximum voltage was observed in MFC4 at 0.726 V with 1.2kΩ external resistance loaded. The maximum power density reached 392 ± 15 mW/m(2) during the 1,700 h of MFC4 operation. With continuous electricity generation, MFC4 removed 27.8% of the total COD, 81.8% of the soluble COD and 32.9% of the total acid extractable organics. Moreover, effective removal of eight heavy metals, includes 97.8% of (78)Se, 96.8% of Ba, 94.7% of (88)Sr, 81.3% for (66)Zn, 77.1% of (95)Mo, 66.9% of (63)Cu, 44.9% of (53)Cr and 32.5% of Pb, was achieved.

Biogeochemical processes controlling the mobility of major ions and trace metals in aquitard sediments beneath an oil sand tailing pond: laboratory studies and reactive transport modeling.

Increased production and expansion of the oil sand industry in Alberta are of great benefit to the economy, but they carry major environmental challenges. The volume of fluid fine tailings requiring storage is 840×10(6) m(3) and growing, making it imperative that we better understand the fate and transport of oil sand process-affected water (OSPW) seepage from these facilities. Accordingly, the current study seeks to characterize both a) the potential for major ion and trace element release, and b) the principal biogeochemical processes involved, as tailing pond OSPW infiltrates into, and interacts with, underlying glacial till sediments prior to reaching down gradient aquifers or surface waters. Objectives were addressed through a series of aqueous and solid phase experiments, including radial diffusion cells, an isotope analysis, X-ray diffraction, and sequential extractions. The diffusion cells were also simulated in a reactive transport framework to elucidate key reaction processes. The experiments indicate that the ingress and interaction of OSPW with the glacial till sediment-pore water system will result in: a mitigation of ingressing Na (retardation), displacement and then limited precipitation of exchangeable Ca and Mg (as carbonates), sulfate reduction and subsequent precipitation of the produced sulfides, as well as biodegradation of organic carbon. High concentrations of ingressing Cl (~375 mg L(-1)) and Na (~575 mg L(-1)) (even though the latter is delayed, or retarded) are expected to migrate through the till and into the underlying sand channel. Trace element mobility was influenced by ion exchange, oxidation-reduction, and mineral phase reactions including reductive dissolution of metal oxyhydroxides - in accordance with previous observations within sandy aquifer settings. Furthermore, although several trace elements showed the potential for release (Al, B, Ba, Cd, Mn, Pb, Si, Sr), large-scale mobilization is not supported. Thus, the present results suggest that in addition to the commonly cited naphthenic acids, remediation of OSPW-impacted groundwater will need to address high concentrations of major ions contributing to salinization.

Indigenous microbes survive in situ ozonation improving biodegradation of dissolved organic matter in aged oil sands process-affected waters

The oil sands industry faces significant challenges in developing effective remediation technologies for process-affected water stored in tailings ponds. Naphthenic acids, a complex mixture of cycloaliphatic carboxylic acids, have been of particular concern because they concentrate in tailings ponds and are a component of the acutely toxic fraction of process water. Ozone treatment has been demonstrated as an effective means of rapidly degrading naphthenic acids, reducing process water toxicity, and increasing its biodegradability following seeding with the endogenous process water bacteria. This study is the first to examine subsequent in situ biodegradation following ozone pretreatment. Two aged oil sands process-affected waters from experimental reclamation tailings ponds were ozonated to reduce the dissolved organic carbon, to which naphthenic acids contributed minimally (<1mgL(-1)). Treatment with an ozone dose of 50mgL(-1) improved the 84d biodegradability of remaining dissolved organic carbon during subsequent aerobic incubation (11-13mgL(-1) removed from aged process-affected waters versus 5mgL(-1) when not pretreated with ozone). The ozone-treated indigenous microbial communities were as capable of degrading organic matter as the same community not exposed to ozone. This supports ozonation coupled with biodegradation as an effective and feasible treatment option.

Partitioning and bioaccumulation of metals from oil sands process affected water in indigenous Parachlorella kessleri.

This paper studies the partitioning and bioaccumulation of ten target metals ((53)Cr, Mn, Co, (60)Ni, (65)Cu, (66)Zn, As, (88)Sr, (95)Mo and Ba) from oil sands tailings pond water (TPW) by indigenous Parachlorella kessleri. To determine the role of extracellular and intracellular bioaccumulation in metal removal by P. kessleri, TPW samples taken from two oil sands operators (Syncrude Canada Ltd. and Albian Sands Energy Inc.) were enriched with nutrient supplements. Results indicate that intracellular bioaccumulation played the main role in metal removal from TPW; whereas extracellular bioaccumulation was only observed to some extent for Mn, Co, (60)Ni, (65)Cu, (88)Sr, (95)Mo and Ba. The FTIR scan and titration of functional groups on the cell surface indicated low metal binding capacity by indigenous P. kessleri. However, it is believed that the dissolved cations and organic ligand content in TPW (such as naphthenic acids) may interfere with metal binding on the cell surface and lower extracellular bioaccumulation. In addition, the total bioaccumulation and bioconcentration factor (BCF) varied during the cultivation period in different growth regimes.

Fate and transport of oil sand process-affected water into the underlying clay till: A field study

The South Tailings Pond (STP) is a ~2300-ha tailing pond operated by Suncor Energy Inc. that has received oil sand process-affected (PA) water and mature fine tailings since 2006. The STP is underlain by a clay till, which is in turn underlain by the Wood Creek Sand Channel (WCSC). The sandy deposits of the WCSC provide greater geotechnical stability but could act as a potential flow pathway for PA water to migrate off site and into the Athabasca River. Preliminary modeling of the STP suggests that PA water from the pond will infiltrate into the underlying sand channel, but the extent and development of this impact is still poorly understood. Suncor Energy Inc. built interception wells and a cut-off-wall to control any potential seepage. Here we present the results of an investigation of the fate and transport of PA water in clay till underlying a 10 m × 10 m infiltration pond that was constructed on the southeastern portion of the STP. The geochemistry of pore water in the till underlying the infiltration pond was determined prior to filling with process-affected water (2008) and two years after the infiltration pond was filled with PA waters (2010). Pore water was analyzed for metals, cations, anions, and isotopes ((2)H and (18)O). The distribution of conservative tracers ((18)O and chloride) indicated migration of the PA waters to approximately 0.9 m, but the migrations of major ions and metals were significantly delayed relative to this depth. Uptake of Na and Mo and release of Ca, Mg, Mn, Ba, and Sr suggest that adsorption and ion exchange reactions are the foremost attenuation processes controlling inorganic solutes transport.

Limitation of fluorescence spectrophotometry in the measurement of naphthenic acids in oil sands process water

Fluorescence spectrophotometry has been proposed as a quick screening technique for the measurement of naphthenic acids (NAs). To evaluate the feasibility of this application, the fluorescence emission spectra of NAs extracted from three oil sands process water sources were compared with that of commercial NAs. The NAs resulting from the bitumen extraction process cannot be differentiated because of the similarity of the fluorescence spectra. Separation of the fluorescent species in NAs using high performance liquid chromatography with fluorescence detector proved unsuccessful. The acidic fraction of NAs is fluorescent but the basic fraction of NAs is not fluorescent, implying that aromatic acids in NAs give rise to the fluorescent signals. The concentrations of NAs in oil sands process water were measured by Fourier transform infrared spectroscopy (FTIR), fluorescence spectrophotometry and ultra high performance liquid chromatography-time of flight/mass spectrometry (UPLC-TOF/MS). Commercial Merichem and Kodak NAs are the best standards to use when measuring NAs concentration with FTIR and fluorescence spectrophotometry. In addition, the NAs concentrations measured by fluorescence spectrophotometry are about 30 times higher than those measured by FTIR and UPLC-TOF/MS. The findings in this study underscore the limitation of fluorescence spectrophotometry in the measurement of NAs.