Papers by Michael MacKinnon
Environmental Technology Letters, 1984
A simple aqueous acetylation method was successfully applied to the analysis of ppb to low ppm le... more A simple aqueous acetylation method was successfully applied to the analysis of ppb to low ppm levels of phenolic compounds in waste‐waters from the Syncrude Canada Ltd. oil sands plant in northern Alberta. Phenolics in process‐affected waters, as well as surface and ground waters were extracted as acetate derivatives from aqueous solution, quantitated by FID‐GC and identified by GC‐MS. Phenol,
Water research, 2005
Polyacrylamides are widely used as flocculants to enhance clarification of drinking waters and do... more Polyacrylamides are widely used as flocculants to enhance clarification of drinking waters and domestic wastewaters, for stabilization of agricultural soils, and to aid in managing mine tailings. The flocs produced with polyacrylamide may be deposited into retention areas that become anaerobic. Although it is unlikely that the carbon backbone of these polymers would be cleaved by microbial activity, the amide group could serve as a nitrogen source for microorganisms. Previous studies have shown that aerobic bacteria utilize the nitrogen from polyacrylamide. This study assessed whether methanogenesis was stimulated when an anionic polyacrylamide (Magnafloc LT27AG) was the sole fixed nitrogen source in serum-bottle microcosms. Microorganisms from two oil sands tailings sources, and a domestic anaerobic sewage sludge were used, with benzoate or acetate provided as carbon and energy sources. In each inoculum-substrate combination, the presence of polyacrylamide-enhanced methane producti...
Water, Air, & Soil Pollution, 2010
Page 1. Growth and Physiological Responses of Triticum aestivum and Deschampsia caespitosa Expose... more Page 1. Growth and Physiological Responses of Triticum aestivum and Deschampsia caespitosa Exposed to Petroleum Coke Colin Nakata & Clara Qualizza & Mike MacKinnon & Sylvie Renault Received: 25 February 2010 ...
Water Research, 2002
The water produced during the extraction of bitumen from oil sands is toxic to aquatic organisms ... more The water produced during the extraction of bitumen from oil sands is toxic to aquatic organisms due largely to a group of naturally occurring organic acids, naphthenic acids (NAs), that are solubilized from the bitumen during processing. NAs are a complex mixture of alkyl-substituted acyclic and cycloaliphatic carboxylic acids, with the general chemical formula C n H 2n+Z O 2 , where n is the carbon number and Z specifies a homologous family. Gas chromatography-electron impact mass spectrometry was used to characterize NAs in nine water samples derived from oil sands extraction processes. For each sample, the analysis provided the relative abundances for up to 156 base peaks, with each representing at least one NA structure. Plotting the relative abundances of NAs as three-dimensional bar graphs showed differences among samples. The relative abundance of NAs with carbon numbers p21 to those in the ''C22+cluster'' (sum of all NAs with carbon numbers X22 in Z families 0 to À12) proved useful for comparing the water samples that had a range of toxicities. A decrease in toxicity of process-affected waters accompanied an increase in the proportion of NAs in the ''C22+cluster'', likely caused by biodegradation of NAs with carbon numbers of p21. In addition, an increase in the proportion of NAs in the ''C22+cluster'' accompanied a decrease in the total NAs in the process-affected waters, again suggesting the selective removal of NAs with carbon numbers of p21. This is the first investigation in which changes in the fingerprint of the NA fraction of process-affected waters from the oil sands operations has corresponded with measured toxicity in these waters.
Water Research, 2001
}Naphthenic acids (NAs) are a complex mixture of naturally occurring acyclic and cyclic aliphatic... more }Naphthenic acids (NAs) are a complex mixture of naturally occurring acyclic and cyclic aliphatic carboxylic acids in petroleum. In the Athabasca oil sands, NAs have been identified as the largest component of dissolved organic matter in the tailings waters from oils sands extraction processes. They are the major contributor to the acute toxicity of the fine tailings wastewaters at the oil sands extraction plants in northeastern Alberta, Canada. In this study, three sources of NAs were studied, including commercially available NAs, those extracted from oil sands process-affected waters, and individual naphthenic-like surrogate compounds. Analysis by gas chromatography-mass spectrometry demonstrated differences between the commercial and extracted NAs. The NAs derived from the process-affected waters showed a short-term inhibition of methanogenesis from H 2 or acetate, but with time the populations resumed methane production. It has been postulated that microbial metabolism of the carboxylated side chains of NAs would lead to methane production. The two NA mixtures failed to stimulate methanogenesis in microcosms that contained either oil sands fine tailings or domestic sewage sludge. However, in microcosms with sewage sludge, methanogenesis was stimulated by some surrogate NAs including 3-cyclohexylpropanoic acid at 400-800 mg/L, 5-cyclohexylpentanoic acid at 200 mg/L or 6-phenylhexanoic acid at 200 and 400 mg/L. When added at 200 mg/L to methanogenic microcosms containing fine tailings, 3-cyclohexylpropanoic and 4-cyclohexylbutanoic acids produced methane yields that suggested mineralization of the side chain and the ring.
Trees, 2008
Abstract In earlier studies, we established that mycor-rhizal associations protect plants against... more Abstract In earlier studies, we established that mycor-rhizal associations protect plants against salt stress. However, elevated boron levels are often present in saline soils and little is known about the effects of boron on salt resistance of mycorrhizal plants. In the present study, we ...
Physiologia Plantarum, 2009
Black spruce (Picea mariana), white spruce (Picea glauca) and jack pine (Pinus banksiana) were in... more Black spruce (Picea mariana), white spruce (Picea glauca) and jack pine (Pinus banksiana) were inoculated with Suillus tomentosus and subjected to potassium fluoride (1 mM KF and 5 mM KF) in the presence and absence of 60 mM NaCl. The NaCl and KF treatments reduced total dry weights in jack pine and black spruce seedlings, but they did not affect total dry weights in white spruce seedlings. The addition of 60 mM NaCl to KF treatment solutions alleviated fluoride-induced needle injury in ectomycorrhizal (ECM) black spruce and white spruce, but had little effect in jack pine seedlings. Both KF and 60 mM NaCl treatments reduced E values compared with non-treated control seedlings. However, with the exception of small reductions of K(r) by NaCl treatments in black spruce, the applied KF and NaCl treatments had little effect on K(r) in ECM plants. Chloride tissue concentrations in NaCl-treated plants were not affected by the presence of KF in treatment solutions. However, shoot F concentrations in ECM black spruce and white spruce treated with 5 mM KF + 60 mM NaCl were significantly reduced compared with the 5 mM KF treatment. The results point to a possible competitive inhibition of F transport by Cl. We also suggest that the possibility that aquaporins may be involved in the transmembrane transport of F should be further investigated.
Journal of Environment Quality, 2002
that entails the remixing of the fine and coarse components along with gypsum (CaSO 4 •2H 2 O at ... more that entails the remixing of the fine and coarse components along with gypsum (CaSO 4 •2H 2 O at dosages of In the processing of oil sands from Alberta's Athabasca formation, 750-1200 g Mg Ϫ1 tailings) as a chemical coagulant to large quantities of alkaline, saline tailings and associated processaffected waters are produced. These waters may have a negative effect produce a nonsegregating material known as consolion plants used in reclamation of mined areas in this region of the dated or composite tailings (CT) (Matthews et al., 2000). northern boreal forest. In the present study, we examined the effects This mixture is deposited as a slurry from which solidsof process-affected water on the growth and elemental composition free water is released. The goal is to produce a deposit of jack pine (Pinus banksiana Lamb.) seedlings. Seedlings were grown that becomes trafficable, and reclaimable, within a in sand culture, and treated with tailings water to which mineral shorter period than without this treatment. A large volnutrients had been added. One-month-old seedlings were treated for ume of the CT water will remain in this material and 14 d, and all measured growth parameters were reduced. Growth and is expected to be expressed over a number of years as shoot elemental composition were also measured in seven-month-old the deposit settles and dewaters further. These tailings seedlings that were treated for 10 wk with process-affected water. and associated pore waters (CT water) are relatively 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 saline, with Na and Cl being derived primarily from the between elemental composition and seedling growth and injury were ore, while most of the SO 4 comes from the gypsum examined using multiple regression. Growth rates, dry weights, and treatment (MacKinnon et al., 2000). carotenoid content were reduced, but were not related to shoot ele-Salinity may affect the growth of plants by altering mental composition. Needle necrosis was positively related to tissue water relations, by direct toxicity of ions, and by altering Na and Cl. Results indicate that reclamation planning must consiionic balance resulting in nutrient deficiency. A reducder substrate Na and Cl levels when planting jack pine on tailingstion in water uptake may lead to a reduction in transpiraaffected sites.
Journal of Environment Quality, 2003
The oil sands industry in Alberta (Canada) has developed the quickly on deposition. The addition ... more The oil sands industry in Alberta (Canada) has developed the quickly on deposition. The addition of the required inorcomposite tailings (CT) process to reduce the fluid fine tails resulting from the processing of oil sands. This process uses a chemical coagulant ganic coagulant aid will result in significant changes (gypsum or alum) to produce aggregated fines (clay), so they are in the ionic content of the CT and CT release water retained with the coarse sand fraction of the extraction tailings to (MacKinnon et al., 2001). Chemical analysis of the CT form CT, from which fines-free water is released relatively quickly mix and its released water has indicated that this matecompared with untreated tailings. The resulting CT and CT waters rial will have a relatively high pH (Ͼ7.6) and high conare saline-sodic, with Na ؉ , SO 2Ϫ 4 , and Cl Ϫ being the dominant ions. centrations of ions including Na ϩ , SO 2Ϫ 4 , and Cl Ϫ (Mac-When freshly deposited, the CT deposits are too soft for access by Kinnon et al., 2001). Furthermore, with subsequent reclamation equipment, and the time required for these deposits to recycling of release water in processing needs, the salinremove the water sufficiently to support traffic is uncertain. A greenity of waters contained on the site will further increase. house study was designed to determine the suitability of barley In addition to the salinity of the tailings and associated (Hordeum vulgare L.) for reclamation of fresh CT deposits and to evaluate benefits of peat amendments. This study assessed germina-waters, concerns have been raised regarding impact and tion, early plant growth, chlorophyll content, and survival of barley availability of trace heavy metals (e.g., Al, B, and Sr) growing in alum-and gypsum-treated CT, with and without peat that may be associated with the CT materials. amendment. Ion and trace metal accumulation in the root and shoot Before mining activities, the oil sands development tissues of barley was determined. Amendment of CT with peat imarea supported a mixed wood boreal forest. The reclamaproved germination, survival, and growth of barley, but did not prevent tion objective is to produce a self-sustaining ecosystem leaf injury (probably due to Na and Cl and possibly multiple nutrient with no long-term toxicity (Fine Tailings Fundamentals deficiency). Field studies will be undertaken to validate our green-Consortium, 1995). The choice of the reclamation plant house results suggesting that barley could be used to improve dewaterspecies will be influenced by their tolerance to pH, gening of the freshly deposited substrates, reduce soil erosion, and facilieral salinity, and specific ions in these tailings. The retate leaching of ions by root penetration into the substrate. sults of previous studies (Renault et al., 1998, 1999) have shown that growth and survival of several boreal forest species, including jack pine (Pinus banksiana
Journal of Environmental Quality, 1999
In the extraction of bitumen from oil sands ore, large volumes of railings water (CT water) conta... more In the extraction of bitumen from oil sands ore, large volumes of railings water (CT water) containing elevated levels of Na, sulfate, bicarbonate and chloride are produced. High salinity process waters will probably affect terrestrial reclamation options. The present study tested the impact of tailings waters on boreal forest species including aspen (Populus tremuloides Michx.), buffalo berry ISheperdia canadensis (L.) Nutt], northwest hybrid poplar (Populus deltoides × Populus balsamifera), dogwood (Comus stolonifera Michx.), jack pine (Pinus banksiana Lamb.), and white spruce |Picea glauca (Moench) Voss]. Seedlings were grown in solution culture containing mineral nutrients and different dilutions of CT water, with and without supplemental salts (Na2SO4 and NaCI). After 4 wk of treatment, dogwood, hybrid poplar, and buffalo berry showed relatively high resistance to saline CT waters. Conifer seedlings developed leaf necrosis in all treatments, while aspen seedlings rapidly lost their foliage and produced new leaves. In comparison to the controls, elevated Na levels were measured in plant tissue of all species grown in CT water. However, some differences between species were observed, with jack pine seedlings showing much higher Na content than aspen, dogwood, or hybrid poplar. In hybrid poplar, the accumulation of Na was accompanied by a significant reduction in K, Mg, Ca, and P. Buffalo berry, aspen, jack pine, and white spruce showed elevated levels of S after growth in the sulfate-enriched CT waters. High tissue Na content did not induce leaf injury in dogwood, hybrid poplar and buffalo berry, suggesting possible Na resistance. A~r nE two commercial oil sands operations in northeastern n Alberta (Syncrude Canada Ltd. and Suncor Energy), a hot water extraction process is used to separate bitumen from oil sand ore. This process produces large volumes of wastes consisting of water and fine tailings (a relatively stable suspension of clays, fines, and unrecovered bitumen) (FTFC, 1995). To duce the volume of fine tailings, a new method of tailings management is being developed. It uses gypsum treatment of densified extraction tailings augmented with fine tailings to produce a nonsegregating deposit (composite or consolidated tailings, CT) (Mikula et. al, 1996). Ions leaching from the oil sand and chemicals added during processing will elevate the ionic level of the CTrelease waters. These ions are mostly Na, sulfate, bicarbonate, and chloride, as well as Ca, and Mg. The land disturbed by the mining is required to be reclaimed to a level that will support productive forest ecosystems. It is anticipated that the reclamation options may be affected by the high salinity process-affected waters associated with the CT technology. The major
Journal of Chromatography A, 2004
Naphthenic acids are found in wastewaters from petroleum refineries and oil sands extraction plan... more Naphthenic acids are found in wastewaters from petroleum refineries and oil sands extraction plants. Currently, the concentrations of these toxic carboxylic acids are determined by extracting them into methylene chloride and measuring the absorption of the carboxyl group by Fourier-transform infrared (FTIR) spectroscopy. An improved HPLC method, that is simpler and faster than the FTIR method, was used to detect the 2-nitrophenylhydrazides of the naphthenic acids at concentrations as low as 5 mg l −1. Analyses of 58 oil sands water samples showed that the naphthenic acids concentrations determined by FTIR were on average 11% higher than those determined by HPLC.
Journal of Applied Microbiology, 2006
Development of the oil sands from the Athabasca deposits of Northeastern Alberta is proceeding ra... more Development of the oil sands from the Athabasca deposits of Northeastern Alberta is proceeding rapidly since it constitutes one of the world's largest oil reserves (CAPP 2005). Currently, oil sands operations produce >200 million barrels of sweet synthetic crude oil per year, and within the foreseeable future, >50% of Canada's oil supply will come from the oil sands. Bitumen extraction from the oil sands using the current aqueous digestion methods requires up to 2 m 3 of water for each barrel of bitumen. The extraction tailings slurries are composed of solids (sand, fines), oil sands process-affected water (OSPW) containing dissolved
Environmental Toxicology and Chemistry, 2000
Two waste products of Syncrude Canada Ltd. (SCL) oilsands mine are mature fine tailings (MFT), a ... more Two waste products of Syncrude Canada Ltd. (SCL) oilsands mine are mature fine tailings (MFT), a toxic aqueous suspension of particles, organic acids, bitumen, and metals, and tailings pond water (TPW), a saline solution containing organic and inorganic contaminants. The chemical profiles of MFT interstitial water and TPW are very similar. Syncrude Canada has proposed disposing of MFT in constructed lakes, which would be lined with MFT and capped with clean water. As the MFT consolidates, MFT-associated water would be released into the overlying watercap. Prototype ponds support fathead minnows (Pimephales promelas), but the long-term viability of these populations is unknown. This study attempts to determine if exposure to MFT and TPW, a related waste product, affected growth of fathead minnow larvae in the laboratory and field. Laboratory larval growth bioassays (7 and 56 d) on whole effluent from numerous prototype ponds yielded no significant differences in dry weight, but one 7-d bioassay showed reduced survival in two SCL sites. A 56-d growth bioassay showed significant increases in length of fish exposed to SCL wastewater at 7 d but not at 28 or 56 d. Larvae exposed as embryos and then introduced into field mesocosms did display significant differences in dry weight. In this instance, fish exposed to wastewater were significantly larger during the laboratory portion of the test (initial), but after 21 d in a field mesocosm (final), they were similar in size or smaller than fish growing in nonprocessed water.
Environmental Science & Technology, 2007
Environmental Science & Technology, 2005
Naphthenic acids (NAs) are natural constituents in many petroleum sources, including bitumen in t... more Naphthenic acids (NAs) are natural constituents in many petroleum sources, including bitumen in the oil sands of Northern Alberta, Canada. Bitumen extraction processes produce tailings waters that cannot be discharged to the environment because NAs are acutely toxic to aquatic species. However, aerobic biodegradation reduces the toxic character of NAs. In this study, four commercial NAs and the NAs in two oil sands tailings waters were characterized by gas chromatography-mass spectrometry. These NAs were also incubated with microorganisms in the tailings waters under aerobic, laboratory conditions. The NAs in the commercial preparations had lower molecular masses than the NAs in the tailings waters. The commercial NAs were biodegraded within 14 days, but only about 25% of the NAs native to the tailings waters were removed after 40-49 days. These results show that low molecular mass NAs (C < or =17) are more readily biodegraded than high molecular mass NAs (C > or =18). Moreover, the results indicate that biodegradation studies using commercial NAs alone will not accurately reflect the potential biodegradability of NAs in the oil sands tailings waters.
Environmental Pollution, 2004
The reclamation of freshly produced composite or consolidated tailings (CT) is a challenge for th... more The reclamation of freshly produced composite or consolidated tailings (CT) is a challenge for the Oil Sands Industry in the boreal forest of Western Canada. CT tailings materials are characterized by a relatively high salinity (dominated by sodium, sulphate and chloride) and a high pH (8-9). A greenhouse study was conducted to determine the germination, survival, injury and early plant growth of two grass species recommended for land reclamation, altai wildrye (Elymus angustus Trin) and slender wheatgrass (Agropyron trachycaulum Link Malte), growing in two different oil sand CT tailings (alum-CT and gypsum-CT), with and without peat amendment. Ion accumulation in the resulting plant tissues was determined. Our results showed that slender wheatgrass was most affected by the tailings at the germination stage, while for altai wildrye, the early growth stage was the most sensitive stage. Alum-CT had similar or less negative impact on plants than gypsum-CT. Amendment of CT with peat limited the reduction in germination and growth that was recorded in plants growing directly in CT. Based on these results, recommendations were made to improve reclamation strategies.
Environmental and Experimental Botany, 2008
Roots of trembling aspen (Populus tremuloides Michx.) and paper birch (Betula papyrifera Marsh.) ... more Roots of trembling aspen (Populus tremuloides Michx.) and paper birch (Betula papyrifera Marsh.) seedlings were inoculated with Hebeloma crustuliniforme or Laccaria bicolor and treated with 25 mM NaCl for 6 weeks. Both tree species appeared to be relatively tolerant of the applied NaCl treatment and did not develop visible leaf symptoms that are characteristic of salt injury. Salt treatment reduced total dry weights in aspen and birch, but did not significantly affect transpiration rates and root hydraulic conductance. Salt-treated ectomycorrhizal aspen maintained higher root hydraulic conductance compared with non-mycorrhizal plants. Na and Cl concentrations increased in shoots and roots of mycorrhizal and nonmycorrhizal aspen and birch in response to NaCl treatment. Roots of NaCl-treated aspen inoculated with H. crustuliniforme had over twofold higher concentrations of Na compared with non-mycorrhizal NaCl-treated plants. Similarly to aspen, Na and Cl concentrations increased in roots and shoots of NaCl-treated birch seedlings. However, in birch, there were no significant differences in Na and Cl concentrations between mycorrhizal and non-mycorrhizal plants. The results suggest that salt exclusion by the ectomycorrhizal associations is host-specific or/and that the processes leading to salt exclusion are activated in ectomycorrhizal plants by a threshold salt level which may vary between plant species.
CORROSION 96, 1996
... Raw water from Mildred Lake is used to supply makeup to the: q potable water plant q three op... more ... Raw water from Mildred Lake is used to supply makeup to the: q potable water plant q three open recirculating cooling towers q fire water system q utility water system q gland seal water system q main boiler feedwa[er treatment plant q makeup water in the Extraction plant ...
Canadian Journal of Microbiology, 2000
In the past decade, the large tailings pond (Mildred Lake Settling Basin) on the Syncrude Canada ... more In the past decade, the large tailings pond (Mildred Lake Settling Basin) on the Syncrude Canada Ltd. lease near Fort McMurray, Alta., has gone methanogenic. Currently, about 60%-80% of the flux of gas across the surface of the tailings pond is methane. As well as adding to greenhouse gas emissions, the production of methane in the fine tailings zone of this and other settling basins may affect the performance of these settling basins and impact reclamation options. Enumeration studies found methanogens (10 5-10 6 MPN/g) within the fine tailings zone of various oil sands waste settling basins. SRB were also present (10 4-10 5 MPN/g) with elevated numbers when sulfate was available. The methanogenic population was robust, and sample storage up to 9 months at 4°C did not cause the MPN values to change. Nor was the ability of the consortium to produce methane delayed or less efficient after storage. Under laboratory conditions, fine tailings samples released 0.10-0.25 mL CH 4 (at STP)/mL fine tailings. The addition of sulfate inhibited methanogenesis by stimulating bacterial competition.
Aquatic Toxicology, 2011
Large volumes of fluid tailings are generated during the extraction of bitumen from oil sands. As... more Large volumes of fluid tailings are generated during the extraction of bitumen from oil sands. As part of their reclamation plan, oil sands operators in Alberta propose to transfer these fluid tailings to end pit lakes and, over time, these are expected to develop lake habitats with productive capabilities comparable to natural lakes in the region. This study evaluates the potential impact of various oil sands process-affected waters (OSPW) on the reproduction of adult fathead minnow (Pimephales promelas) under laboratory conditions. Two separate assays with aged OPSW (>15 years) from the experimental ponds at Syncrude Canada Ltd. showed that water containing high concentrations of naphthenic acids (NAs; >25 mg/l) and elevated conductivity (>2000 S/cm) completely inhibited spawning of fathead minnows and reduced male secondary sexual characteristics. Measurement of plasma sex steroid levels showed that male fathead minnows had lower concentrations of testosterone and 11-ketotestosterone whereas females had lower concentrations of 17-estradiol. In a third assay, fathead minnows were first acclimated to the higher salinity conditions typical of OSPW for several weeks and then exposed to aged OSPW from Suncor Energy Inc. (NAs ∼40 mg/l and conductivity ∼2000 S/cm). Spawning was significantly reduced in fathead minnows held in this effluent and male fathead minnows had lower concentrations of testosterone and 11-ketotestosterone. Collectively, these studies demonstrate that aged OSPW has the potential to negatively affect the reproductive physiology of fathead minnows and suggest that aquatic habitats with high NAs concentrations (>25 mg/l) and conductivities (>2000 S/cm) would not be conducive for successful fish reproduction.
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Papers by Michael MacKinnon