No description available.

The persistent organic pollutants (POPs) refer to many different chemicals that, upon release into the environment, remain intact for several decades. These contaminants travel long distances through repeated cycles of deposition and evaporation, and eventually deposit in the Arctic regions. The purpose of this work was to examine the potential human health implications of POP exposures among the Canadian Inuit, using modelling and epidemiological approaches. Blood guideline values were developed for the organochlorine pesticides, chlordane and toxaphene, and the polychlorinated biphenyls (PCBs) using the concept of biomonitoring equivalents (BEs), which are based on toxicity endpoints and toxicokinetic modelling to convert an oral reference dose to an equivalent blood concentration. The biomonitoring data from the Adult Inuit Health Survey (2007-2008) and the Canadian Health Measures Survey (CHMS, Cycle 1 2007-2009) were compared with the derived guideline values to assess population-level risks of exposures for the Inuit and the general Canadian population, respectively. Epidemiological analyses were also conducted to explore if POPs were associated with diabetes and high cholesterol, using data from the Inuit Health Survey. A set of BE values were derived for chlordane isomers and metabolite, three abundant toxaphene isomers, and the PCBs. The derived values are in a similar range of the BEs of other POPs in the literature. Among the Inuit, a large percentage exceeded the trans-nonachlor guideline value, particularly among the elderly. Fewer exceedances were observed for cis-nonachlor and oxychlordane, none for toxaphene, and minimally for the PCBs. In comparison, no exceedances for any of the POPs were observed in the general Canadian population. Highest vs. lowest quartile exposures to PCBs and p,p’-DDE were associated with increased risk of diabetes and an increase in fasting glucose among the Inuit. In addition, PCBs were associated with increased risk of high cholesterol, and higher levels of serum triglycerides, total cholesterol, and low-density lipoprotein cholesterol (LDL-C), but not high-density lipoprotein cholesterol (HDL-C). The results of this work suggest that exposures to POPs remain a potential health concern among the Canadian Inuit. Future research efforts should be devoted to collecting updated contaminant concentrations for the Inuit, measuring contaminants in prepared food samples, conducting cohort studies on contaminant exposures and health outcomes, and assessing the effects of chemical mixtures using statistical approaches and toxicokinetic modelling.

<p>An extensive use of chemicals in countless consumer products has resulted in human exposure to several persistent organic pollutants (POPs). Sufficient knowledge about their chemical composition properties and environmental faith is required, to be able to proper risk assess and regulate the substances. Significant data gaps exist regarding knowledge of actual exposure to humans and toxicological effect data.</p><p>The objective of this thesis was to add human exposure data of a few POPs from four case studies. The analytes discussed in this thesis are polychlorinated dibenzo-p-dioxins and furans (PCDDs/PCDFs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD).</p><p>Three European populations were studied. Milk was analysed from a group of women, who were accidentally exposed to high levels of 2,3,7,8-TetraCDD (TCDD) in Seveso, 1976. Still today, twice as high TCDD levels were recorded in the milk, compared to background concentrations. Serum was analysed from mothers and their infants from The Netherlands. Cord serum contained equal amounts of POPs as in mother’s blood, indicating non-hindered placenta transfer. Serum analysed from Swedish men and women with a high fish intake had elevated PCB and PCB metabolite (OH-PCB) levels. Additionally, butter was collected worldwide and shown to be a suitable matrix for dairy product survey of POPs.</p><p>The exposure levels in the four papers were compared to recently reported exposure levels in Europe. It is indicated in the thesis that the PCDDs/PCDFs and PCBs toxic equivalency (TEQ) levels are of concern, i.e. the ratio between threshold levels for adverse health effects and TEQ exposure levels is lower than requested margin of safety. Average levels of PBDE/HBCDD in the European population are estimated to be of no concern today, but for individuals with intakes at the 95th percentile are the current margins of safety small.</p>

Recruitment of American eels (Anguilla rostrata) to Lake Ontario has declined rapidly over the past few decades. The commercial yellow eel fishery in Lake Ontario was closed in 2004 due to a lack of eel abundance. Researchers have been attempting to ascertain the reasons for the decline, although thus far, without definitive answers. In this thesis, the question of chemical contamination is addressed as it relates to female eel spawner quality. Spatial concentration trends of halogenated persistent organic pollutants (POPs) are described in eels collected from across eastern Canada, as well as temporal concentration trends in eels collected from a historically important area of northeastern Lake Ontario, Canada. Chlorinated POPs in eels, namely, organochlorinated pesticides, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans are all significantly less than historic values which peaked in the 1960-70s. Measured concentrations of chlorinated POPs in eels from Lake Ontario have decreased by up to 3-fold over the past three decades, and exceeded toxicity thresholds historically for surrogate species (European eel and lake trout). Thus, chlorinated POPs may have had an effect on spawner quality. Concentrations of legacy POPs in eels were dependent on their origin, with eels from highly urbanized and industrialized areas having significantly higher concentrations than eels captured in less developed regions. Similar trends were observed for polybrominated diphenyl ethers and chlorinated norbornene flame retardants. A number of emerging brominated compounds were also measured in these eels by non-target analysis including bromophenols, bromobenzenes, and bromoanisoles. This thesis demonstrates that eels are an ideal species to investigate local sources of pollution, and provide chemical data that may be used in the future, when more toxicity information is available for eels, to assess the health risks posed by accumulated chemical contaminants. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-05-23 09:27:59.593

An extensive use of chemicals in countless consumer products has resulted in human exposure to several persistent organic pollutants (POPs). Sufficient knowledge about their chemical composition properties and environmental faith is required, to be able to proper risk assess and regulate the substances. Significant data gaps exist regarding knowledge of actual exposure to humans and toxicological effect data. The objective of this thesis was to add human exposure data of a few POPs from four case studies. The analytes discussed in this thesis are polychlorinated dibenzo-p-dioxins and furans (PCDDs/PCDFs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD). Three European populations were studied. Milk was analysed from a group of women, who were accidentally exposed to high levels of 2,3,7,8-TetraCDD (TCDD) in Seveso, 1976. Still today, twice as high TCDD levels were recorded in the milk, compared to background concentrations. Serum was analysed from mothers and their infants from The Netherlands. Cord serum contained equal amounts of POPs as in mother’s blood, indicating non-hindered placenta transfer. Serum analysed from Swedish men and women with a high fish intake had elevated PCB and PCB metabolite (OH-PCB) levels. Additionally, butter was collected worldwide and shown to be a suitable matrix for dairy product survey of POPs. The exposure levels in the four papers were compared to recently reported exposure levels in Europe. It is indicated in the thesis that the PCDDs/PCDFs and PCBs toxic equivalency (TEQ) levels are of concern, i.e. the ratio between threshold levels for adverse health effects and TEQ exposure levels is lower than requested margin of safety. Average levels of PBDE/HBCDD in the European population are estimated to be of no concern today, but for individuals with intakes at the 95th percentile are the current margins of safety small.

The remote sub-Arctic/Arctic environment has due to human activities become a sink for organohalogen contaminants (OHCs). These OHC include traditional contaminants such as polychlorinated biphenyls (PCBs), DDTs and technical mixtures of polybrominated diphenyl ethers (PBDEs), all included in the Stockholm Convention list of persistent organic pollutants (POPs). Other OHCs, currently under evaluation to be included among the POPs i.e. short chain chlorinated paraffins (SCCPs) and hexabromocyclododecane (HBCDD) are also found in these environments as well as a whole range of other OHCs. The main objective of this thesis is to increase the knowledge about the presence of OHCs in a high trophic Arctic shark species, the Greenland shark (Somniosus microcephalus). The Greenland shark is an opportunistic feeder, occasionally feeding at the top of the Arctic marine food chain. Furthermore may this species have a life span in excess of 100 years and is probably among the oldest of any fish species. These traits make the shark prone to accumulate elevated concentrations of OHCs. This has shown to be true for the Greenland sharks studied and most of the targeted OHCs were determined in the species. The highest concentrations were observed for the DDTs, ranging up to 26 μg/g fat. Other OHCs reported that are of special interest are SCCPs and brominated flame retardants used as replacement products to PBDEs; pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Also a range of OHCs whose origin is assumed to be natural, were shown to be present in Greenland sharks. This thesis is stressing the fact that even though the use of certain OHCs has been banned for decades they are still present at high concentrations in the deep waters of the Arctic. Therefore it is of major importance to continue to monitor the fate of traditional and emerging OHCs in the environment, and for this purpose the Greenland shark is an excellent species. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Synthesis of heat shock proteins (Hsps) in response to elevated temperatures and other denaturing agents (including UV, heavy metals, and energy depletion) is a common productive response of prokaryotic and eukaryotic cells. Therefore, increasing in production of heat shock protein has been considered a sign of cells under stress. The phylum Sipuncula comprises of about 300 species worldwide; they are bilaterally symmetrical, unsegmented, and deposit feeding marine worms common in the substrate of wetland. In this research, I studied the dominant species Sipunculus nudus and analyzed it proteomics to reveal how it responses to persistent organic pollution. In order to compare the difference between HSP70 and HSP90, Sipunculans were sampling from two wetland (Xiangshan and Wanggong) in Hsinchu and Changhua,, respectively. The results showed that the concentrations of PAHs and OCPs both in substrate and S. nudus tissues from Xiangshan were higher than Wanggong. The concentrations of PAHs and OCPs in both areas showed that the environmental- sediment levels were higher than the sediment inside the gut or the body tissues. Principal component analysis showed that the compositions in S. nudus from both area were similar; however PAHs compositions from the environmental sediment or the sediment of the gut were similar. When the concentrations of HSP70 and HSP90 between both areas were compared, HSP70 expressions did not significant differed in both areas, while HSP90 express was higher in the S. nudus from Xiangshan than Wanggong. For S. nudus Hsp90 was upregulated in highly polluted area (i.e. Xiangshan). I propose that tissue expression of HSP90 plays an important role in the survival of S. nudus, and detection of HSP90 may provide pollution information of the surrounding environment.

Polybrominated diphenyl ethers (PBDEs) are anthropogenic chemicals whose environmental behavior is similar to the well-known polychlorinated biphenyls (PCBs). Few studies have quantified the amount and distribution of PBDEs in the southern hemisphere and Antarctica. The analyses reported in this dissertation document the levels of PBDEs in lichens, mosses and seabird eggs collected at King George Island, Antarctic Peninsula. The analyses were carried out using Gas Chromatography/Electron Impact-Mass Spectrometry (GC/EI-MS). Employing the ion stacking technique lowered detection limits and ensured instrument selectivity and sensitivity to the compounds of interest. Lichens and mosses absorb PBDEs directly from the atmosphere and their contamination indicates that long-range transport is the primary source of these chemicals to King George Island. The congener patterns of PBDEs in plants indicate that commercial mixtures of Penta-BDE and Octa-BDE have reached Antarctica. Differences in the levels of PBDEs observed in lichens and mosses are probably due to factors that govern the uptake of PBDEs from the atmosphere. Contamination in lichens showed a positive correlation with local precipitation. Conversely, absorption of PBDEs in mosses appears to be controlled by other plant-specific factors. Marine phytoplankton-derived aerosols are hypothesized to play an important role in the atmospheric transport of PBDEs to the Antarctic environment. PBDEs in south polar skua eggs revealed much higher concentration than in penguin eggs. This is likely associated with the northward migration of these seabirds during the non-breeding season. While penguins reside year-round in Antarctica, south polar skuas migrate northward and can be seen in boreal oceans during the austral winter. Distribution of PBDEs in penguin eggs matches the pattern found in local vegetation suggesting a common source for the chemicals. In contrast, the congener pattern of south polar skuas suggests that birds breeding at King George Island are wintering in the northwestern Pacific Ocean. A potential metabolism of PBDEs in penguin eggs during the incubation period seems to be limited. Most congeners were unaltered from source material in the eggs of chinstrap and gentoo penguins. Low levels of PBDEs, short incubation periods and energy constraints may explain these observations.

Chemical species carry information in two dimensions, in their concentrations and their isotopic signatures. The concentrations of metabolites or synthetic compounds describe the composition of a chemical or biological system, while isotopic signatures describe processes in the system by their reaction pathways, regulation, and responses to external stimuli. Stable isotopes are unique tracers of these processes because their natural abundances are modulated by isotope effects occurring in physical processes as well as in chemical reactions. Nuclear magnetic resonance (NMR) spectroscopy is a prime technique not only for identification and quantification of small molecules in complex systems but also for measuring intramolecular distribution of stable isotopes in metabolites and other small molecules. In this thesis, we use quantitative NMR in three fields: in food science, environmental pollutant tracing, and plant-climate science. The phospholipid (PL) composition of food samples is of high interest because of their nutritional value and technological properties. However, the analysis of PLs is difficult as they constitute only a small fraction of the total lipid contents in foods. Here, we developed a method to identify PLs and determine their composition in food samples, by combining a liquid-liquid extraction approach for enriching PLs, with specialized 31P,1H-COSY NMR experiments to identify and quantify PLs. Wide-spread pollution with synthetic compounds threatens the environment and human health. However, the fate of pollutants in the environment is often poorly understood. Using quantitative deuterium NMR spectroscopy, we showed for the nitrosamine NDMA and the pesticide DDT how intramolecular distributions (isotopomer patterns) of the heavy hydrogen isotope deuterium reveal mechanistic insight into transformation pathways of pollutants and organic compounds in general. Intramolecular isotope distributions can be used to trace a pollutant’s origin, to understand its environmental transformation pathways and to evaluate remediation approaches. The atmospheric CO2 concentration ([CO2]) is currently rising at an unprecedented rate and plant responses to this increase in [CO2] influence the global carbon cycle and will determine future plant productivity. To investigate long-term plant responses, we developed a method to elucidate metabolic fluxes from intramolecular deuterium distributions of metabolites that can be extracted from historic plant material. We show that the intramolecular deuterium distribution of plant glucose depends on growth [CO2] and reflects the magnitude of photorespiration, an important side reaction of photosynthesis. In historic plant samples, we observe that photorespiration decreased in annual crop plants and natural vegetation over the past century, with no observable acclimation, implying that photosynthesis increased. In tree-ring samples from all continents covering the past 60 – 700 years, we detected a significantly smaller decrease in photorespiration than expected. We conclude that the expected “CO2 fertilization” has occurred but was significantly less pronounced in trees, due to opposing effects. The presented applications show that intramolecular isotope distributions not only provide information about the origin and turnover of compounds but also about metabolic regulation. By extracting isotope distributions from archives of plant material, metabolic information can be obtained retrospectively, which allows studies over decades to millennia, timescales that are inaccessible with manipulation experiments.

Many of the factors that shape contaminant accumulation profiles in marine mammals also strongly influence fat soluble vitamin accumulation. Vitamin A and E are essential fat soluble nutrients for numerous biological processes, including reproduction, growth, endocrine and immune function. Contaminants, such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), can alter vitamin dynamics; as such these vitamins have been proposed as sensitive biomarkers of contaminant exposure in wildlife. In light of these considerations, the present thesis was aimed at better understanding the factors that influence the accumulation of lipophilic contaminants and vitamins in western Arctic beluga whales, and to determine if there was an interaction between the two. Maternal offloading to neonates during gestation reduced overall contaminant (PCBs and PBDEs) and vitamin (A and E) concentrations in reproductively active female whales. The PCB and PBDE congener pattern in mothers changed during gestation as a result of preferential transfer of light-low Log KOW congeners to the fetus. Overall, female beluga whales transferred approximately 11% of their PCB and PBDE blubber burden to their fetus. In terms of vitamins transfer, lower concentrations of tocopherols, retinol and retinyl esters were found in reproductively active females relative to males and reproductively inactive females. Metabolism was also found to be an important factor for contaminant and vitamin accumulation in beluga tissues. In a principal components analysis, PCBs clustered into metabolically-derived structure-activity groups, which separated along the first principal component according to its metabolic potential (metabolizable vs. recalcitrant). Contaminant-related up-regulation of metabolizing enzymes, including cytochrome P450, likely explained changes in the concentration and pattern of PCB and PBDE congeners, as well as hepatic, plasma, and blubber vitamin A and E. Since vitamins and lipophilic contaminants accumulated in beluga whales in the same way in relation to most biological processes, including sex, reproduction, size, condition, and feeding ecology, it was important to control and reduce the number of these confounding factors before claiming any tissue vitamin change was indeed the result of chemical exposure. In doing so, it was found that vitamin A and E homeostasis was influenced by PCBs in beluga whales, resulting in reduced hepatic storage and increased plasma and blubber concentrations. Overall, these results suggest that liver, plasma, and inner blubber vitamin A and E concentrations can be sensitive biomarkers of contaminant exposure only if major confounding effects are taken into consideration. The implications of altered vitamin dynamics on the health of beluga whales is unknown at this time; however, as Arctic marine mammals face continued stress related to climate change, increased human disturbance and emergence of infectious diseases, this study can serve as essential baseline data that can be used to monitor the health status of western Arctic beluga whales. / Graduate / 0383 / 0329 / 0768 / jpdesforges@gmail.com