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).     

Flux capacities and acclimation costs in Trichodesmium from the Gulf of Mexico

Phytoplankton function and acclimation are driven by catalytic protein complexes that mediate key physiological transformations, including generation of photosynthetic ATP and reductant, and carbon and nitrogen fixation. Quantitation of capacities for these processes allows estimation of rates for key ecosystem processes, and identification of factors limiting primary productivity. We herein present molar quantitations of PSI, PSII, ATP synthase, RuBisCO and the Fe protein of nitrogenase of Trichodesmium collected from the Gulf of Mexico, in comparison to determinations for a range of cyanobacteria growing in culture. Using these measurements, estimates were generated for Trichodesmium capacities for carbon fixation of 1–3.4 g C g chl a ⁻¹ h⁻¹ and nitrogen fixation of 0.06–0.17 g N g chl a ⁻¹ h⁻¹, with diel variations in capacities. ATP synthase levels show that ATP synthesis capacity is sufficient to support these levels of carbon and nitrogen fixation, and that ATP synthase levels change over the day in accordance with the ATP demands of nitrogenase and RuBisCO activity. Levels of measured complexes indicate that Trichodesmium manifests n-type diel light acclimation through rapid changes in RuBisCO:PSII, supported by significant investment of cellular nitrogen. The plasticity in the levels and stoichiometry of these core complexes show that changes in the abundance of core protein complexes are an important component of acclimation and regulation of metabolic function by Trichodesmium populations. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Laboratory-scale in situ chemical oxidation of a perchloroethylene pool using permanganate

In situ chemical oxidation (ISCO) is an emerging technology for the destruction of some chlorinated solvents present in subsurface environments. A laboratory investigation using a physical model was designed to assess the effectiveness of using permanganate as an oxidant to reduce the mass of a perchloroethylene (PCE) pool. The physical model was filled with silica sand overlying a silica flour base, simulating a two-dimensional saturated sand zone overlying a capillary barrier. PCE was introduced into the model so that it rested on top of the silica flour base, forming a dense nonaqueous phase liquid pool. The experimental methodology involved flushing the model with a permanganate solution for 146 days. During this period, measurements of chloride were used to assess the extent of pool oxidation. Before and after the oxidant flush, the quasi-steady state dissolution from the PCE pool was evaluated. Additionally, tracer studies were completed to assess changes in the flow field due to the oxidation process. At the termination of the experiment nine soil cores extracted from the model were used to detect the presence of MnO2 deposits and to quantify the mass of PCE remaining in the system. Excavation of the remaining material in the model revealed that the MnO2 distribution throughout the model was consistent with that observed in the cores. The oxidant flush was concluded before all of the pure phase PCE had been completely oxidized; however, approximately 45% of the PCE mass was removed, resulting in a fourfold decrease in the quasi-steady state aqueous phase mass loading of PCE from the pool. Measurements of chloride during the oxidant flush and of PCE in the soil cores suggested that the oxidation reaction occurred primarily at the upgradient edge of the PCE pool. MnO2 deposits within the model aquifer decreased the velocity of water directly above the pool, and the overall mass transfer from the remaining PCE pool. The results of this experimental study indicate that ISCO using permanganate is capable of removing substantial mass from a DNAPL pool; however, the performance of ISCO as a pool removal technology will be limited by the formation and precipitation of hydrous MnO2 that occurs during the oxidation process.     

Effects of consolidated tailings water on red-osier dogwood (Cornus stolonifera Michx) seedlings

As part of their tailings management, the oil sand industries plan on producing consolidated (composite) tailings (CT), in which an inorganic coagulant aid (gypsum) is added to create a non-segregating deposit. The water associated with this treatment contains potentially phytotoxic levels of sodium, sulfate, chloride, boron, aluminum, fluoride and strontium. Since CT water is expected to saturate deposits in the reclamation areas, it may affect successful reclamation of these sites. Red-osier dogwood (Cornus stolonifera Michx) was demonstrated to be relatively salt resistant and to have high potential for the reclamation of mining areas. In the present study, we used red-osier dogwood to examine the effects of CT water on the accumulation of ions within plant tissue, growth, gas exchange, water potentials and chlorophyll concentration. CT water reduced shoot lengths and dry weights in treated plants. The roots of treated plants accumulated higher concentrations of sodium and chloride than did shoots. The accumulation of sodium and chloride was accompanied by an increase in magnesium and calcium and a decrease in potassium in the roots, while the levels of potassium increased in the leaves. CT water altered gas exchange and water potentials in seedlings, and resulted in a decrease in chlorophyll's a and b. The results suggest that the mechanisms of salt resistance in red-osier dogwood seedlings involve the restriction of sodium transport from roots to shoots.     

Barley, a potential species for initial reclamation of saline composite tailings of oil sands

The oil sands industry in Alberta (Canada) has developed the composite tailings (CT) process to reduce the fluid fine tails resulting from the processing of oil sands. This process uses a chemical coagulant (gypsum or alum) to produce aggregated fines (clay), so they are retained with the coarse sand fraction of the extraction tailings to form CT, from which fines-free water is released relatively quickly compared with untreated tailings. The resulting CT and CT waters are saline-sodic, with Na+, SO4(2-), and Cl- being the dominant ions. When freshly deposited, the CT deposits are too soft for access by reclamation equipment, and the time required for these deposits to remove the water sufficiently to support traffic is uncertain. A greenhouse study was designed to determine the suitability of barley (Hordeum vulgare L.) for reclamation of fresh CT deposits and to evaluate benefits of peat amendments. This study assessed germination, early plant growth, chlorophyll content, and survival of barley growing in alum- and gypsum-treated CT, with and without peat amendment. Ion and trace metal accumulation in the root and shoot tissues of barley was determined. Amendment of CT with peat improved germination, survival, and growth of barley, but did not prevent leaf injury (probably due to Na and Cl- and possibly multiple nutrient deficiency). Field studies will be undertaken to validate our greenhouse results suggesting that barley could be used to improve dewatering of the freshly deposited substrates, reduce soil erosion, and facilitate leaching of ions by root penetration into the substrate.     

Isolation and characterization of naphthenic acids from Athabasca oil sands tailings pond water

A laboratory bench procedure was developed to efficiently extract naphthenic acids from bulk volumes of Athabasca oil sands tailings pond water (TPW) for use in mammalian oral toxicity testing. This solvent-based procedure involved low solvent losses and a good extraction yield with low levels of impurities. Importantly, labour-intensive centrifugation of source water to remove solids was avoided, allowing processing of much larger volumes of water compared with previous protocols. Naphthenic acids, present at an estimated concentration of 81 mg/l, were procured from 515.5 l of TPW at an overall extraction efficiency of approximately 85%. By using distillation to recover and recycle solvent, a high solvent:water ratio was maintained while actual solvent consumption was limited to 70 ml per liter of water processed. Electrospray ionization mass spectrometry suggested a highly heterogeneous naphthenic acid mixture that exhibited nearly identical proportions of monocyclic, polycyclic, and acyclic acids with molecular weights primarily between 220 and 360. Biphenyls, naphthalenes, and phenanthrene/anthracene were the most prominent impurities detected, but their levels were low (< or = 13 microg/l) even in a concentrated solution of the naphthenic acids (8549 mg/l). Naphthenic acids stored at 4 degrees C at this concentration were stable, exhibiting no significant change in concentration over a 10-month period. This bulk isolation procedure should be useful to others needing to process large volumes of tailings or other source water for the purpose of procuring moderate amounts of naphthenic acids.     

Effects of oil sands process-affected waters and naphthenic acids on yellow perch (Perca flavescens) and Japanese medaka (Orizias latipes) embryonic development

Syncrude Canada Ltd. is currently developing environmentally acceptable oil sands process-affected water management methods as part of their land reclamation strategy. Surface waters of the “wet landscape” reclamation option characteristically have elevated concentrations of sodium sulphate and naphthenic acids (NAs), with low levels of PAHs. The following experiment compared early-life stage responses of yellow perch (Perca flavescens) to those of Japanese medaka (Oryzias latipes) when exposed to Mildred Lake settling basin (MLSB) surface water and a commercial sodium naphthenate (Na-NA) standard. Perch eggs were fertilized and incubated in: 100%, 50%, 20%, 4%, 0.8%, and 0.16% dilutions of MLSB water, as well as 20, 10, 5, 2.5, and 1.25 mg/l solutions of the commercial standard. Medaka embryos were exposed to the same treatments, post-fertilization. Both species demonstrated an increase in the incidence of deformity, and a decrease in length at hatch as NA concentrations increased. MLSB surface water contained higher levels of NAs than the commercial standard, however, showed consistently higher NA threshold effect concentrations for both species. Significant differences between the MLSB water and the Na-NA standard suggest that they contain NA congeners with different toxicity, or other compounds such as PAHs. Species differences in thresholds could be explained by the difference in developmental stage in which the exposures were initiated.     

The influence of cosolvent and heat on the solubility and reactivity of organophosphorous pesticide DNAPL alkaline hydrolysis

The presented research concerned the compatibility of cosolvents with in situ alkaline hydrolysis (ISAH) for treatment of organophosphorous (OPP) pesticide contaminated sites. In addition, the influence of moderate temperature heat increments was studied as a possible enhancement method. A complex dense non-aqueous phase liquid (DNAPL) of primarily parathion (~50 %) and methyl parathion (~15 %) obtained from the Danish Groyne 42 site was used as a contaminant source, and ethanol and propan-2-ol (0, 25, and 50 v/v%) was used as cosolvents in tap water and 0.34 M NaOH. Both cosolvents showed OPP solubility enhancement at 50 v/v% cosolvent content, with slightly higher OPP concentrations reached with propan-2-ol. Data on hydrolysis products did not show a clear trend with respect to alkaline hydrolysis reactivity in the presence of cosolvents. Results indicated that the hydrolysis rate of methyl-parathion (MP3) decreased with addition of cosolvent, whereas the hydrolysis rate of ethyl-parathion (EP3) remained constant, and overall indications were that the hydrolysis reactions were limited by the rate of hydrolysis rather than NAPL dissolution. In addition to cosolvents, the influence of low-temperature heating on ISAH was studied. Increasing reaction temperature from 10 to 30 °C provided an average rate of hydrolysis enhancement by a factor of 1.4–4.8 dependent on the base of calculation. When combining 50 v/v% cosolvent addition and heating to 30 °C, EP3 solubility was significantly enhanced and results for O,O-diethyl-thiophosphoric acid (EP2 acid) showed a significant enhancement of hydrolysis as well. However, this could not be supported by para-nitrophenol (PNP) data indicating the instability of this product in the presence of cosolvent.

     

Jack pine growth and elemental composition are affected by saline tailings water

In the processing of oil sands from Alberta's Athabasca formation, large quantities of alkaline, saline tailings and associated process-affected waters are produced. These waters may have a negative effect on plants used in reclamation of mined areas in this region of the northern boreal forest. In the present study, we examined the effects of process-affected water on the growth and elemental composition of jack pine (Pinus banksiana Lamb.) seedlings. Seedlings were grown in sand culture, and treated with tailings water to which mineral nutrients had been added. One-month-old seedlings were treated for 14 d, and all measured growth parameters were reduced. Growth and shoot elemental composition were also measured in seven-month-old seedlings that were treated for 10 wk with process-affected water. Shoots had significantly elevated levels of Na, Cl, S, P, B, and Sr, and significantly reduced levels of Fe, Mo, Ba, and K. The relationships between elemental composition and seedling growth and injury were examined using multiple regression. Growth rates, dry weights, and carotenoid content were reduced, but were not related to shoot elemental composition. Needle necrosis was positively related to tissue Na and Cl. Results indicate that reclamation planning must consider substrate Na and Cl levels when planting jack pine on tailings-affected sites.