Motorboat activity can adversely effect the water quality of a reservoir. The potential impacts of motorboat activity on the Occoquan Reservoir's water and sediments were evaluated. Thirty-one sites, both marina and nonmarina, along the reservoir were selected. Sediment and water samples were collected in 1990, during peak boating activity, and in October, during low boating activity. The objectives of this research were to determine the concentrations of polyaromatic hydrocarbons (PAHs) in water and sediment samples and to determine if their presence was related to boating activity. The presence of other non-PAH organics was also determined. Contours of total PAH concentrations, boxplots and ANOVA analyses between marina and nonmarina sites were generated from gathered data in order to meet these objectives. PAHs were present in the water during peak boating activity and not detected during low boating activity, while PAHS were detected in the sediments during both sampling periods. The aqueous and sediment PAH concentrations were at or below the method detection limits. The PAH ratios of unalkylated PAHs confirmed PAH contamination to be of a combustion source. Boating was shown to be a PAH source to the water column, during peak boating activity, throughout the entire Occoquan Reservoir. An ANOVA between marina and nonmarina sites for the aqueous total PAH concentrations did not show a significant difference in June. This implied that boating did not cause any localized impacts to the water column and that there was another PAH source. There was a significant difference for total PAH concentrations between the marina and nonmarina sites for the sediment samples in June, showing localized impacts at marina areas due to boating activity. PAH profiles showed urban runoff as another major contributor to the PAH concentration in the water and sediments. The urbanization of Hooes Run and the hydrology of the reservoir caused urban runoff to impact localized areas. Finally, atmospheric deposition was also a source of PAHs to the sediments throughout the entire reservoir. Non-PAH organics found in a few of the water and sediment samples were the pesticides atrazine and p,p'-DDD, alkyl phosphates, alcohols and C₈ to C₁₂ hydrocarbons. / Master of Science

In this work the organic markers that serve for identification of sources of aerosols are monitored. Theoretic part deals with detailed survey of organic markers emitted from the most significant sources of atmospheric aerosols (biomass combustion, combustion of fossil fuels and traffic) as well as with sampling of aerosols and analysis of organic markers by analytical techniques. Monosaccharide anhydrides (emissions from biomass combustion) and polyaromatic hydrocarbons (emissions from traffic and incomplete combustion) were observed especially. Hopanes and steranes (traffic, coal combustion) and fatty acids (cooking) were next groups of monitored organic markers. Markers were studied mainly in size fraction PM1 because this fraction of aerosols is the most harmful to human health. Aerosols were sampled in two seasons (winter and summer) in two towns in 2009. Higher concentrations of aerosols and organic compounds were found in winter season, which resulted from increased combustion of biomass, coal and other organic material while traffic was the most significant source of aerosols in summer.

La réduction des inégalités d’exposition environnementale constitue un axe majeur en santé publique en France comme en témoignent les priorités des différents Plan Nationaux Santé Environnement (PNSE). L’objectif de cette thèse est de développer une approche intégrée pour la caractérisation des inégalités environnementales et l’évaluation de l’exposition spatialisée de la population aux HAP en France.Les données produites dans le cadre des réseaux de surveillance de la qualités des milieux environnementaux sont le reflet de la contamination réelle des milieux et de l’exposition globale des populations. Toutefois, elles ne présentent généralement pas une représentativité spatiale suffisante pour caractériser finement les expositions environnementales, ces réseaux n’ayant pas été initialement conçus dans cet objectif. Des méthodes statistiques sont développées pour traiter les bases de données d’entrée (concentrations environnementales dans l’eau, l’air et le sol) et les rendre pertinentes vis à vis des objectifs définis de caractérisation de l’exposition. Un modèle multimédia d’exposition, interfacé avec un Système d’Information Géographique pour intégrer les variables environnementales, est développé pour estimer les doses d’exposition liées à l’ingestion d’aliments, d’eau de consommation, de sol et à l’inhalation de contaminants atmosphériques. La méthodologie a été appliquée pour trois Hydrocarbures Aromatiques Polycycliques (benzo[a]pyrène, benzo[ghi]pérylène et indéno[1,2,3-cd]pyrène) sur l’ensemble du territoire français. Les résultats permettent de cartographier des indicateurs d’exposition, d’identifier les zones de surexposition et de caractériser les déterminants environnementaux. Dans une logique de caractérisation de l’exposition, la spatialisation des données issues des mesures environnementales pose un certain nombre de questions méthodologiques qui confèrent aux cartes réalisées de nombreuses incertitudes et limites relatives à l’échantillonnage et aux représentativités spatiales et temporelles des données. Celles-ci peuvent être réduites par l’acquisition de données supplémentaires et par la construction de variables prédictives des phénomènes spatiaux et temporels considérés.Les outils de traitement statistique de données développés dans le cadre de ces travaux seront intégrés dans la plateforme PLAINE pour être déclinés sur d’autres polluants en vue de prioriser les mesures de gestion à mettre en œuvre. / Reducing environmental exposure inequalities has become a major focus of public health efforts in France, as evidenced by the French action plans for health and the environment. The aim of this thesis is to develop an integrated approach to characterize environmental inequalities and evaluate the spatialized exposure to PAH in France.The data produced as part of the monitoring quality networks of environmental media reflect the actual contamination of the environment and the overall exposure of the populations. However they do not always provide an adequate spatial resolution to characterize environmental exposures as they are usually not assembled for this specific purpose. Statistical methods are employed to process input databases (environmental concentrations in water, air and soil) in the objective of characterizing the exposure. A multimedia model interfaced with a GIS, allows the integration of environmental variables in order to yield exposure doses related to ingestion of food, water and soil as well as atmospheric contaminants' inhalation.The methodology was applied to three Polycyclic Aromatic Hydrocarbon substances, (benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene), in France. The results obtained, allowed to map exposure indicators and to identify areas of overexposure and characterize environmental determinants. In the context of exposure characterization, the direct spatialization of available data from environmental measurement datasets poses a certain number of methodological questions which lead to uncertainties related to the sampling and the spatial and temporal representativeness of data. These could be reduced by acquiring additional data or by constructing predictive variables for the spatial and temporal phenomena considered.Data processing algorithms and calculation of exposure carried out in this work, will be integrated in the French coordinated integrated environment and health platform-PLAINE in order to be applied on other pollutants and prioritize preventative actions.

Analytical Characterization of complex mixtures, such as crude oil, environmental samples, and biological mixtures, is challenging because of the large diversity of molecular components. Mass spectrometry based techniques are among the most powerful tools for the separation of molecules based on their molecular composition, and the coupling of ion mobility spectrometry has enabled the separation and structural elucidation using the tridimensional structure of the molecule. The present work expands the ability of analytical chemists by furthering the development of IMS-MS instrumentation by coupling Trapped Ion Mobility Spectrometry to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (TIMS-FT-ICR MS). The TIMS-FT-ICR MS platform combines the high-resolution separation of TIMS, which has mobility resolving powers up to 400, and ultra-high mass resolution of FT-ICR MS, with mass resolving power over 1,000,000. This instrumentation allows the assignment of exact chemical composition for compounds in a complex mixture, as well as measurement of the collision cross-section of the molecule. Herein, the principles of the TIMS separation and its coupling to FT-ICR MS are described, as well as how the platform can be applied to targeted analysis of molecules, and untargeted characterization of complex mixtures. Molecular standards were analyzed by TIMS-MS in order to develop a computational workflow that can be utilized to elucidate molecular structure, using the measured collision cross-section of the ion. This workflow enabled identification of structural, cis/trans isomers, and chelated molecules and provides the basis for unsupervised structural elucidation of a complex mixture, and in particular for the elucidation of hydrocarbons from fossil fuels. In summary, this work presents the coupling of TIMS-FT-ICR MS and provides examples of applications as a proof of concept of the potential of this platform for solving complex analytical challenges.

<p>In this work, a simple, less time consuming electrochemical method in the form of an electrochemical sensor has been developed for the detection of PAHs. The sensor was fabricated by the deposition of silver-gold (1:3) alloy nanoparticles (Ag-AuNPs) on ultrathin overoxidized polypyrrole (PPyox) film which formed a PPyox/Ag-AuNPs composite on glassy carbon electrode (PPyox/Ag-AuNPs/GCE). The silver-gold alloy nanoparticles deposited to form the composite were chemically prepared by simultaneous reduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) using sodium citrate and characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the alloy nanoparticles.</p>

<p>In this work, a simple, less time consuming electrochemical method in the form of an electrochemical sensor has been developed for the detection of PAHs. The sensor was fabricated by the deposition of silver-gold (1:3) alloy nanoparticles (Ag-AuNPs) on ultrathin overoxidized polypyrrole (PPyox) film which formed a PPyox/Ag-AuNPs composite on glassy carbon electrode (PPyox/Ag-AuNPs/GCE). The silver-gold alloy nanoparticles deposited to form the composite were chemically prepared by simultaneous reduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) using sodium citrate and characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the alloy nanoparticles.</p>

Magister Scientiae - MSc / Polyaromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants that have been shown to be teratogenic, mutagenic and carcinogenic and pose serious threats to the health of aquatic and human life. Several methods have been developed for their determination such as immunoassay, gas chromatography and high performance liquid chromatography (HPLC) in combination with fluorescence or absorbance detection. However, these methods are known to manifest underlying disadvantages such as complicated pretreatment, high costs and time consuming processes. In this work, a simple, less time consuming electrochemical method in the form of an electrochemical sensor has been developed for the detection of PAHs. The sensor was fabricated by the deposition of silver-gold (1:3) alloy nanoparticles (Ag-AuNPs) on ultrathin overoxidized polypyrrole (PPyox) film which formed a PPyox/Ag-AuNPs composite on glassy carbon electrode (PPyox/Ag-AuNPs/GCE). The silver-gold alloy nanoparticles deposited to form the composite were chemically prepared by simultaneous reduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) using sodium citrate and characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the alloy nanoparticles. Transmission electron microscopy showed that the synthesized nanoparticles were in the range of 20-50 nm. The properties of the composite formed upon deposition of the nanoparticles on the PPyox film were investigated by electrochemical methods. The PPyox/Ag-AuNPs/GCE sensor showed strong catalytic activity towards the oxidation of anthracene, phenanthrene and pyrene, and was able to simultaneously detect anthracene and phenanthrene in a binary mixture of the two. The catalytic peak currents obtained from square wave voltammetry increased linearly with anthracene, phenanthrene and pyrene concentrations in the range of 3.0 x 10-6 to 3.56 x 10-4 M,3.3 x 10-5 to 2.83 x 10-4 M, 3.3 x 10-5 to 1.66 x 10-4 M and with detection limits of 0.169 μM, 1.59 μM and 2.70 μM, respectively. The PPyox/Ag-AuNPs/GCE sensor is simple, has antifouling properties and is less time consuming with a response time of 4 s. / South Africa

Under våren 2021 upptäcktes förhöjda halter av polyaromatiska kolväten (PAH) i Björklinges dricksvattennät. Då ett vattenprov taget hos användare påvisade halter som låg över Livsmedelsverkets gränsvärden och källan till föroreningen inte identifierats, rekommenderades hushållen i Björklinge att inte använda kranvattnet till mat och dryck under en period. Efter sektionering av nätet och provtagning identifierades en äldre, nyligen reparerad, ledningssträcka av gjutjärn som trolig föroreningskälla. Denna typ av ledning är relativt vanligt förekommande i delar av Uppsala Vattens nät. Syftet med denna studie var att få en djupare förståelse för orsakerna till PAH-föroreningen i Björklinge och bedöma risken för att liknande föroreningar ska hända igen, samt att tillhandahålla ett beslutsunderlag för Uppsala Vattens hantering av äldre gjutjärnsledningar.En litteraturstudie genomfördes och data från Björklinge analyserades. Resultaten av litteraturstudien visade att frisättning av PAH från äldre gjutjärnsrör med korrosionsskydd innehållande stenkolstjära eller bitumen är ett välkänt fenomen. Biofilmen har en skyddande effekt och graden av frisättning kan därför påverkas av faktorer som klorering eller syrehalt i vattnet. Även mekaniskt slitage i form av reparationsarbete och tryckvågor kan leda till förhöjda nivåer av PAH. Korrosion av ledningarna är troligen också en viktig faktor.Utifrån litteraturstudien och resultaten från användarprover tagna i Björklinge respektive Skuttunge kunde det konstateras att problemen i Björklinge hade ett samband med frisättning av PAH från gjutjärnsrör. Vid tidpunkten för studien kunde ökande PAH-halter observeras på vissa platser i ledningsnätet även efter ledningsbytet i Björklinge våren 2021, vilket tydde på fortsatt kontaminering. Inga uppmätta halter i användarprover låg dock över något av Livsmedelsverkets gränsvärden och PAH i dricksvattnet anses inte vara ett stort hälsomässigt problem i dagsläget. Det är däremot viktigt att fortsätta monitorera halterna av PAH i Uppsala Vattens nät då denna typ av problem kan uppstå igen. Man bör också vara försiktig med åtgärder som kan påverka biofilmen samt vara återhållsam med spoling av denna typ av ledningar. De ledningar som identifierats som föroreningskällor bör åtgärdas. Med tanke på ledningarnas stigande ålder, begränsad kunskap om PAH och dess hälsoeffekter, samt WHOs rekommendationer bör man dock initiera ett långsiktigt arbete med att byta ut eller renovera denna typ av ledningar i Uppsala Vattens nät. / During the spring of 2021 elevated levels of polyaromatic hydrocarbons (PAH) were discovered in the drinking water supply network of Björklinge. Levels above the limit set by the Swedish Food Agency were observed in one user sample, which led to the inhabitants of Björklinge being recommended not to use the tap water for drinking or cooking while the source of the contamination was being identified. After sectioning and sampling the network, an older, recently repaired cast iron pipe was identified as the probable source of the contamination. This type of pipe is not uncommon in the drinking water network of Uppsala Vatten. The purpose of this study was to gain a deeper understanding of the causes of the PAH contamination in Björklinge and to determine the risk of similar contaminations happening again. Further, it aimed to provide a basis for future decisions regarding the handling of older cast iron pipes in the drinking water network of Uppsala Vatten.A literature study was done and data from Björklinge was analysed. The results of the literature study showed that the release of PAH from older cast iron pipes with coal tar or bitumen coating is a well-known phenomenon. The biofilm has protective properties, and the degree of PAH release can hence be affected by factors such as chlorination or oxygen concentration of the water. Mechanical wear in the form of repair work or pressure waves can also cause increased levels of PAH in the water.Based on the literature study as well as the results from the user samples of Björklinge and Skuttunge, it could be determined that the PAH contamination in Björklinge was related to the release of PAH from old cast iron pipes. At the time of this study, increasing levels of PAH could be observed in some parts of the drinking water network even after the suspected pipes had been replaced during the spring of 2021. This might indicate that the contamination was still ongoing. However, no samples were above the limits set by the Swedish Food Agency and PAH is currently not considered a major health problem. Despite this, it is important to keep monitoring the levels of PAH in the drinking water since the PAH levels might increase again. It is also important to be careful with measures that might affect the biofilm and when flushing cast iron pipes. The pipes that have already been identified as sources of contamination should be replaced. Given the increasing age of the cast iron pipes, the limited knowledge of PAH and its health effects, as well as the recommendations from the WHO, a long-term plan for how to remove or renovate this type of pipes from the drinking water network of Uppsala Vatten should be initiated.

Exposomics applies metabolomics methods and technologies to the comprehensive analysis of all low molecular weight molecules (< 1.5 kDa) in complex biological samples to characterize the interaction between cellular metabolism and exogenous lifestyle exposures that determine health and quality of life. To fully access the diverse classes of biological molecules related to an individual’s metabolic profile, metabolomics frequently requires the use of complementary analytical platforms, and employs targeted and untargeted molecular profiling strategies to identify biomarkers that are clinically relevant to an individual’s health status. Chapter 2 describes a quinoline-based boronic acid biosensor for N-acetylneuraminic acid that undergoes a striking binding enhancement under strongly acidic conditions. For the first time, this work allows for direct analysis of acidic sugars with high selectivity when using UV absorbance or fluorescence detection based on formation of a highly stable boronate ester complex with metabolites containing an α-hydroxycarboxylate moiety. Chapter 3 describes a targeted analysis of 24 different organic contaminants using GC-MS that can serve as biomarkers of recent smoke exposure following search-and-rescue training exercises by firefighters located at three different sites across the province of Ontario. Importantly, skin and possible respiratory uptake of various polycyclic aromatic hydrocarbons, methoxyphenols, and resin acids was confirmed by peak excretion of several wood smoke biomarkers in urine within 6 h following acute exposure. Chapter 4 applied a cross-platform metabolomics strategy based on CE-MS and GC-MS in order to identify and validate dietary biomarkers in matching plasma and urine samples collected from healthy participants in the pilot Diet and Gene Interaction Study (DIGEST). For the first time, we demonstrate that a panel of metabolites can serve as reliable biomarkers following contrasting Prudent and Western diets over 2 weeks of food provisions, which correlated well with self-reported diet records. This work paves the way for the development of objective biomarkers for accurate assessment of wood smoke exposures, as well as complex dietary patterns as required for new advances in occupational health and nutritional epidemiology. / Dissertation / Doctor of Philosophy (PhD) / Exposomics is an emerging multidisciplinary science aimed at deciphering the complex interactions that impact human health and gene expression, such as lifestyle choices (i.e., habitual diet) and lifelong environmental exposures. There is growing interest in identifying biomarkers that can be readily measured for chronic disease prevention given an alarming global prevalence of obesity and cardiometabolic disorders, including heart disease, type 2 diabetes and cancer. The research in this thesis focuses on developing new analytical methods for identifying and quantifying metabolites that may allow for better assessments of human health, and has contributed to the development of novel biosensors for the targeted analysis of N-acetylneuraminic (sialic) acid and related acidic sugars, as well as high resolution methods for broad spectrum analysis of biotransformed organic contaminants from smoke exposure by GC-MS, and plasma and urinary metabolites that differentiate contrasting Prudent and Western diets and correlate well with self-reported diet records.

Polycyclic aromatic hydrocarbons, derivates of polycyclic aromatic hydrocarbons, chromatography