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Petroleum hydrocarbons are emitted into the environment via natural and anthropogenic activities. Once emitted, these hydrocarbons can be transported globally, persisting and accumulating in aquatic ecosystems. In the Alberta oil sands region (AOSR), mining activities have significantly altered and polluted the surrounding aquatic and terrestrial environments with heavy metals and various petroleum hydrocarbons including polycyclic aromatic hydrocarbons (PACs). Though PACs have been tracked through time using dated lake sediment cores, separating natural and anthropogenic PACs can be difficult. In the Peace Athabasca Delta (PAD) this task is especially difficult as this region has been receiving annual inputs of naturally eroded bitumen throughout history. Petroleum biomarkers are unique petrogenic compounds (i.e. derived from petroleum) which may provide a secondary proxy to track mining impacts. This thesis investigated the impacts of mining activities on the AOSR and the PAD using two different proxies, PAC and petroleum biomarkers. These two regions were compared to reference lakes to the south and northwest of the Athabasca oil sands formation, in order to provide a natural signal, with minimal oil sands mining contamination. Historically deposited PACs and petroleum biomarkers were analysed in radiometrically dated lake sediment cores from the AOSR and the PAD, Alberta. Sediment profiles in the AOSR (Saline Lake) showed increases in PAC fluxes for both alkylated and parent compounds coeval with mining activities. Alkylated PAC fluxes in reference lakes (Mariana Lake and BM11) increased at the height of oil sands development (1990s). PAD lakes showed no statistical increase in PAC flux through time due to high levels of naturally eroded bitumen entering the system. Parent PAC diagnostic ratios, however, showed clear shifts from pyrogenic (primarily wood burning) in pre-development sediments to petrogenically derived PACs in modern sediments, in both AOSR and PAD lakes, coeval with oil sands development. Petroleum biomarker diagnostic ratios in Saline Lake and PAD lakes remained stable through time, indicating a clear current and historical petroleum signal originating from the AOSR. Reference lakes (Mariana Lake and BM11) showed the greatest change in petroleum biomarkers. Historically, these lakes had signatures uncommon of petroleum sources, however, in recent years petroleum inputs from mining development were revealed by these petroleum biomarkers. This study compared the historical trends of several petroleum hydrocarbons in lake sediment to the historical emissions of these petroleum hydrocarbons from oil sands mining operations. Notably, we show the potential for petroleum biomarkers to trace petroleum hydrocarbon contamination in the environment.

1 / Yue Sun

Thesis (Ph. D.)--Oregon State University, 2007. / Printout. Includes bibliographical references. Also available on the World Wide Web.

Polycyclic aromatic hydrocarbons (PAH) have been identified as a serious environmental problem. In past research it has been proven that naphthalene, the simplest PAH, could be biodegraded using roller bioreactors and Pseudomonas putida. In this previous work it became apparent that the mass transfer rate of the hydrophobic naphthalene was the rate limiting factor in biodegradation, as the bacteria could degrade the naphthalene as fast as it entered solution. The challenge for the present research was to find a simple, inexpensive method for increasing the mass transfer rates within the framework of the previously successful reactor. <p>After some deliberation, the addition of inert particles (glass beads) was determined to be the preferred option to increase mass transfer. The inert particles visibly increased the turbulence in the reactor and significant increases in both mass transfer and bioremediation rates were achieved. The augmentation of mass transfer rates was found to be dependent on the type, size and relative loading of the particles. Two types of inert particles were investigated to increase mass transfer rates, spherical glass beads and Raschig rings. Glass beads were found to be far superior to Raschig rings for the intended purpose. Three sizes of spherical glass beads were then compared experimentally (1, 3, and 5mm). It was discovered that the 3mm beads were vastly superior to 1mm beads and 5 mm beads were slightly superior to 3mm beads. Different bead loadings (volume of particles / total working volume) were then explored with 10%, 25% and 50% bead loading investigated. Although slight increases in mass transfer were observed at higher bead loadings, the reduction in working volume for biodegradation meant that 50% was accepted as the optimum loading parameter. <p>The optimum conditions for maximum mass transfer occurred using 5 mm spherical glass beads at 50% loading. The increase in mass transfer and biodegradation rates compared to a traditional roller bioreactor were found to be 10 fold and 11 fold, respectively. The optimum mass transfer conditions were then applied to 2-methylnaphthalene with increases in mass transfer and biodegradation equal to 6 fold and 8 fold, respectively. The candidate bacteria used in this study was found incapable of degrading 1,5 dimethylnaphthalene although the mass transfer results demonstrate promise for the developed technology. To determine the effects of scale on the process, two larger reactors were finally studied. They were eight times and twenty-one times the size of the initial bioreactor. The process was shown to speed up at larger scale which shows great promise for future applications. The maximum degradation rate achieved in the larger reactor was 148 mgL-1h-1. This compares very well with the best result found in literature, 119 mgL-1h-1, which was achieved in a much more complex system. Clearly, the bead mill bioreactor designed during the present work is a simple concept that shows superior performance for the bioremediation of PAHs.

Polycyclic aromatic hydrocarbons (PAHs) and metals are co-contaminants of aquatic environments near industrial and urbanized areas. Mixtures could result in synergistic toxicity impairing macrophyte growth and potentially causing bioaccumulation and biomagnification throughout the ecosystem. In this study, combinations of 1,2-dihydroxyanthraquinone (1,2-dhATQ) and copper (Cu) at low concentrations synergistically inhibited Lemna gibba (duckweed) growth. Further analysis using fluorescence techniques showed an increase in reactive oxygen species (ROS) levels upon Cu exposures possibly through redox cycling in the chloroplasts. Pulse amplitude modulated (PAM) and fast repetition rate fluorometry (FRRF) indicated that plants exposed to 1,2-dhATQ had impaired photosynthetic electron transport that manifested as a decrease in the yield of photosynthesis and change in the redox status of the plastoquinone (PQ) pool. At the gene expression level acetyl coA carboxylase (ACC), a key enzyme in membrane repair, and serine decarboxylase (SDC), another enzyme needed for membrane repair were up-regulated in response to copper and 1,2-dhATQ, respectively. The mechanism for mixtures toxicity is thought to involve the reduced PQ pool which could serve as a source of electrons for copper redox cycling thereby increasing ROS production and causing synergistic growth inhibition. When the antioxidant glutathione (GSH) was added, copper toxicity was ameliorated but 1,2-dhATQ toxicity increased possibly through formation of reactive conjugates or suppression of the native antioxidant system. This study emphasizes that mixtures of toxicants at low concentrations can cause more biological damage than individual toxicants via alterations of the redox status and increases in ROS production.

Polycyclic aromatic hydrocarbons (PAHs) and metals are co-contaminants of aquatic environments near industrial and urbanized areas. Mixtures could result in synergistic toxicity impairing macrophyte growth and potentially causing bioaccumulation and biomagnification throughout the ecosystem. In this study, combinations of 1,2-dihydroxyanthraquinone (1,2-dhATQ) and copper (Cu) at low concentrations synergistically inhibited Lemna gibba (duckweed) growth. Further analysis using fluorescence techniques showed an increase in reactive oxygen species (ROS) levels upon Cu exposures possibly through redox cycling in the chloroplasts. Pulse amplitude modulated (PAM) and fast repetition rate fluorometry (FRRF) indicated that plants exposed to 1,2-dhATQ had impaired photosynthetic electron transport that manifested as a decrease in the yield of photosynthesis and change in the redox status of the plastoquinone (PQ) pool. At the gene expression level acetyl coA carboxylase (ACC), a key enzyme in membrane repair, and serine decarboxylase (SDC), another enzyme needed for membrane repair were up-regulated in response to copper and 1,2-dhATQ, respectively. The mechanism for mixtures toxicity is thought to involve the reduced PQ pool which could serve as a source of electrons for copper redox cycling thereby increasing ROS production and causing synergistic growth inhibition. When the antioxidant glutathione (GSH) was added, copper toxicity was ameliorated but 1,2-dhATQ toxicity increased possibly through formation of reactive conjugates or suppression of the native antioxidant system. This study emphasizes that mixtures of toxicants at low concentrations can cause more biological damage than individual toxicants via alterations of the redox status and increases in ROS production.

Polycyclic aromatic hydrocarbons (PAH) have been identified as a serious environmental problem. In past research it has been proven that naphthalene, the simplest PAH, could be biodegraded using roller bioreactors and Pseudomonas putida. In this previous work it became apparent that the mass transfer rate of the hydrophobic naphthalene was the rate limiting factor in biodegradation, as the bacteria could degrade the naphthalene as fast as it entered solution. The challenge for the present research was to find a simple, inexpensive method for increasing the mass transfer rates within the framework of the previously successful reactor. <p>After some deliberation, the addition of inert particles (glass beads) was determined to be the preferred option to increase mass transfer. The inert particles visibly increased the turbulence in the reactor and significant increases in both mass transfer and bioremediation rates were achieved. The augmentation of mass transfer rates was found to be dependent on the type, size and relative loading of the particles. Two types of inert particles were investigated to increase mass transfer rates, spherical glass beads and Raschig rings. Glass beads were found to be far superior to Raschig rings for the intended purpose. Three sizes of spherical glass beads were then compared experimentally (1, 3, and 5mm). It was discovered that the 3mm beads were vastly superior to 1mm beads and 5 mm beads were slightly superior to 3mm beads. Different bead loadings (volume of particles / total working volume) were then explored with 10%, 25% and 50% bead loading investigated. Although slight increases in mass transfer were observed at higher bead loadings, the reduction in working volume for biodegradation meant that 50% was accepted as the optimum loading parameter. <p>The optimum conditions for maximum mass transfer occurred using 5 mm spherical glass beads at 50% loading. The increase in mass transfer and biodegradation rates compared to a traditional roller bioreactor were found to be 10 fold and 11 fold, respectively. The optimum mass transfer conditions were then applied to 2-methylnaphthalene with increases in mass transfer and biodegradation equal to 6 fold and 8 fold, respectively. The candidate bacteria used in this study was found incapable of degrading 1,5 dimethylnaphthalene although the mass transfer results demonstrate promise for the developed technology. To determine the effects of scale on the process, two larger reactors were finally studied. They were eight times and twenty-one times the size of the initial bioreactor. The process was shown to speed up at larger scale which shows great promise for future applications. The maximum degradation rate achieved in the larger reactor was 148 mgL-1h-1. This compares very well with the best result found in literature, 119 mgL-1h-1, which was achieved in a much more complex system. Clearly, the bead mill bioreactor designed during the present work is a simple concept that shows superior performance for the bioremediation of PAHs.

<p>Dibenzothiophene (DBT) is a constituent of creosote and petroleum waste contamination, it is a model compound for more complex thiophenes, and its degradation by mixed microbial communities has received little attention. The chemical characteristics, environmental fate and ecotoxicology of DBT degradation products are not well understood. This research investigated DBT degradation in an enrichment culture derived from creosote-contaminated estuarian sediment using a suite of assays to monitor bacterial populations, bacterial growth, degradation products, DBT loss, and toxicity. Ultraviolet (UV) irradiation was evaluated as a sequential treatment following biodegradation. Additionally, to advance SYBR-Green qPCR methodology for characterizing mixed microbial communities, an alternative approach for evaluating qPCR data using a sigmoidal model to fit the amplification curve was compared to the conventional approach in artificial mixed communities. The overall objective of this research was to gain a comprehensive understanding of the degradation of a model heterocyclic PAH, DBT, by a mixed microbial community, particularly within the context of remediation goals.</p><p>DBT biodegradation was evaluated in laboratory scale cultures with and without pH control. The microbial community was monitored with 10 primer sets using SYBR-Green quantitative polymerase chain reaction (qPCR). Twenty-seven degradation products were identified by gas chromatography and mass spectrometry (GC/MS). The diversity of these products indicated that multiple pathways functioned in the community. DBT degradation appeared inhibited under acidic conditions. Toxicity to bioluminescent bacteria <italic>Vibrio fischeri</italic> more than doubled in the first few days of degradation, was never reduced below initial levels, and was attributed in part to one or more degradation products. UV treatment following biodegradation was explored using a monochromatic (254 nm) low-pressure UV lamp. While DBT was not extensively photooxidized, several biodegradation products were susceptible to UV treatment. At higher doses, UV treatment following DBT biodegradation exacerbated cardiac defects in <italic>Fundulus heteroclitus</italic> embryos, but slightly reduced toxicity to <italic>V. fischeri</italic>.</p><p>This research provides a uniquely comprehensive view of the DBT degradation process, identifying bacterial populations previously unassociated with PAH biodegradation, as well as potentially hazardous products that may form during biodegradation. Additionally, this research contributes to development of unconventional remediation strategies combining microbial degradation with subsequent UV treatment.</p> / Dissertation

Thesis (M.Sc.)(Microbiology))--University of Pretoria, 2009. / Summary in English. Includes bibliographical references.