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Dissipation and phytotoxicity of oil sands naphthenic acids in wetland plants



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Naphthenic acids (NAs) are toxic organic acid compounds released during the caustic hot-water extraction of crude oil from oil sands in north-eastern Alberta, Canada. NAs subsequently accumulate in the large volume of oil sands process water (OSPW) produced daily by oil sands operations. The complexity of dealing with a mixture of over 200 individual NA compounds, combined with their acute aquatic toxicity and large volume of production has made them an emerging pollutant of concern for western Canada. The following thesis outlines a variety of experiments designed to determine the potential to use wetland plants to enhance the dissipation of NAs from OSPW (phytoremediation). Investigations were carried out with three native emergent macrophyte species cattail (Typha latifolia), common reed (Phragmites australis subsp. americanus), and hard-stem bulrush (Scirpus acutus) to see if they enhanced the dissipation of NAs from a hydroponic system. Dissipation of NAs (at 30 mg L⁻¹ and 60 mg L⁻¹) was investigated with both a commercially available NA mixture as well as with a NA mixture extracted from the OSPW. Dissipation of NAs was also investigated under the different ionized forms of NAs (ionized, pH = 7.8; and non-ionized, pH = 5.0) to better elucidate the mechanisms of NA uptake and toxicity in plants. Phytotoxicity of NAs was investigated in hydroponic experiments through fresh weight gain and evapotranspiration was monitored throughout the experiment by water uptake. Commercially available NA mixture was more phytotoxic than oil sands NAs mixture. As well, NAs were found to be more phytotoxic in their non-ionized form therefore indicating that they may be taken up through an 'ion-trap' mechanism. However despite this, no significant dissipation of total NAs was observed from planted hydroponic systems. Nevertheless there was a significant change in the distribution (percent abundance) of individual NA families of certain size. These changes were related to the one- and two-ring NA compounds (Z = -2 and Z = -4). Despite not detecting any dissipation of total NAs from the systems, plants were able to reduce the toxicity of a NA system over 30 days by 45% as determined by Daphnia magna acute toxicity bioassays; a 11% greater reduction than unplanted systems. Studies were also conducted investigating the microbial community inhabiting cattail roots exposed to NAs. It was observed that the rhizosphere community changed with NA exposure, with a general increase in potentially pathogenic bacteria and a decrease in bacteria previously found to be beneficial to plant growth. The observed microbial community change could be an indirect effect of the Phytotoxicity experienced by aquatic macrophytes exposed to NAs. Synchrotron-sourced, fourier transform microspectroscopy analysis of root cross sections revealed that there were significant physiological changes to those roots exposed to NAs. These changes were identified as being cell death in the plant root epidermis as well as a change in the chemistry of parenchyma cells in the root pith. It is not known if these changes are a direct effect of NAs to the plant or due to changes of the associated rhizosphere community in the roots or some combination of both these factors.



naphthenic acid mixtures, naphthenic acid chemical form, plant biotransformation, rhizosphere bacteria, dried tailings runoff water, pressurized liquid extraction, FTIR microspectroscopy



Doctor of Philosophy (Ph.D.)






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