Dissertationen zum Thema „Pollution – Origines“

Le sol est essentiel à toute société humaine notamment pour la production d'aliments. Son fonctionnement repose sur des réseaux d'interactions entre les éléments qui le composent et toute perturbation modifie ces réseaux. Les microorganismes eucaryotes représentent une composante importante de l'écosystème édaphique car ils sont impliqués dans des processus essentiels comme la régulation de populations de procaryotes. Mais paradoxalement, ils restent peu étudiés comparés aux bactéries notamment lorsqu'on s'intéresse aux cycles biogéochimiques autres que celui du carbone comme par exemple ceux des métaux. Suite à une pollution par des métaux, certains de ces microorganismes eucaryotes développent des mécanismes « de résistance » cellulaires. Dans ce contexte, le laboratoire d'accueil a isolé, directement à partir d'extraits d'ARN de sol, des gènes eucaryotes impliqués dans la résistance cellulaire au Cd. Ces nouveaux gènes forment une famille codant des protéines riches en cystéines dont les positions sont conservées au sein de cette famille. Mon projet de thèse a eu pour but de caractériser l'origine taxonomique et la fonction de cette famille de gènes. Dans un premier temps, la purification de cinq de ces protéines produites dans Escherichia coli et leurs caractérisations biochimiques par des méthodes spectrométriques ont permis de montrer que cette famille génique constitue une nouvelle famille de métallothionéines capables de chélater in vitro le Zn, le Cu et le Cd. Dans un second temps, une méthode de quantification par PCR quantitative de l'expression de ces gènes, extraits à partir de sol provenant de microcosmes, a été mise au point. Dans un troisième temps, nous avons tenté d'obtenir les régions génomiques bordant ces gènes environnementaux afin d'affilier les organismes qui les portent à un groupe taxonomique et d'analyser les régions promotrices de ces gènes par capture ciblée de gènes
Soil is essential to human societies, especially for food production. Its functioning relies on interaction networks sensitive to environmental alterations. Eukaryotic microorganisms are an important component of the soil ecosystem where they are involved in essential processes such as the regulation of prokaryotic populations. However, they remain poorly studied compared to bacteria, especially concerning their roles in biogeochemical cycles other than the carbon one such as metal cycles. In response to soil metal contamination, some of these eukaryotic microorganisms develop cellular "resistance" mechanisms. In this context, the host laboratory has previously isolated, directly from soils, eukaryotic genes able to confer Cd resistance. These genes form a family coding for cysteine-rich proteins whose cysteine positions are conserved within this sequences. My thesis project aimed at characterizing the function and taxonomic origin of this gene family. First, the purification of five of these proteins produced in Escherichia coli and their biochemical characterizations by spectrometric methods demonstrated that this gene family constitutes a new family of metallothioneins capable of chelating in vitro Zn, Cu and Cd. Some of these proteins are also able to confer Zn resistance when expressed in a sensitive yeast strain. In a second step, quantitative PCR methods for measuring expression levels of these genes in soil microcosms were developed. This will allow to evaluate the level of expression of these genes as a function of an increasing supply of exogenous metal. In a third step, we tried to obtain the genomic regions flanking these environmental genes in order to be able to associate the organisms from which they originate to a taxonomic group and to analyze the promoter regions of these genes using targeted capture

Subsurface oil and surface seep samples from the Niger Delta Nigeria, Tano and Cape Three Points Basins in Ghana, and the Orcadian Basin in Scotland were analysed using an organic geochemistry approach. Source organofacies, oil thermal maturity and the effect of alteration processes were evaluated, with the aim of developing a better understanding of the origin, nature and type of petroleum present. Biomarker analyses suggested that undegraded oils are found with biodegraded oils with a range of levels of biodegradation in the Niger Delta. On the commonly used Peters and Moldowan scale of biodegradation, the samples rank between PM level 0 and 7. The Ghanaian and Scottish oils and seeps showed a range of biodegradation levels between PM level 2 and 7. Biodegradation appeared to be the major control on the composition and physical properties of the oils and seeps from Niger Delta and Ghana while there is evidence that a stage of water washing was important for the Scottish seeps. Key aspects of the biodegradation process were reflected in the variable occurrence of hopanoids and other biomarkers. 25-Norhopanes were detected in all samples biodegraded in subsurface reservoirs but absent in seeps degraded at surface conditions. This was observed for both the Ghanaian and Nigeria samples. The inverse relationship of hopane to 25- norhopanes in the Niger Delta is presented for the first time. This evidence supports the hypothesis that 25-norhopanes are a product of hopane demethylation. Furthermore a pathway for the formation of 25-norhopane from 25-norhopanoic acid by decarboxylation is evidence by nature of the covariation in relative concentration of these compounds. Seeps from Scotland show that only moderate levels of biodegradation (PM 3) have significantly reduced monoaromatic and triaromatic steroids abundances. The most likely cause for this is by water washing at surface conditions. Reservoir temperature and oil charge histories appeared to have had a significant influence on the extent of biodegradation in the Niger Delta. The late migration of oil from deeper hotter subsurface regions to shallow reservoirs accounts for the presence of undegraded oils amidst the biodegraded oils in the Niger Delta.

Emission limits for diesel engine exhaust pollutants are being continually reduced in line with increasingly stringent emissions legislation. Essential to the task of reducing diesel exhaust emissions is an understanding of the origin of the exhaust pollutants. This research has investigated the origin of a group of compounds, polycyclic aromatic hydrocarbons (PAH), in diesel exhaust emissions using 14C-radiotracer techniques developed specifically to investigate the origin of the organic components in diesel emissions. The use of radiotracers in this research has enabled both the extent to which individual PAH survive combustion and the extent to which PAH are pyrosynthesized during combustion to be measured accurately. No other diesel emissions research technique has yielded information which is so unequivocal. Radio-chromatographic techniques were developed specifically for the identification and quantification of radioactive species present in diesel emissions resulting from the combustion of a single 14C-radiolabelled precursor. Radio-high performance liquid chromatography (radio-HPLC) was the main technique used and was applicable as both a tool for sample fractionation and for analytical measurement. Radio-gas chromatographic techniques (radio-GC) were also developed and applied to the identification of radioactive species in the exhaust emissions. Diesel exhaust samples were collected from a 2L direct injection Perkins Prima diesel engine using a novel exhaust sampling device, the Total Exhaust Solvent Stripping Apparatus (TESSA) devised previously to sample organic species from automobile exhausts. Diesel combustion experiments were performed on three 14C-radiolabelled PAH, fluorene, pyrene and benzo[α]pyrene (B[α]P), and 14C-n-hexadecane. These were spiked into the diesel fuel and were combusted in the Prima Engine. The extent of survival was 0.04% for B[α]P, 0.17% for pyrene and 0.87% for fluorene. The amount of each PAH in the exhaust emissions derived from pyrosynthetic sources ranged from <20% for B[α]P, to 26.5% for fluorene and 71% for pyrene. The extent to which individual PAH survive the diesel combustion process was correlated with the molecular orbital distribution of the molecule, and especially the energy levels of the lowest unoccupied molecular orbital (LUMO). It is concluded that the relationship between PAH survival and PAH molecular orbitals (MOs) is owing to the kinetics of combustion reactions and the chemical reactivity of the P AH. The extent to which individual PAH molecules are formed during combustion varies considerably. From the limited number of experiments performed in the current research it has not been possible to determine the mechanisms responsible for the formation of these PAH during combustion. Mass balance calculations have demonstrated that the degree of pyrosynthesis of the parent PAH molecules investigated in this research may be accounted for by comparatively low rates of dealkylation of alkyl-substituted derivatives present in diesel fuel. The importance of dealkylation reactions during diesel combustion, was investigated by combusting a low aromatic fuel spiked with a non-radiolabelled alkyl-PAH, 2- and 3-ethylphenanthrene (2- and 3-EtPa), which were synthesized for this purpose. The 2 and 3-EtPa isomers were recovered in yields of 0.35% and 0.3% respectively. No dealkylation of the EtPa was detected. A statistically significant increase in the emissions of 3-methylphenanthrene (3-MePa) was detected and was equivalent to a conversion rate of 0.0004% of the EtPa spike. It is proposed that the ease with which individual alkyl-PAH isomers are dealkylated varies for specific isomers, and is dependent on the position of the alkyl-substituent on the aromatic nucleus. The major product from the combustion of the EtPa was vinylphenanthrene (ViPa) which produced in a yield equivalent to a conversion of 0.01% of the EtPa spike. Radiotracer experiments with 14C-n-hexadecane were performed to investigate the origin of the aliphatic component of diesel emissions. The extent of hexadecane survival was 0.35%. Approximately two thirds of the hexadecane in the emissions was derived from pyrosynthetic sources. The most probable source of the pyrosynthesized hexadecane in the emissions was 'thermal cracking of higher molecular weight aliphatic species in diesel fuel during the combustion process. This process may account for a significant proportion of lower molecular weight n-alkanes emitted in diesel emissions.

Le but de ce travail multidisciplinaire était la caractérisation globale et fine de la matière organique et minérale des produits issus de l'assainissement pluvial. La fraction minérale des sédiments des bassins de retenue et des produits de balayage a été étudiée par différentes méthodes chimiques et physiques ; cette étude a concerné les éléments majeurs et les métaux traces. Les résultats montrent que les sédiments sont souvent pollués, avec des concentrations supérieures aux valeurs de référence pour les sols pollués. L'étude de la fraction organique montre que les différentes fractions lipidiques sont essentiellement constituées d'hydrocarbures et de HAP à des concentrations élevées. Les acides humiques et l'humine ont été étudiés par des techniques globales et de thermochimiolyse en présence de divers agents alkylants. La technique avec TMAH montre que les substances humiques étudiées contiennent des biopolymères d'origine végétale ou microbienne et des fibres ligneuses. L'utilisation de TEAAc permet de montrer que les composés libérés sont pour partie piégés dans le réseau macromoléculaire humique et sont libérés dès que celui-ci est altéré. La dernière partie de ce travail a concerné la mobilité des métaux traces dans les différentes fractions organiques extraites et suivant le schéma d'extraction séquentielle du BCR. Les métaux peuvent être classés par ordre croissant de mobilité au sein de l'environnement de la manière suivante : Cr £ Ni < Pb £ Cu < Zn £ Cd. Tous ces résultats pourront servir de base à l'élaboration d'un cahier des charges pour les collectivités locales de manière à leur apporter des solutions efficaces de gestion des produits de l'assainissement
The objective of this multidisciplinary work was to characterise the mineral and organic matters in the sediments from storm water drainage systems. Several physical chemical techniques were used to study the mineral fraction of sediments from retention ponds and street sweeping. This study concerned major elements and trace metals. The results show that the sediments are often polluted, with concentrations higher than the reference values for polluted soils. The study of organic matter shows that the lipid fractions are mainly composed of hydrocarbons and PAHs at high concentrations. Humic acids and humine were studied by global techniques and by thermochimiolysis with different alkyl agents. The TMAH technique shows that the studied humic substances contain biopolymers from plant and bacterial origins, as well as ligneous fibres. The use of TEAA allows to show that the released compounds are partly trapped in the humic macromolecular net and are released as soon as this one is altered. The last part of the work was devoted to trace metal mobility in the different organic fractions and using the BCR sequential extraction scheme. The mobility sequence of trace metals appears to be : Cr £ Ni < Pb £ Cu < Zn £ Cd. These results could be used as a basis for recommendations to local governments in order to improve the management of sediments from storm water drainage systems

La pollution atmosphérique particulaire constitue l'un des facteurs de risques impliqués dans l'incidence élevée de pathologies respiratoires et cardio-vasculaires. Afin d'intégrer les variations liées aux sources d'émission et aux saisons, des aérosols atmosphériques particulaires (PM₂.₅) ont été prélevés à Dunkerque sous influence urbaine (U) et/ou industrielle (I) et à Rubrouck sous influence rurale (R), au printemps-été 2008 (1) et à l'automne 2009 (2). La caractérisation physico-chimique des six échantillons particulaires a montré une granulométrie fine (79 à 98 % < PM₂.₅) et des aires spécifiques de 3 à 6 m²/g. Leurs concentrations en espèces ioniques différaient, comme celles en éléments métalliques majoritaires (Fe > Al > Mn > Zn > Cu > Ti ; I > U > R). Des différences ont également été observées quant à leurs concentrations en éléments organiques (HAP : I2 > U2 > I1 > U1 > R2 > R1 ; PCDD/F et PCB : I2 > I1 > U2 > U1 > R1 > R2) ; eu égard des influences considérées (PMindustriel > PMurbain > PMrural), et des saisons de prélèvements. Après évaluation de la cytotoxicité globale in vitro des échantillons particulaires, dans les cellules épithéliales bronchiques humaines (BEAS-2B), nous avons montré la capacité des composés organiques absorbés à la surface de ces particules à induire l'expression génique des enzymes de métabolisation (CYP 1A1 et 1B1, et à moindre mesure NQO1). De plus, la production excessive des ERO intracellulaires dans les cellules BEAS-2B exposées aux six PM₂.₅ a induit des dommages oxydatives (production de MDA, formation de 8-OHdG et/ou altération du statut de glutathion). Un développement d'une réponse inflammatoire excessive a aussi été observé par l'expression et/ou la sécrétion significative des cytokines (notamment IL-6 et IL-8). Ces réponses ont été observées d'une manière dose et/ou temps dépendante. En revanche, nous n'avons pu observer de mutations géniques au niveau des acteurs principaux de la voie EGFR/KRAS/BRAF
Particulate air pollution constitutes one of the major risk factors implicated in the high incidence of respiratory and cardio-vascular pathologies. In order to integrate the variation linked to emission sources and seasons, atmospheric particulate matter (PM₂.₅) were collected at Dunkerque under urban (u) and/or industrial influence (I) and at Rubrouck (R) under rural influence, in spring-summer 2008 and autumn-winter 2009. The physico-chemical characterization of the six particulate samples has shown a fine granulometry (79 to 98 % < PM₂.₅) and a specific surface of 3 to 6 m²/g. Their concentrations in ionic species as well as in major metallic elements were different (Fe > Al > Mn > Zn > Cu > Ti ; I > U > R). Differences were also been observed in their organic element constitution (PAH : I2 > U2 > I1 > U1 > R2 > R1 ; PCDD/F and PCB : I2 > I1 > U2 > U1 > R1 > R2) with respect to considered influences (PMindustriel > PMurban > PMrural) and sampling seasons. After in vitro evaluation of particulate samples global cytotoxicity in human bronchial epithelial cells (BEAS-2B), we had shown the capacity of the organic components absorbed to the surface of these particles to induce gene expression of xenobiotic-metabolizing enzymes (CYP 1A1 and 1B1, and to a lesser extent, NQO1). Moreover, excessive intracellular production of reactive oxygen species within BEAS-2B cells exposed to the six PM₂.₅ samples induced oxidative damage (MDA production, 8-OHdG formation and/or glutathione status alteration). There was also a development of an excessive inflammatory response based on statistically significant increases in gene expression and/or protein secretion of cytokines (notably IL-6 and IL-8). These obtained responses were dose and/or time dependant. However, we couldn't observe mutations in the principal acting genes in the pathway EGFR/KRAS/BRAF

Ce travail s'inscrit dans les grandes problématiques actuelles traitant des interactions environnement-santé en contexte minier. L'objectif est de décrire l'origine et l'impact sur l'environnement et la santé des pollutions liées aux activités d'extraction et de fonte polymétalliques (Ag, Au, Cd, Cu, Pb, Sb, Sn, Zn) dans la ville minière d'Oruro, en Bolivie. Des échantillons d'eaux de consommation et de surface, de sols, de poussières de sol, d'aérosols (PM2,5 et PM10) et de bioaccumulateurs de la contamination atmosphérique (Tillandsias capillaris) ont été caractérisés géochimiquement (ICP-MS) et minéralogiquement (DRX, MEB). L'ensemble des compartiments " eaux ", " sols " et " atmosphère " de la zone urbaine est contaminé en Eléments Trace Métalliques (ETM), notamment à proximité des mines et des fonderies (atteignant 16000 µ/g de Pb dans les sols ou 200 ng/m3 d'As dans les PM10 prés de la fonderie). Les différentes sources de contamination atmosphérique (érosion des terrils miniers, émissions des fonderies, transport de minerais) et leurs zones d'influence sont identifiées à l'aide d'études statistiques et d'interpolations spatiales. L'étude des sols et des poussières indique d'autres sources de contamination plus locales, comme une ancienne zone de stockage de minerais. Les séparations granulométriques des poussières montrent que les ETM sont globalement plus concentrés dans les fractions fines, mais pas nécessairement dans la fraction argileuse (< 2µm), généralement considérée comme étant la fraction la plus contaminée. La bioaccessibilité des poussières, mesurée par la méthode UBM, est globalement plus faible prés de la mine que de la fonderie, et varie en fonction de la fraction granulométrique et de l'élément considéré (jusqu'à 90% pour As et inférieure à 5% pour Sb et Sn). Le bilan d'exposition aux ETM des enfants selon leur quartier d'habitation (" centre ville ", " mine " et " fonderie ") est réalisé en prenant en compte l'ingestion et l'inhalation des poussières de sol et des aérosols. La prise en compte de la granulométrie et de la bioaccessibilité par fraction influe fortement sur les calculs de doses absorbées par l'organisme. Les doses absorbées calculées et les concentrations précédemment mesurées dans les cheveux des enfants sont corrélées. Dans cette étude, le Pb présente un comportement particulier : il présente des tenenurs très hautes dans les sols mais très faibles dans l'atmosphère. L'exposition est donc particulièrement liée au type et au lieu d'activité du sujet considéré et expliquerait la variabilité observée dans une étude épidémiologique antérieure.

Ce travail s'inscrit dans les grandes problématiques actuelles traitant des interactions environnement-santé en contexte minier. L'objectif est de décrire l'origine et l'impact sur l'environnement et la santé des pollutions liées aux activités d'extraction et de fonte polymétalliques (Ag, Au, Cd, Cu, Pb, Sb, Sn, Zn) dans la ville minière d'Oruro, en Bolivie. Des échantillons d'eaux de consommation et de surface, de sols, de poussières de sol, d'aérosols (PM2,5 et PM10) et de bioaccumulateurs de la contamination atmosphérique (Tillandsias capillaris) ont été caractérisés géochimiquement (ICP-MS) et minéralogiquement (DRX, MEB). L'ensemble des compartiments " eaux ", " sols " et " atmosphère " de la zone urbaine est contaminé en Eléments Trace Métalliques (ETM), notamment à proximité des mines et des fonderies (atteignant 16000 µ/g de Pb dans les sols ou 200 ng/m3 d'As dans les PM10 prés de la fonderie). Les différentes sources de contamination atmosphérique (érosion des terrils miniers, émissions des fonderies, transport de minerais) et leurs zones d'influence sont identifiées à l'aide d'études statistiques et d'interpolations spatiales. L'étude des sols et des poussières indique d'autres sources de contamination plus locales, comme une ancienne zone de stockage de minerais. Les séparations granulométriques des poussières montrent que les ETM sont globalement plus concentrés dans les fractions fines, mais pas nécessairement dans la fraction argileuse (< 2µm), généralement considérée comme étant la fraction la plus contaminée. La bioaccessibilité des poussières, mesurée par la méthode UBM, est globalement plus faible prés de la mine que de la fonderie, et varie en fonction de la fraction granulométrique et de l'élément considéré (jusqu'à 90% pour As et inférieure à 5% pour Sb et Sn). Le bilan d'exposition aux ETM des enfants selon leur quartier d'habitation (" centre ville ", " mine " et " fonderie ") est réalisé en prenant en compte l'ingestion et l'inhalation des poussières de sol et des aérosols. La prise en compte de la granulométrie et de la bioaccessibilité par fraction influe fortement sur les calculs de doses absorbées par l'organisme. Les doses absorbées calculées et les concentrations précédemment mesurées dans les cheveux des enfants sont corrélées. Dans cette étude, le Pb présente un comportement particulier : il présente des tenenurs très hautes dans les sols mais très faibles dans l'atmosphère. L'exposition est donc particulièrement liée au type et au lieu d'activité du sujet considéré et expliquerait la variabilité observée dans une étude épidémiologique antérieure
This work deals with current problematic issues of environment-health interactions. This thesis describes the origin of mining and smelting polymetallic pollution (Ag, Au, Cd, Cu, Pb, Sb, Sn, Zn) and its impact on environment and health in the mining city of Oruro, Bolivia. Samples of tap water, the hydrographic network, soils, dusts, aerosols (PM2,5 et PM10) and bioindicators of atmospheric contamination (Tillandsias capillaris) were geochemically (ICP-MS) and mineralogically (DRX, SEM) characterized. All the compartments of the urban area studied ("water ", "soil" and "atmosphere") were contaminated by trace elements, especially near smelters and mines (reaching 16000 µg/g Pb in dust and 200 ng/m3 As in PM10 close to the smelting area). Statistical studies and spatial interpolations helped in the identification of atmospheric contamination sources and their scope. Soil and dust studies also indicated other more local sources, such as old ore stockage areas. Granulometric separation of dusts showed that trace elements were more highly concentrated in fine fractions, but not necessarily in the clay (< 2µm), which is generally considered to be the most contaminated fraction. Oral bioaccessibility of dust fractions (UBM method), is higher overall in the smelting area than in the mining one. Bioaccessibility greatly varies depending on the granulometric fraction or elements considered (up to 90% for As and less than 5% for Sn and Sb). Exposure to trace elements in children depending on their place of residence was calculated considering dust and aerosol inhalation and ingestion. Taking into account granulometry and bioaccessibility can considerably change the absorbed dose calculated. Estimated exposure and trace element content in children's hair previously measured prove to be correlated. In this study, Pb showed a particular behaviour, with soil Pb concentrations were very high when compared to weak aerosol concentrations. Child exposure is thus greatly linked to type and location of the child's activities, which can explain the variability observed in a previous epidemiological study

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are persistent organic pollutants of global concern as they are persistent, toxic and can biomagnify through the food chain. PCDD/Fs are generally regarded as trace contaminants in a number of chemical products and they are formed as by-products from various industrial, chemical and combustion processes. The pollution with PCDD/Fs occurs with the release of these chemicals into the environment, resulting in the contamination of various compartments including; air, soil, sediment and biota. Studies that have investigated the distribution of PCDD/Fs in the environment suggest that the highest concentrations of these pollutants are found in locations with a history of industrial or chemical PCDD/F sources. Queensland is the north-eastern state of Australia. Queensland has a low population density, few industrial activities and is considered predominantly rural. Therefore it was somewhat surprising that elevated concentrations of PCDD/Fs (in particular the higher chlorinated PCDDs) have been observed in soil and sediments samples collected from various locations along the Queensland coast. The concentrations of PCDDs in Queensland samples were comparable to or higher than concentrations in similar matrices from highly polluted regions elsewhere. To investigate the origin of PCDDs in Queensland, the geographical distribution of PCDD/Fs in topsoil was investigated in the coastal and inland environments to provide information on the potential sources and to estimate the extent of the PCDD contamination. Distinct east-west gradients were detected in topsoil collected from bushland areas across the state with elevated PCDD concentrations confined to the coastal region. Within the coastal region, the contamination could not be associated with specific land uses. In fact, the PCDD/F congener profile was similar in the majority of samples from the coastal region, with a dominance of the higher chlorinated PCDDs (in particular OCDD), whereas PCDFs were low or below the limit of detection. The similarity in the PCDD/F congener profiles in the soils along the coastal region indicated that a source of PCDDs of similar origin has resulted in the contamination of soil extending more than 3000 km and estimations suggest that more than 50 tonnes of OCDD is stored in the topsoil of Queensland.s coastal region. Investigation into the vertical distribution of PCDDs in Queensland coastal soils revealed elevated concentrations of PCDDs, (in particular OCDD) in soils to at least 3.5 m. These results indicated that the extent of the PCDD contamination is significantly greater than anticipated and it was estimated that there is in the order of 3 000 tonnes of OCDD stored in Queensland's coastal soils. The specific PCDD/F congener profile in Queensland coastal soils is unlike known PCDD/F source profiles which led to the suggestion that some yet unidentified formation mechanism may have resulted in the contamination. Potential natural sources of PCDD/Fs, including forest fires, geogenic and biogenic processes were assessed as possible origins for the PCDD contamination in Queensland. Elevated concentrations of PCDDs were detected in the atmosphere during a 'prescribed burn'. This study demonstrated that although forest fires influence atmospheric PCDD/F concentrations substantially, forest fires are not the source of PCDDs in Queensland; rather they are an important mechanism for the redistribution of PCDDs and may have attributed to the widespread PCDD contamination. In this study geological materials (oil shale and kaolin) were analysed as a proxy to assess a geogenic origin of PCDDs. Elevated concentrations of PCDDs were observed in the kaolin samples, however similar and higher concentrations were detected in surface and sub-surface soils, suggesting that specific geogenic formation processes investigated are not the source of PCDDs in Queensland. A preliminary indication for a biogenic origin of PCDDs was identified during the anaerobic incubation of sugarcane irrigation sediments. An increase in the concentration of OCDD in the anaerobic treatment, compared to the control was observed after incubation for 90 days. In these same experiments, a dechlorination of OCDD to lower chlorinated (1,4,6,9-substituted) PCDDs was also observed. Similar transformation processes were observed in other anaerobic environments in Queensland, which led to the suggestion that a biogenic formation of PCDDs (possibly from a precursor) may be responsible for the origin of PCDDs in Queensland.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are persistent organic pollutants of global concern as they are persistent, toxic and can biomagnify through the food chain. PCDD/Fs are generally regarded as trace contaminants in a number of chemical products and they are formed as by-products from various industrial, chemical and combustion processes. The pollution with PCDD/Fs occurs with the release of these chemicals into the environment, resulting in the contamination of various compartments including; air, soil, sediment and biota. Studies that have investigated the distribution of PCDD/Fs in the environment suggest that the highest concentrations of these pollutants are found in locations with a history of industrial or chemical PCDD/F sources. Queensland is the north-eastern state of Australia. Queensland has a low population density, few industrial activities and is considered predominantly rural. Therefore it was somewhat surprising that elevated concentrations of PCDD/Fs (in particular the higher chlorinated PCDDs) have been observed in soil and sediments samples collected from various locations along the Queensland coast. The concentrations of PCDDs in Queensland samples were comparable to or higher than concentrations in similar matrices from highly polluted regions elsewhere. To investigate the origin of PCDDs in Queensland, the geographical distribution of PCDD/Fs in topsoil was investigated in the coastal and inland environments to provide information on the potential sources and to estimate the extent of the PCDD contamination. Distinct east-west gradients were detected in topsoil collected from bushland areas across the state with elevated PCDD concentrations confined to the coastal region. Within the coastal region, the contamination could not be associated with specific land uses. In fact, the PCDD/F congener profile was similar in the majority of samples from the coastal region, with a dominance of the higher chlorinated PCDDs (in particular OCDD), whereas PCDFs were low or below the limit of detection. The similarity in the PCDD/F congener profiles in the soils along the coastal region indicated that a source of PCDDs of similar origin has resulted in the contamination of soil extending more than 3000 km and estimations suggest that more than 50 tonnes of OCDD is stored in the topsoil of Queensland.s coastal region. Investigation into the vertical distribution of PCDDs in Queensland coastal soils revealed elevated concentrations of PCDDs, (in particular OCDD) in soils to at least 3.5 m. These results indicated that the extent of the PCDD contamination is significantly greater than anticipated and it was estimated that there is in the order of 3 000 tonnes of OCDD stored in Queensland.s coastal soils. The specific PCDD/F congener profile in Queensland coastal soils is unlike known PCDD/F source profiles which led to the suggestion that some yet unidentified formation mechanism may have resulted in the contamination. Potential natural sources of PCDD/Fs, including forest fires, geogenic and biogenic processes were assessed as possible origins for the PCDD contamination in Queensland. Elevated concentrations of PCDDs were detected in the atmosphere during a 'prescribed burn'. This study demonstrated that although forest fires influence atmospheric PCDD/F concentrations substantially, forest fires are not the source of PCDDs in Queensland; rather they are an important mechanism for the redistribution of PCDDs and may have attributed to the widespread PCDD contamination. In this study geological materials (oil shale and kaolin) were analysed as a proxy to assess a geogenic origin of PCDDs. Elevated concentrations of PCDDs were observed in the kaolin samples, however similar and higher concentrations were detected in surface and sub-surface soils, suggesting that specific geogenic formation processes investigated are not the source of PCDDs in Queensland. A preliminary indication for a biogenic origin of PCDDs was identified during the anaerobic incubation of sugarcane irrigation sediments. An increase in the concentration of OCDD in the anaerobic treatment, compared to the control was observed after incubation for 90 days. In these same experiments, a dechlorination of OCDD to lower chlorinated (1,4,6,9-substituted) PCDDs was also observed. Similar transformation processes were observed in other anaerobic environments in Queensland, which led to the suggestion that a biogenic formation of PCDDs (possibly from a precursor) may be responsible for the origin of PCDDs in Queensland.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Public Health
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Thesis (MSc Food Sc)--Stellenbosch University, 2013.
ENGLISH ABSTRACT: Over the past two decades, there has been an increase in the use of water sources for irrigation, as well as an increase in Escherichia coli outbreaks linked to fresh produce. The full extent and type of E. coli contamination present in natural water sources is unknown and the contamination sources have also not been confirmed. The aim of this study was to enumerate and characterise E. coli from both irrigation water and potential contamination source sites. Total coliform and E. coli counts found in contamination source sites were as high as log 7.114 and log 6.912 MPN.100 mL-1, respectively. Total coliform and E. coli counts for irrigation sites were lower, with maximum counts of log 5.788 and log 5.768 MPN.100 mL-1, respectively. It was found that more than one third (5/14 = 35.71%) of the irrigation sites had E. coli counts exceeding the guidelines (<1 000 counts.100 mL-1) for ‘safe’ irrigation water for fresh produce (<1 000 counts.100 mL-1) as set by the Department of Water Affairs (DWA) and World Health Organisation (WHO), making the water unsuitable for the irrigation of fresh produce. Phylogenetic subgroups (A0, A1, B1, B22, B23, D1 and D2) and the MALDI Biotyper system (PCA dendrogram) were used to create a fingerprint of each E. coli isolated from the environment. These were then used to link E. coli strains from irrigation water to their most probable contamination origin. Escherichia coli population structure was found in this study, to be better suited for linking E. coli strains from irrigation water to their most likely source, than just applying the phylogenetic grouping. The MALDI Biotyper data in combination with the phylogenetic subgroup assignment was then used to group similar strains and link E. coli from irrigation water to their contamination sources by comparing population structures. Strains isolated from surface and groundwater showed similar distribution patterns, but groundwater strains showed a population structure more indicative of porcine and bovine origin, while surface water showed population characteristics which could not be used to make conclusive links between the irrigation water and suspected contamination sources. When investigating the population structures of individual sample sites, it was found that phylogenetic subgroups A0, A1 and B1 frequently made up the bulk of the E. coli population. It was also found that linking individual irrigation sites to contamination sources was successful, as irrigation site Berg-2 was found to have a similar population structure to contamination source site Plank-1 which represents human pollution from an informal settlement. This led to the conclusion that Berg-2 was being contaminated by human pollution, most probably from an informal settlement. Upon further investigation it was found that Berg-2 is downstream of an informal settlement, proving that E. coli population structure is a successful means of microbial source tracking (MST). Virulence factors of the 153 E. coli isolated during the study were identified and the potential risk associated with using the investigated irrigation water for irrigation of fresh produce, was determined. Two enteropathogenic E. coli (EPEC) strains were isolated from the irrigation water, one from the Plankenburg River water, and the other from a borehole in the Drakenstein area. The latter indicates that borehole water is not as safe as was once thought, and that there are bacterial contaminants finding their way into groundwater. The occurrence of an EPEC strain in river water shows that neither ground nor surface water is guaranteed to be safe, and that treatment of water being used for the irrigation of fresh produce should be implemented.
AFRIKAANSE OPSOMMING: Oor die afgelope twee dekades was daar nie net 'n toename in die gebruik van alternatiewe waterbronne vir besproeiing nie, maar ook 'n toename in uitbrake van Escherichia coli uitbrake wat aan vars produkte gekoppel kan word. Die tipe E. coli-besmetting wat in natuurlike waterbronne teenwoordig is, is onbekend en die besmettingsbron is ook nog nie bevestig nie. Daarom was die doel van hierdie studie om die voorkomssyfer van E. coli van beide besproeiingswater en potensiële kontaminasiebronne te bepaal, asook om die E. coli te karakteriseer. Totale kolivorme en E. coli-tellings wat in kontaminasiebronne gevind is, het ‘n maksimum van log 7,114 en log 6,912 MPN.100 mL-1 onderskeidelik bereik, terwyl die totale kolivorme en E. coli-tellings vir besproeiingswater laer was, met 'n maksimum van log 5,788 en 5,768 MPN.100 mL-1, onderskeidelik. Dit is bevind dat meer as 1/3 (5/14 = 35,71%) van die besproeiingswaterbronne meer E. coli bevat as wat toegelaat word in die riglyne vir "veilige" besproeiingswater vir vars produkte (<1 000 fekale koliforme.100 mL-1) wat deur die Departement Waterwese (DWA) en die Organisasie vir Wêreldgesondheid (WHO) aanbeveel word. Filogenetiese subgroepe (A0, A1, B1, B22, B23, D1 en D2) en die ‘MALDI Biotyper’-stelsel (PKA dendrogram) is gebruik om unieke profiele vir elke geïsoleerde E. coli te skep. Dié profiele is daarna gebruik om E. coli-stamme van besproeiingswater te koppel aan die mees waarskynlike oorsprong van kontaminasie. Daar is in hierdie studie bevind dat die E. coli-populasiestruktuur beter geskik was vir die koppeling van E. coli-stamme van besproeiingswater na hul mees waarskynlikste bron, as net die toepassing van die filogenetiese groepering. Dit was toe gevind dat E. coli wat uit oppervlak- en grondwater geïsoleer is, soortgelyke verspreidingspatrone het, maar grondwaterstamme se bevolkingstruktuur is meer aanduidend van fekale besmetting deur varke en beeste, terwyl oppervlakwater se bevolkingseienskappe nie duidelik genoeg was om ‘n gevolgtrekking oor moontlike bronne van besmetting te maak nie. Toe die populasiestruktuur van die individuele bemonsteringspunte ondersoek is, is daar bevind dat die filogenetiese subgroepe A0, A1 en B1 dikwels die meeste tot die E. coli bevolking bydra. Daar is ook bevind dat die koppeling van isolate in individuele besproeiingswaterbronne met hul mees waarskynlike bronne van kontaminasie suksesvol was. Besproeiingswater van Berg-2 het 'n soortgelyke populasiestruktuur as Plank-1 wat beskou is as ‘n kontaminasiebron. Dit het gelei tot die gevolgtrekking dat Berg-2 heel waarskynlik deur menslike besoedeling beïnvloed word, soos Plank-1, en dat daar moontlik ook ‘n informele nedersetting by Berg-2 betrokke is. Na verdere ondersoek is gevind dat Berg-2 inderdaad ook stroomaf van 'n ander informele nedersetting geleë is, wat bewys dat die E. coli-populasiestruktuur 'n suksesvolle manier is om E. coli kontaminasie te verbind met besproeiingswater. Patogeniese faktore, wat in E. coli voorkom en maagkieme veroorsaak, is vooraf getoets in elkeen van die 153 E. coli-isolate wat tydens die studie geïdentifiseer is. Twee ‘enteropathogenic’ E. coli (EPEC)-stamme is uit die besproeiingswater geïsoleer: een uit die Plankenburgrivier (Plank-3), en die ander uit 'n boorgat in die Drakenstein-gebied (Boorgat A1). Hierdie inligting dui aan dat boorgatwater nie so veilig is as wat voorheen vermoed is nie, en dat bakteriese kontaminasie wel vookom wat nie alleen die grondwater besmet nie, maar ook daarin oorleef. Die voorkoms van die EPEC-stamme in hierdie studie is ‘n aanduiding dat beide grond- en opppervlakwater ewe gevaarlik kan wees, en dat daar dus geen waarborg vir die veiligheid van die water is nie. Die behandeling van grond- en oppervlakwater, wat vir die besproeiing van vars produkte gebruik word, moet daarom ernstig oorweeg word om moontlike uitbrake van E. coli op vars produkte te verhoed.

Plusieurs études sur la toxicité des particules dans l'air ambiant montrent que la phase polaire, qui contient entre autres des Hydrocarbures Aromatiques Polycycliques oxygénés et nitrés (OHAP et NHAP), est plus toxique que la fraction aromatique contenant les HAP classiques. Dans ce contexte, l'objectif de ce travail était de caractériser chimiquement les NHAP et OHAP dans l'air ambiant de différents milieux (trafic, urbain, péri-urbain, rural et altitude). Les prélèvements ont été réalisés dans le cadre du programme de recherche POllution des Vallées Alpines (POVA) au cours de l'hiver 2002-2003 et de l'été 2003 et dans la région de Marseille l'été 2004. Les deux phases, gazeuse et particulaire, ont été étudiées et une caractérisation des particules par tranche granulométrique a également été effectuée. Les résultats obtenus sur les OHAP et les NHAP ont permis d'alimenter la base de données très limitée sur ce type de composés et ce pour des atmosphères variées. Le développement d'une méthode d'analyse simultanée par GC/NICI-MS des NHAP et OHAP sur des matrices complexes, facile à mettre en œuvre et utilisable en routine, nous a permis de montrer que les niveaux de concentrations des OHAP dans l'air ambiant sont du même ordre de grandeur que ceux des HAP alors que les concentrations des NHAP sont de 1 à 2 ordres de grandeur inférieures. L'estimation du risque cancérigène à partir de facteurs d'équivalence toxique montre que le risque attribué aux NHAP peut atteindre 20% du risque total. L'étude de rapports spécifiques de NHAP a montré que sur les sites proches des sources de pollution, les NHAP ont une origine primaire forte alors que leur formation par réaction en phase gazeuse est évidente en été sur les sites ruraux éloignés des sources directes de pollution et qu'elle a lieu principalement de jour, initiée par OH. Il apparaît que les émissions des véhicules essence sont une source non négligeable de NHAP et de OHAP dans l'atmosphère. Le OHAP 9,10-anthraquinone présente une double origine (primaire diesel et formée par photochimie) sans pour autant pouvoir distinguer le lieu de la formation (sur le support du prélèvement ou dans l'atmosphère). La partition entre les deux phases des HAP, OHAP et NHAP, est extrêmement dépendante de la masse moléculaire du composé considéré et de la température. L'étude de cette partition semble pouvoir apporter des informations quant à l'origine primaire ou secondaire des dérivés des HAP. Enfin, les HAP, OHAP et NHAP sont essentiellement (>80%) associés à la fraction fine de l'aérosol (Dp<1,3 µm) et ce quelque soit la saison considérée (hiver et été). Les caractéristiques chimiques des différentes classes de composés (polarité…) peuvent néanmoins jouer un rôle quant à leur distribution en taille.

Des études épidémiologiques récentes suggèrent que certains polluants atmosphériques jouent un rôle dans le développement et la progression de l'insulino-résistance, associée au diabète de type 2. L'ozone, un polluant photochimique majeur des zones urbaines, est associé t à des concentrations augmentées de glucose et d'insuline plasmatiques à jeun, cependant de nombreux aspects de cette association restent à élucider. En utilisant une concentration réaliste, représentative des pics de pollution (0,8 ppm), nous avons démontré que l'exposition de rats à de l'ozone induit une insulino-résistance systémique et un stress oxydant, associé à un stress du réticulum endoplasmique (RE), une activation de JNK et donc, une perturbation du signal insulinique dans le muscle. Les lavages broncho-alvéolaires réalisés chez des rats exposés à l'ozone, reproduisent ces effets sur des myotubes C2C12, suggérant que des médiateurs pulmonaires toxiques sont responsables de ce phénotype. Des prétraitements avec le chaperon chimique acide 4-phénylbutyrique, l'inhibiteur de JNK SP600125, ou l'antioxydant N-acétylcystéine préviennent l'insulino-résistance, démontrant que l'ozone induit séquentiellement un stress oxydant, un stress du RE et une activation de JNK, entraînant une perte de la sensibilité à l'insuline dans le muscle. Notre étude est la première à montrer que la pollution à l'ozone provoque le développement de l'insulino-résistance, suggérant qu'elle pourrait accélérer la progression du diabète. Nous proposons ainsi un mécanisme liant exposition à des polluants et augmentation de l'incidence des maladies métaboliques
A growing body of evidence suggests that exposure to traffic-related air pollution is a risk factor for type 2 diabetes. Ozone, a major photochemical pollutant in urban areas, is negatively associated with fasting glucose and insulin concentrations but most aspects of this association remain to be elucidated. Using an environmentally realistic concentration (0.8 ppm), we demonstrated that exposition of rats to ozone induced whole body insulin resistance and oxidative stress, with associated endoplasmic reticulum (ER) stress, JNK activation and disruption of insulin signaling in skeletal muscle. Bronchoalveolar lavage fluids from ozone-treated rats reproduced this effect in C2C12 myotubes, suggesting that toxic lung mediators were responsible for the phenotype. Pre-treatments with the chemical chaperone 4-phenyl butyric acid, the JNK inhibitor SP600125 or the antioxidant N-acetylcysteine alleviated insulin resistance, demonstrating that ozone sequentially triggered oxidative stress, ER stress and JNK activation to impair insulin signaling in muscle. This study is the first to report that ozone plays a causative role in the development of insulin resistance, suggesting that it could boost the development of diabetes. We therefore provide a potential mechanism linking pollutant exposure and the increased incidence of metabolic diseases

Les particules atmosphériques ont des impacts économiques, sanitaires et environnementaux importants à l'échelle mondiale. La réduction de leurs émissions afin d’améliorer la qualité de l'air ambiant exige une connaissance approfondie de leurs sources, qui peut être apportée par l'étude de leur composition chimique. La présente thèse vise à identifier les principales sources et origines géographiques des PM10 sur 5 sites d'échantillonnage (3 urbains, 1 trafic et 1 distant) représentatifs du Nord de la France, fréquemment soumis à des dépassements des valeurs réglementaires. La méthodologie a consisté en : (i) une caractérisation chimique complète des PM10 sur les 5 sites ; (ii) l’identification et la quantification des sources primaires et des processus secondaires pour chaque site par factorisation par matrice positive (PMF) ; (iii) l’estimation des champs de concentration (CF) des sources lointaines identifiées par PMF par combinaison avec les rétrotrajectoires de masses d’air, afin de localiser les zones d’émissions.La matière organique et le nitrate d'ammonium prédominent, avec quelques différences selon le type de site. De fortes contributions en aérosols secondaires (riches en nitrate, sulfate et oxalate) ont été observées, ainsi qu’un impact significatif du trafic et de la combustion de biomasse. Les zones d’émission identifiées pour les particules naturelles sels marins frais et vieillis (principalement de l'océan Atlantique) et biogéniques marins (principalement de la mer du Nord), et les contributions continentales anthropiques de particules secondaires riches en nitrate et sulfate, valident l’approche utilisée
Airborne particles have significant economical, health and environmental impacts at a global scale. Mitigating their emissions to improve ambient air quality demands a deep knowledge on their sources, which can be determined by investigating their chemical composition. The present thesis aims at identifying major PM10 sources and geographical origins at 5 sampling sites (3 urban background, 1 traffic and 1 remote) representative of Northern France, which is frequently submitted to exceedances of limit values as defined by European Directives. The first step of this study included a comprehensive chemical characterization of PM10 filter samples collected every third day at the 5 sites. Organic matter and ammonium nitrate were confirmed as the main PM10 species in the investigated area with some differences according to the site type. Positive Matrix Factorization (PMF) was used to identify and quantify the contributions of primary sources as well as secondary processes impacting each sampling site. Large contributions of secondary aerosols (mainly grouped as nitrate-, sulfate- and oxalate-rich aerosols) were obtained at all sites, as well as significant traffic and biomass burning. The use of specific tracers like MSA and polyols also proved to be useful to identify marine and continental biogenic aerosols, respectively. Statistical trajectory-based model was applied to PMF outputs to calculate Concentration Field maps and locate emission sources of marine particles, namely fresh and aged sea salts (primarily from the Atlantic Ocean) and marine biogenic aerosols (mainly from the North Sea), as well as continental contributions of nitrate-and sulfate-rich secondary particles

Etude des emissions naturelles de carbone particulaire et evaluation des perturbations induites par les activites humaines sur le cycle atmospherique du carbone. Travail s'appuyant sur des mesures de concentration et de granulometrie d'aerosol preleve au cours de nombreuses campagnes en milieu continental tempere et tropical ainsi qu'en zone oceanique des deux hemispheres. L'origine et le transport a grande echelle des aerosols sont determines par des mesures de composition isotopique (**(13)c/**(12)c) au spectrometre de masse

Nitrogen pollution in water is common in our environment, especially in places affected by agriculture and livestock, industry or wastewater discharge areas. Ammonium and nitrate are the most common pollutants and can be removed primarily by microorganisms. This removal is carried out by a series of microorganisms that live in these environments as communities, the study of which is essential to evaluate the efficiency of the N removal from water. In this thesis, a variety of methods have been used to study these microorganisms accurately in two types of highly sensitive environments for pollution, wetlands and groundwater.
La contaminació de l’aigua per excés de nitrogen és habitual en el nostre entorn, especialment en llocs impactats per l’agricultura i la ramaderia, zones de descàrrega d’aigües residuals, o com a resultat de l’activitat industrial. L’amoni i el nitrat són els contaminants més freqüents i poden ser eliminats principalment pels microorganismes. Aquesta eliminació la duen a terme diferents microorganismes que habiten en aquests ambients en forma de comunitats, l’estudi de les quals és cabdal per a valorar l’eficiència de l’eliminació del N de l’aigua. En aquesta tesi es desenvolupen mètodes per a fer un estudi acurat d’aquests microorganismes en dos tipus d’ambients altament sensibles a la contaminació, els aiguamolls i l’aigua freàtica.

Depuis une trentaine d'années, les eaux de ruissellement sont considérées comme une source importante de pollution des milieux naturels en raison de leur concentration élevée en micropolluants. Les dépôts atmosphériques, l'érosion des surfaces imperméables (toitures, chaussées, trottoirs et parkings) et le lessivage des dépôts générés principalement par le transport, les chauffages et les industries sont les principales sources identifiées. L'objectif du travail présenté dans ce mémoire est de caractériser et déterminer des sources de métaux traces, hydrocarbures aromatiques polycycliques (HAP) et pesticides transportés par les rejets de temps de pluie issus de deux bassins versants séparatifs situés à l'Est de Nantes (bassins du Pin Sec et des Gohards). Ce travail s'inscrit dans le cadre d'un projet fédératif de recherche de l'Institut de Recherches en Sciences et Techniques de la Ville (IRSTV). L'étude détaillée des concentrations et des flux de substances polluantes dans les retombées atmosphériques et les eaux de ruissellement de toitures et de chaussées a été effectuée pour estimer l'apport de ces différents compartiments à la pollution transportée par les eaux pluviales s'écoulant aux exutoires des réseaux séparatifs. À partir de ce suivi, cette étude établit et dans certains cas confirme l'origine et les vecteurs principaux de transfert de polluants aux eaux pluviales générées en zones périurbaines peu denses et avec une densité de trafic faible à modérée. Les retombées atmosphériques s'avèrent une source de chrome et cadmium, les toitures et leurs accessoires sont source de zinc et de plomb, les chaussées apportent cuivre, nickel et zinc. En termes de pollution organique, le trafic automobile semble être la principale source de HAP, tandis que les pratiques de désherbage de la municipalité et des particuliers continuent à être la cause principale de présence de pesticides dans les eaux pluviales.

La qualité microbiologique des eaux de baignade diminue progressivement d’années en années, et peut être un problème majeur de santé publique. Ainsi, des surveillances sanitaires de la qualité microbiologique des eaux de baignade sont effectuées conformément à la directive européenne (2006/7/EC) pour assurer la sécurité sanitaire des baigneurs et préserver l’image de ces écosystèmes. Depuis de nombreuses années, la baie d’Aytré (Charente Maritime, France), a été classée en « qualité insuffisante » et cette plage est interdite à la baignade depuis 2018. Les enjeux sanitaires et le rôle prépondérant de cette plage sur le développement touristique et l’économie locale ont conduit à rechercher l’origine et le déterminisme spatiotemporel de cette contamination fécale. Cette thèse présente une approche intégrée de l’analyse de la contamination fécale de la baie d’Aytré par une étude pluridisciplinaire de différentes hypothèses analysées depuis le début des années 2000 par les collectivités locales. Le niveau de contamination fécale des eaux de baignade durant une année était relativement faible avec une variation saisonnière notable de l’abondance des indicateurs de contamination fécale Escherichia coli et entérocoques. Les dépassements des seuils réglementaires sur 24% et 32% des échantillons d’eau du Platin Nord et du Platin Sud, les deux sites de baignade de la baie d’Aytré étaient principalement dus aux entérocoques. La qualité microbiologique du sédiment au cours du temps a montré que le sédiment n’était pas une source diffuse de contamination dans l’eau. L’analyse combinée des marqueurs protéiques, génétiques et chimiques a révélé la présence d’une part d’espèces d’entérocoques d’origine environnementale et d’autre part une contamination d’origine animale principalement et une faible contribution de l’origine humaine. La stratégie d’analyse élaborée et les outils développés au cours de cette étude permettront d’améliorer les méthodes de surveillance sanitaire des eaux de baignade
The microbiological quality of bathing water is progressively decreasing from year to year, and can constitute a major public health problem. Thus, sanitary monitoring of the microbiological quality of bathing waters is carried out in accordance with the European directive (2006/7/EC) to ensure the sanitary safety of bathers and preserve the image of these recreational ecosystems. For many years, the bay of Aytré (Charente Maritime, France), has been classified as "poor quality" and this beach is prohibited for bathing since 2018. The health issues and the preponderant role of this beach on the tourism development and the local economy led to investigate the origin and the spatiotemporal determinism of this fecal contamination. This thesis presents an integrated approach to the analysis of the fecal contamination of Aytré Bay through a multidisciplinary study of different hypotheses analysed since the beginning of the 2000s by the local authorities. The level of fecal contamination of the bathing water during a year was relatively low with a notable seasonal variation in the abundance of the fecal contamination indicators Escherichia coli and enterococci. Exceedances of the regulatory thresholds on 24% and 32% of the water samples from Platin Nord and Platin Sud, the two bathing sites in Aytré Bay, were mainly due to enterococci. The microbiological quality of the sediment over time showed that the sediment was not a diffuse source of contamination in the water. The combined analysis of protein, genetic and chemical markers revealed the presence of enterococci species of environmental origin on the one hand, and on the other hand, a contamination of mainly animal origin and a small contribution from human origin. The analytical strategy and tools developed during this study will help to improve the sanitary surveillance methods of bathing waters

Human activities such as mining and smelting of lead (Pb) ores and combustion of alkyllead additives in gasoline have resulted in extensive global Pb pollution. Since the late 1960's studies of polar ice and snow have been undertaken to evaluate the extent of anthropogenic Pb emissions in recent times as well as to investigate changes in anthropogenic Pb emissions in the more distant past. The polar ice sheets have been used to investigate Pb pollution as they offer a long-term record of human activity located far from pollution sources and sample aerosol emissions on a hemispheric scale. Lead isotopes have been previously used to identify sources of Pb in polar snow and ice, while new evaluations of Pb isotopic compositions in aerosols and Pb ore bodies allow more thorough evaluations of anthropogenic Pb emissions. Lead isotopic compositions and Pb and Barium (Ba) concentrations have been measured in snow and ice core samples from Law Dome, East Antarctica, to produce a detailed pollution history between 1530 AD and 1989 AD. Such a record has been produced to evaluate changes in anthropogenic Pb emission levels and sources over the past 500 years, to determine when industrial (anthropogenic) activities first began to influence Antarctica and also to investigate natural Pb fluxes to Antarctica. Additional samples were also collected from Law Dome snow and ice cores to respectively investigate seasonal variations in Pb and Ba deposition, and the influence of the 1815 AD volcanic eruption of Tambora, Indonesia. All samples were measured by thermal ionisation mass spectrometry, for which techniques were developed to reliably analyse Pb isotopic compositions in Antarctic samples containing sub-picogram per gram concentrations of Pb.Particular attention was given to the quantity of Pb added to the samples during the decontamination and sample storage stages of the sample preparation process. These stages, including the use of a stainless steel chisel for the decontamination, contributed ~5.2 pg to the total sample analysed, amounting to a concentration increase of ~13 fg g-1. In comparison, the mass spectrometer ion source contributed typically 89 +/- 19 fg to the blank, however its influence depended upon the amount of Pb available for analysis and so had the greatest impact when small volumes of samples with a very low concentration were analysed. As a consequence of these careful investigations of the Pb blank contributions to the samples, the corrections made to the Pb isotopic ratios and concentrations measured are smaller than previously reported evaluations of Pb in Antarctica by thermal ionisation mass spectrometry. The data indicate that East Antarctica was relatively pristine until -1884 AD, after which the first influence of anthropogenic Pb in Law Dome is observed. "Natural", pre-industrial, background concentrations of Pb and Ba were - 0.4 pg/g and - 1.3 pg/g, respectively, with Pb isotopic compositions within the range 206Pb/207Pb = 1.20 - 1.25 and 208Pb/207Pb = 2.46 - 2.50 and an average rock and soil dust Pb contribution of 8-12%. A major pollution event was observed at Law Dome between 1884 and 1908 AD, elevating the Pb concentration fourfold and changing 206Pb/207Pb ratios in the ice to ~1.12. Based on Pb isotopic systematics and Pb emissions statistics, this was attributed to Pb mined at Broken Hill and smelted at Broken Hill and Port Pirie, Australia.Anthropogenic Pb inputs to Law Dome were most significant from ~1900 to 1910 and from ~1960 to 1980. During the 20th century, Ba concentrations were consistently higher than "natural" levels. This was attributed to increased dust production, suggesting the influence of climate change and/or changes in land coverage with vegetation. Law Dome ice dated from 1814 AD to 1819 AD was analysed for Pb isotopes and Pb, Ba and Bismuth (Bi) concentrations to investigate the influence of the 1815 AD volcanic eruption of Tambora, Indonesia. The presence of volcanic debris in the core samples was observed from late-1816 AD to 1818 AD as an increase in sulphate concentrations and electrical conductivity of the ice. Barium concentrations were approximately three times higher than background levels from mid-1816 to mid1818, consistent with increased atmospheric loading of rock and soil dust, while enhanced Pb/Ba and Bi/Ba ratios, associated with deposition of volcanic debris, were observed at mid-1814 and from early-1817 to mid-1818. From the results, it appeared likely that Pb emitted from Tambora was removed from the atmosphere within the 1.6 year period required to transport aerosols to Antarctica. Increased Pb and Bi concentrations observed in Law Dome ice ~1818 AD were attributed to either increased heavy metal emissions from Mount Erebus, or increased fluxes of heavy metals to the Antarctic ice sheet resulting from climate and meteorological modifications following the Tambora eruption.A non-continuous series of Law Dome snow core samples dating from 1980 to 9185 AD were analysed to investigate seasonal variations in the deposition of Pb and Ba. It was found that Pb and Ba at Law Dome do exhibit seasonal variations in deposition, with higher concentrations of Pb and Ba usually observed during Summer and lower concentrations of Pb and Ba usually observed during the Autumn and Spring seasons. At Law Dome, broad patterns of seasonal Pb and Ba deposition are evident however these appear to be punctuated by short-term deposition events or may even be composed of a continuum of short-term deposition events. This variability suggests that complex meteorological systems are responsible for the transport of Pb and Ba to Law Dome, and probably Antarctica in general.

Etude de l'origine du comportement de la matiere organique dans l'estuaire du huang he et en mer de bohai. Trois environnements sont envisages: le fleuve, la zone de turbidite maximum, la zone marine. Des analyses d'hydrocarbures non aromatiques, d'acides gras, de lactones et d'organochlores sont menees sur les fractions dissoutes et particulaires et le sediment. Les empreintes terrigenes, anthropiques et biologiques sont discutees. L'utilisation de methodes statistiques appliquees aux acides gras permet de comprendre et confirmer l'origine de ces composes. Une evolution de la qualite de l'environnement a ete effectuee. On presente un etat de reference de quelques contaminants organiques dans l'estuaire du huang he

Human activities such as mining and smelting of lead (Pb) ores and combustion of alkyllead additives in gasoline have resulted in extensive global Pb pollution. Since the late 1960's studies of polar ice and snow have been undertaken to evaluate the extent of anthropogenic Pb emissions in recent times as well as to investigate changes in anthropogenic Pb emissions in the more distant past. The polar ice sheets have been used to investigate Pb pollution as they offer a long-term record of human activity located far from pollution sources and sample aerosol emissions on a hemispheric scale. Lead isotopes have been previously used to identify sources of Pb in polar snow and ice, while new evaluations of Pb isotopic compositions in aerosols and Pb ore bodies allow more thorough evaluations of anthropogenic Pb emissions. Lead isotopic compositions and Pb and Barium (Ba) concentrations have been measured in snow and ice core samples from Law Dome, East Antarctica, to produce a detailed pollution history between 1530 AD and 1989 AD. Such a record has been produced to evaluate changes in anthropogenic Pb emission levels and sources over the past 500 years, to determine when industrial (anthropogenic) activities first began to influence Antarctica and also to investigate natural Pb fluxes to Antarctica. Additional samples were also collected from Law Dome snow and ice cores to respectively investigate seasonal variations in Pb and Ba deposition, and the influence of the 1815 AD volcanic eruption of Tambora, Indonesia. All samples were measured by thermal ionisation mass spectrometry, for which techniques were developed to reliably analyse Pb isotopic compositions in Antarctic samples containing sub-picogram per gram concentrations of Pb.
Particular attention was given to the quantity of Pb added to the samples during the decontamination and sample storage stages of the sample preparation process. These stages, including the use of a stainless steel chisel for the decontamination, contributed ~5.2 pg to the total sample analysed, amounting to a concentration increase of ~13 fg g-1. In comparison, the mass spectrometer ion source contributed typically 89 +/- 19 fg to the blank, however its influence depended upon the amount of Pb available for analysis and so had the greatest impact when small volumes of samples with a very low concentration were analysed. As a consequence of these careful investigations of the Pb blank contributions to the samples, the corrections made to the Pb isotopic ratios and concentrations measured are smaller than previously reported evaluations of Pb in Antarctica by thermal ionisation mass spectrometry. The data indicate that East Antarctica was relatively pristine until -1884 AD, after which the first influence of anthropogenic Pb in Law Dome is observed. "Natural", pre-industrial, background concentrations of Pb and Ba were - 0.4 pg/g and - 1.3 pg/g, respectively, with Pb isotopic compositions within the range 206Pb/207Pb = 1.20 - 1.25 and 208Pb/207Pb = 2.46 - 2.50 and an average rock and soil dust Pb contribution of 8-12%. A major pollution event was observed at Law Dome between 1884 and 1908 AD, elevating the Pb concentration fourfold and changing 206Pb/207Pb ratios in the ice to ~1.12. Based on Pb isotopic systematics and Pb emissions statistics, this was attributed to Pb mined at Broken Hill and smelted at Broken Hill and Port Pirie, Australia.
Anthropogenic Pb inputs to Law Dome were most significant from ~1900 to 1910 and from ~1960 to 1980. During the 20th century, Ba concentrations were consistently higher than "natural" levels. This was attributed to increased dust production, suggesting the influence of climate change and/or changes in land coverage with vegetation. Law Dome ice dated from 1814 AD to 1819 AD was analysed for Pb isotopes and Pb, Ba and Bismuth (Bi) concentrations to investigate the influence of the 1815 AD volcanic eruption of Tambora, Indonesia. The presence of volcanic debris in the core samples was observed from late-1816 AD to 1818 AD as an increase in sulphate concentrations and electrical conductivity of the ice. Barium concentrations were approximately three times higher than background levels from mid-1816 to mid1818, consistent with increased atmospheric loading of rock and soil dust, while enhanced Pb/Ba and Bi/Ba ratios, associated with deposition of volcanic debris, were observed at mid-1814 and from early-1817 to mid-1818. From the results, it appeared likely that Pb emitted from Tambora was removed from the atmosphere within the 1.6 year period required to transport aerosols to Antarctica. Increased Pb and Bi concentrations observed in Law Dome ice ~1818 AD were attributed to either increased heavy metal emissions from Mount Erebus, or increased fluxes of heavy metals to the Antarctic ice sheet resulting from climate and meteorological modifications following the Tambora eruption.
A non-continuous series of Law Dome snow core samples dating from 1980 to 9185 AD were analysed to investigate seasonal variations in the deposition of Pb and Ba. It was found that Pb and Ba at Law Dome do exhibit seasonal variations in deposition, with higher concentrations of Pb and Ba usually observed during Summer and lower concentrations of Pb and Ba usually observed during the Autumn and Spring seasons. At Law Dome, broad patterns of seasonal Pb and Ba deposition are evident however these appear to be punctuated by short-term deposition events or may even be composed of a continuum of short-term deposition events. This variability suggests that complex meteorological systems are responsible for the transport of Pb and Ba to Law Dome, and probably Antarctica in general.

碩士
國立臺灣大學
環境工程學研究所
97
In these years, the pollution of ozone becomes worse in Yunlin-Chiayi-Tainan (Y-C-T) area in Taiwan. This study used multivariate statistical analysis and trajectory photochemical air quality model to analyze the database of air quality monitoring station. The goal of this study was to understand the pollution magnitude produced by sources of pollution, and provided the basis for control of ozone. This study investigated that the change on spatial and temporal variations of (Y-C-T) area. The results indicated that the percentage of over-standard of ozone was 57% in 2003 to 2005, and the ozone pollution was worse in Tainan in fall due to the direction of the wind. The study used top 5% of component scores to choose the representative ozone episodes. Compare with non-ozone episodes, the results indicated that the highest concentration of ozone was produced by sources of pollution when the climate was not conductive to diffuse. For decrease the magnitude of ozone, ozone precursors should be controlled. This study used cluster analysis to classify (Y-C-T) area to be four regions, and used analysis of backward trajectory to understand the main reason of ozone pollution in each cluster. The result indicated that the pollution of ozone was fine with less NOx in first region. And the serious ozone population was occurred in the second region due to accumulation of VOC and NOx. In the third region, there was low percentage of the trajectory lines across the region of industry, and some of ozone came from north of the cluster. There were widespread sources of ozone pollution in the fourth region, and the occurred time of high concentration of ozone is later than the other regions. Overall, the percentage of the trajectory lines across the regions of industry was 48%, so the VOC was the main reason to produce high concentration of ozone in (Y-C-T) area. When the climate was not conductive to diffuse, the air mass sucked in more VOC and caused high concentration of ozone. Therefore, the emission of VOC should be controlled in order to prevent the occurrence of high concentration of ozone.

No
This study aims to determine the concentration of 16 Polycyclic Aromatic Hydrocarbons (PAHs) in urban soils from Leeds in order to determine what the factors are controlling their distribution and abundances. Soil samples were collected across an area from Leeds. Gas chromatography with mass spectrometry (GC-MS) using selected ion monitoring (SIM) was used to identify and quantify PAHs in the soil samples with the aid of PAH external standards. The results showed the highest concentrations of total PAHs in sample L8 (1344 ng/g) taken from an area located near a parking site and road in Leeds and the lowest total concentration of the 16 PAHs in sample L16 (87 ng/g) taken from a private garden. The ratio of anthracene to anthracene plus phenanthrene AN/(AN + PH), fluoranthene to fluoranthene plus pyrene FLU/(PY+FLU) and benzo[a]anthracene to 228 (BaA/228) implied that the PAHs pollution originated from pyrogenic, biomass and petroleum combustion in the samples which were collected from Leeds city.