The purpose of this work was to estimate metals bioaccessibility in soil samples from 15 city parks in Toronto, Ontario, Canada. Total metals concentrations were analyzed to identify contaminants that exceeded the Canadian Council of Ministers of the Environment (CCME) guidelines for residential/parkland use. Arsenic, barium, cadmium, cobalt, copper, lead, nickel and zinc were of particular interest as they have been known to have major effects on human health. Metal concentrations were below the CCME guidelines except for lead at three of the parks. Lead, copper and cadmium bioaccessibility in the soil samples as determined by an in-vitro physiologically based extraction test (PBET) were relatively high. Based on linear regression analyses there were no significant relationships between total metals and soil properties such as pH and total organic carbon (TOC). Generally there was negative correlation between metal bioaccessibility and TOC and positive correlation between bioaccessibility and soil pH.

There is a growing need to develop rapid and cost-effective ecotoxicological tools for risk assessment because traditional methods examine endpoints such as mortality, which do not provide any insight into the mode of action (MOA) of the chemical. Research presented within this thesis illustrates the potential of 1H NMR-based metabolomics as a rapid and routine ecotoxicological tool that can elucidate a chemical’s MOA and also aid in the identification of metabolites of exposure. Metabolomics involves measuring the fluctuations in the endogenous metabolites of an organism within a cell, tissue, bio-fluid or whole organism in response to an external stressor. We focused on the model polycyclic aromatic hydrocarbon (PAH) phenanthrene, and the perfluoroalkyl acids (PFAAs) perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), due to their recalcitrant nature and widespread prevalence in soil environments. 1H NMR-based metabolomics analysis of the exposure of Eisenia fetida earthworms to sub-lethal phenanthrene exposure via filter paper contact tests revealed a concentration-dependent two-phased MOA: a linear correlation between the metabolic response and exposure concentration at low concentrations followed by a plateau in the responses at high concentrations. Alanine, glutamate, maltose, cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. An increased energy demand and an interruption in the conversion of succinate to fumarate in the Krebs cycle were observed due to phenanthrene exposure. Sub-lethal PFOA and PFOS exposure to E. fetida via contact tests for two days revealed heightened responses with higher PFOA and PFOS concentrations. Leucine, arginine, glutamate, maltose, and ATP were identified as potential indicators of PFOA or PFOS exposure. E. fetida responses were then investigated after exposure for two, seven and fourteen days to an artificial soil that was spiked with sub-lethal PFOS concentrations. An exposure time-dependent operation of two separate MOAs were identified. Both the contact tests and artificial soil exposure studies identified an elevation in fatty acid oxidation, a disruption in energy metabolism and biological membrane structure, and also an interruption of ATP synthesis following PFOA and PFOS exposure. This thesis illustrates the promise of NMR-based metabolomics as a routine tool for ecotoxicological assessment of contaminated sites.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

There is a growing need to develop rapid and cost-effective ecotoxicological tools for risk assessment because traditional methods examine endpoints such as mortality, which do not provide any insight into the mode of action (MOA) of the chemical. Research presented within this thesis illustrates the potential of 1H NMR-based metabolomics as a rapid and routine ecotoxicological tool that can elucidate a chemical’s MOA and also aid in the identification of metabolites of exposure. Metabolomics involves measuring the fluctuations in the endogenous metabolites of an organism within a cell, tissue, bio-fluid or whole organism in response to an external stressor. We focused on the model polycyclic aromatic hydrocarbon (PAH) phenanthrene, and the perfluoroalkyl acids (PFAAs) perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), due to their recalcitrant nature and widespread prevalence in soil environments. 1H NMR-based metabolomics analysis of the exposure of Eisenia fetida earthworms to sub-lethal phenanthrene exposure via filter paper contact tests revealed a concentration-dependent two-phased MOA: a linear correlation between the metabolic response and exposure concentration at low concentrations followed by a plateau in the responses at high concentrations. Alanine, glutamate, maltose, cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. An increased energy demand and an interruption in the conversion of succinate to fumarate in the Krebs cycle were observed due to phenanthrene exposure. Sub-lethal PFOA and PFOS exposure to E. fetida via contact tests for two days revealed heightened responses with higher PFOA and PFOS concentrations. Leucine, arginine, glutamate, maltose, and ATP were identified as potential indicators of PFOA or PFOS exposure. E. fetida responses were then investigated after exposure for two, seven and fourteen days to an artificial soil that was spiked with sub-lethal PFOS concentrations. An exposure time-dependent operation of two separate MOAs were identified. Both the contact tests and artificial soil exposure studies identified an elevation in fatty acid oxidation, a disruption in energy metabolism and biological membrane structure, and also an interruption of ATP synthesis following PFOA and PFOS exposure. This thesis illustrates the promise of NMR-based metabolomics as a routine tool for ecotoxicological assessment of contaminated sites.

Rivers all around the world have become increasingly polluted with heavy metals, largely due to industrialization and urbanization. Organisms exposed to high concentrations of heavy metals have shown evidence of biotoxicity and physical deformities. With biomagnification in mind, the possibility that this contamination may soon directly affect humans is a real concern, and policies in manufacturing industries worldwide may have to be reformed. In this study, we measured the concentrations of arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), and lead (Pb) in the Hatillo River and compared these values to those measured in the Tarcoles River, a highly polluted river, and Terciopelo Creek, a relatively clean river. The results showed that the Hatillo River had significantly lower levels of most detected heavy metals than both the Tarcoles and Terciopelo. Overall, sediments in all rivers showed high levels of heavy metal content--especially in chromium, copper, nickel, and lead--which could build up and affect organisms over a long period of time.

Irthing Road is situated 20 kilometres north of the small town of Lumsden in Northern Southland, New Zealand. Irthing Road is accessed from State Highway 97 and leads north-west for 7 kilometres up the Irthing Creek Valley. The research site is situated 4.4 kilometres from the Irthing Road - State Highway 97 intersection and the area is at 300 metres elevation above sea level on gently south sloping Quaternary alluvial deposits. The study was initiated by Environment Southland and Southern Geophysical Ltd with the intention of investigating the potential uses of near surface geophysics in the mapping of shallow groundwater contamination, specifically agriculturally sourced nitrates and leachates. The changes in land use and the introduction of high density grazing of dairy cattle on free draining soils in Southland has created cause for concern around the ease at which large volumes of contaminants could potentially gain access to the shallow groundwater system. The investigation of the Irthing Road field site included: (1) background research into historical land use changes that may have affected the area 2) a study of the Lumsden area geological and hydrogeological setting 3) six trips to the field site throughout the year to collect near surface geophysical data using a Geonics Ltd EM31-MK2, Dualem Inc. DUAL-EM 421s, and Sensors & Software pulseEKKO Pro GPR system; 4) ground- water testing conducted by Environment Southland; 5) an evaluation of the geophysical and groundwater data sets to identify whether leachate concentrations were high enough to register an anomalous response 6) the identification of how the groundwater system at the Irthing Road field site behaves 7) a conclusion as to the effectiveness of all three near surface geophysical techniques in this application. The major conclusions that emerged from this study are: (1) the groundwater system is transporting a large volume of water beneath the site and this leads to such effi- cient removal of contaminants that the concentrations are not high enough to register a response in the geophysical data 2) the groundwater system is highly sensitive to rain- fall and this is a contributing factor to the variation within the geophysical data 3) the Geonics Ltd EM31-MK2 and Sensors & Software pulseEKKO Pro GPR system returned highly consistent results and have great potential in further contaminated groundwater applications 4) Environment Southlands' DUAL-EM 421s needs more consistency, how- ever the device has a lot of potential once reliability can be ensured 5) further research is needed to determine the contamination ow paths and destinations at a larger, regional scale.

Neurodegenerative diseases have been shown to correlate positively with an ageing population. The most common neurodegenerative diseases are amyotrophic lateral sclerosis (ALS), Parkinson’s disease and Alzheimer’s disease. The cause of these diseases is believed to be the interaction between genetic and environmental factors, synergistically acting with ageing. BMAA (β-methylamino-L-alanine) is one kind of toxin present in our environment and might play an important role in the development of those diseases. BMAA was initially isolated from cycad seeds in Guam, where the incidence of ALS/Parkinsonism-dementia complex among the indigenous people was 50 – 100 times higher than the rest of the world in the 1950’s. BMAA can induce toxic effects on rodents and primates. Furthermore, it can potentiate neuronal injury on cell cultures at concentrations as low as 10 µM. BMAA was reported to be produced by cyanobacteria, and could bio-magnify through the food chain. In this thesis, work was initially focused on the improvement of an existing analytical method for BMAA identification and quantification using liquid chromatography coupled with tandem mass spectrometry.  Subsequently, the refined method was applied to environmental samples for probing alternative BMAA producer(s) in nature and to seafood samples for estimation of human exposure to this toxin. In Paper I, a systematic screening of the isomers of BMAA in a database was performed and seven potential isomers were suggested. Three of them were detected or suspected in natural samples. In Paper II, a deuterated internal standard was synthesized and used for quantifying BMAA in cyanobacteria. In Paper III, Diatoms were discovered to be a BMAA producer in nature. In Paper IV, ten popular species of seafood sold in Swedish markets were screened for BMAA. Half of them were found to contain BMAA at a level of 0.01 – 0.90 µg/g wet weight. In Future perspectives, the remaining questions important in this field are raised.

With rapidly urbanizing societies, waste management needs attention. In 2008, EUs Waste Framework Directive (WFD) set new concepts, like reducing usage of natural materials. Thus, the interest for alternative materials increased. In Skellefteå, since the 1970’s, iron sand has often substituted natural gravel in road construction. But, today stricter regulations might forbid iron sand for further use. The issue is whether leachate from iron sand causes heavy metal pollution or not. This thesis tried to provide more knowledge into iron sand’s environmental impact. In order to investigate this, a sediment sample (<53 cm deep) collected in Inre-viken, a lake 50m from a road with iron sand, were analyzed for Zn, Pb and Cu concentrations. Enrichment factor (EF), national benchmarks, and reference data were used to evaluate anthropogenic impact and age-determine the sediment. The results showed: (1) Inre-viken has elevated heavy metal levels compared to pre-industrial levels, with highest Cu (133 mg/kg) and Zn(204 mg/kg) concentrations found in the surface layer. (2) Zn and Cu showed an increase between 41-0 cm depth (1970-2015), but only Cu reaches high concentrations, while Zn and Pb range between low to very low concentrations. (3) The metal enrichment is low compared to the reference lake. The findings show that there are elevated levels in Inre-viken compared to pre-industrial levels. However, identifying the main source of pollution is difficult, because many pollution sources exist in the area. To determine if iron sand is the culprit, further studies are necessary.

Le contrôle de l'aérocontamination fongique est devenu un objectif majeur pour préserver la santé humaine et animale. L'évaluation de l'aérocontamination fongique fait classiquement appel aux techniques de mise en culture ou de dosage de composants fongiques présents dans l'air. Ces techniques présentent des inconvénients. C'est la raison pour laquelle, nous nous sommes fixés comme objectif de mettre au point des méthodes d'analyse alternatives utilisant des outils de biologie moléculaire. Dans un premier temps, nous avons comparé plusieurs techniques de prélèvements d'air dans des environnements intérieurs présentant une contamination plus ou moins élevée. Nous avons, par la suite, optimisé les conditions d'extraction de l'ADN fongique à partir de prélèvements d'air. L'ADN extrait a été amplifié par PCR " semi-nichée " avec des amorces universelles permettant d'amplifier une partie de l'ARNr 18S de champignons. Par la suite, nous avons utilisé la TTGE (Temporal Temperature Gradient Electrophoresis) et la D-HPLC (Denaturing High Performance Liquid Chromatography) pour séparer les amplificats. Chaque produit de PCR a été identifié par séquençage direct après purification. La comparaison des espèces identifiées par ces techniques avec celles qui sont obtenues par la méthode classique (culture) apporte de meilleurs renseignements sur la qualité fongique d'un même prélèvement d'air. L'application de ces techniques dans des environnements à différents niveaux de contamination a permis de déduire que l'étude de l'évaluation de l'aérocontamination fongique se fait par l'association de la culture et des méthodes moléculaires

The bacterium Aeromonas hydrophila is a known fish and opportunistic human pathogen commonly occurring in surface waters supplying drinking water distribution systems. The major concern of government and drinking water providers is that A. hydrophila may invade and become established in the biofilm of a distribution system, thus potentially leading to outbreaks of disease. The purpose of this study was to survey source water, distribution system biofilm, and to establish a simulated distribution system to explore the possibility of A. hydrophila invading and becoming established under normal and disrupted treatment conditions. A. hydrophila (AH) medium and the API-20E system were used for identification, while Ampicillin-Dextrin Agar (ADA) was used for enumeration. Presumptive counts were high in source water approaching 103 CFU/ml during summer months. Biofiim from an actual distribution system showed the presence of A. hydrophila in 10 % of the samples. In the simulated distribution system A. hydrophila was never found in the bulk water or biofilm under normal treatment condition, showing disinfectant efficiency. Under disrupted treatment conditions A. hydrophila was not able to colonize a pre-established biofilm over a 14 week period. / Department of Biology