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Mercury poses significant challenges to human health and fisheries management. Historical industrial practices in Waynesboro, Virginia left portions of the Shenandoah River basin contaminated with mercury and stringent health advisories for fish consumption. I investigated processes affecting the bioaccumulation of mercury in Catostomus commersoni, Ictalurus punctatus, Lepomis auritus, and Micropterus dolomieu by studying food habits, total mercury and methylmercury in common prey items, and bioaccumulation dynamics of methylmercury in the mercury contaminated South River and South Fork of the Shenandoah River and uncontaminated North River. Additionally, I evaluated sexual and seasonal variations of total mercury in M. dolomieu in the South Fork of the Shenandoah River. Algae, aquatic insects, crayfish, detritus, and fish accounted for 75-97% of the diet. Total mercury in aquatic invertebrates and forage fish in contaminated rivers ranged from 66.7-398.3 and 198.0-594.9 ng/g wet weight, while total mercury in aquatic invertebrates and forage fish in the reference river were 4.4 and 29.3 ng/g. Model simulations indicated that dietary pathways accounted for 87% of methylmercury uptake by fish in contaminated rivers, but only 57% in the reference river. Total mercury in M. dolomieu was 19-20% higher in females than males and 14-21% higher during spring than summer and fall. Results of this study indicate that bioenergetics-based bioaccumulation models are valuable tools for evaluating field data, identifying processes critical to contaminant accumulation, and comparing outcomes of alternative management options associated with pollution control, ecosystem management, and/or restoration activities for management guidance prior to costly expenditures. / Master of Science

Methylmercury (MeHg) is a hazardous neurotoxin that bioaccumulates throughout the food web, which is converted from inorganic mercury (Hg) by microorganisms in oxygen-deprived (hypoxic, or anoxic) conditions. Climate change challenges the ability to limit Hg methylation in the environment since increasing temperatures are predicted to increase the prevalence of hypoxic and anoxic conditions in water columns. My Master thesis project aimed to investigate the diversity, abundance, composition, and structure of Hg-methylating communities to tie together the influence of environmental conditions. To do so, I used bioinformatic tools to analyze a dataset containing freshwater environmental DNA sequences from a broad diversity of metagenomes. The dataset was collected in tandem with environmental metadata (e.g., oxygen) which was used to compare the abundance of one of the two Hg-methylating genes; hgcA. I found that the majority of hgcA genes came from metagenomes collected in hypoxic and anoxic water layers. Interestingly, certain metagenomes in hypoxic and anoxic water layers did not contain any hgcA genes and thus potentially no Hg methylators. Some hgcA genes were found in metagenomes from oxic water layers, which could be explained by settling particles originating from the sediment-water interface acting as oxygen deprived niches. These findings are crucial as they imply that the anticipated changes in freshwater oxygenation, resulting from climate change, will lead to increased niches for Hg-methylating microorganisms. Particularly, increasing algal blooms and persistent lake stratification leads to more deoxygenated water columns, which explains why MeHg can become an increasing hazard to animal and human well-being.

Indiana University-Purdue University Indianapolis (IUPUI) / Methylmercury (MeHg) exposure from occupational, environmental and food sources is a significant threat to public health. MeHg poisonings in adults may result in severe psychological and neurological deficits, and in utero exposures can confer significant damage to the developing brain and impair neurobehavioral and intellectual development. Recent epidemiological and vertebrate studies suggest that MeHg exposure may contribute to dopamine (DA) neuron vulnerability and the propensity to develop Parkinson’s disease (PD). I have developed a novel Caenorhabditis elegans (C. elegans) model of MeHg toxicity and have shown that low, chronic exposure confers embryonic defects, developmental delays, reduction in brood size, decreased animal viability and DA neuron degeneration. Toxicant exposure results in an increase in reactive oxygen species (ROS) and the robust induction of several glutathione-S-transferases (GSTs) that are largely dependent on the PD-associated phase II antioxidant transcription factor SKN-1/Nrf2. I have also shown that SKN-1 is expressed in the DA neurons, and a reduction in SKN-1 gene expression increases MeHg-induced animal vulnerability and DA neuron degeneration. Furthermore, I incorporated a novel genome wide reverse genetic screen that identified 92 genes involved in inhibiting MeHg-induced animal death. The putative multidrug resistance protein MRP-7 was identified in the screen. I have shown that this transporter is likely expressed in DA neurons, and reduced gene expression increases cellular Hg accumulation and MeHg-associated DA neurodegeneration. My studies indicate that C. elegans is a useful genetic model to explore the molecular basis of MeHg-associated DA neurodegeneration, and may identify novel therapeutic targets to address this highly relevant health issue.

Methylmercury (MeHg) is a neurotoxic compound that threatens the well-being of humans and wildlife. It is formed through the methylation of inorganic mercury (HgII) under suboxic/anoxic conditions in soils, sediment and waters. The chemical speciation of HgII, including specific HgII species in aqueous and solid/adsorbed phases, plays a key role in MeHg formation. Chemical forms of HgII which have been reported to be available for uptake in methylating bacteria include neutral HgII–sulfide complexes, HgII complexes with specific low molecular mass (LMM) thiols, and nanoparticulate HgS(s). Accurate determination of the chemical speciation of HgII is thus crucial when elucidating the mechanism of MeHg formation. The concentration of HgII–LMM thiols complexes is predicted to be extremely low (sub fM range). Current analytical methods do not allow direct quantification of HgII complexes due to the very low concentration of these complexes, and therefore determination rely on thermodynamic modeling. Accurate stability constants for HgII–LMM thiols complexes and quantification of LMM thiol ligands in environments are thus required to precisely determine the concentration of such complexes. In this thesis, a novel analytical method was developed based on online pre-concentration coupled with liquid chromatography tandem mass spectrometry to determine the concentration of 16 LMM thiols (Paper I). This method was successful in detecting 8 LMM thiols in boreal wetland porewaters, with mercaptoacetic acid and cysteine being the most abundant. The total concentration of individual detected LMM thiols ranged from sub nM (LOD=0.1 nM) to 77 nM. Moreover, the stability constant (β2) for HgII complexes with 15 LMM thiols were directly determined for the first time by competing ligand exchange experiments combined with liquid chromatography ICPMS analysis (Paper II). Values of log β2 for the reaction Hg2+ + 2LMM-RS- = Hg(LMM-RS)2 ranged from 34.6 for. Based on the determined constants of Hg(LMM-RS)2 complexes and state-of-the-art constants from literature for other HgII complexes, we established comprehensive thermodynamic speciation models for MeHg and HgII in boreal wetlands (Paper III). The speciation of HgII was coupled with the HgII methylation rate constant (km) determined with different enriched Hg isotope tracers (Paper IV). There was a good correlation (R2=0.88) between the km determined by a HgII(aq) tracer added as Hg(NO3)2 with high bioavailability and a tracer where HgII was bond to thiol groups in natural organic matter (HgII-NOM(ads)) and has a lower bioavailability. The HgII(aq) tracer was consistently methylated at 5 times higher rate than the HgII-NOM(ads) tracer. A good correlation was observed between the concentration of biologically produced LMM thiols and km in the boreal wetlands. In a mesocosm study of estuarine sediment-brackish water systems, increased concentration of phytoplankton chlorophyll α due to macro nutrient additions led to an increase in HgII methylation rate of the HgII(aq) but not of the HgII-NOM(ads) tracer or ambient HgII species (Paper V). Furthermore, simulated newly deposited HgII species from atmospheric and terrestrial sources were exhibited significantly higher HgII methylation rates when compared with simulated aged sediment HgII pools. Through the development and adoption of novel analytical methods, this thesis reveals the significance of LMM thiols in Hg biogeochemistry by precise determination of HgII–LMM thiol complexes in natural environmental systems.

Le mercure est un contaminant présent dans l'ensemble des compartiments de l'environnement et l'homme y est directement exposé via l'alimentation. Actuellement, les organismes gouvernementaux évaluent la sécurité des produits alimentaires en se basant essentiellement sur la concentration totale de cet élément. Cependant, la toxicité du mercure dépend, entre autre, de l'espèce absorbée (dont le méthylmercure, sa forme la plus toxique). Par conséquent, l'analyse de spéciation, c'est à dire la détection et quantification des différentes formes chimiques de cet élément, présente un intérêt croissant. Le principal objectif de ce projet a donc été de développer et de valider, sous assurance qualité, une méthode sensible et d'une grande exactitude, basée sur l'utilisation de la dilution isotopique. Elle sera par la suite appliquée comme méthode de référence par l'agence pour l'analyse en spéciation du mercure dans les produits de la pêche afin de permettre une meilleure évaluation des risques encourus par le consommateur. La première partie de ce travail a porté sur l'étude du cycle biogéochimique du mercure et de l'état de l'art des diverses méthodes de préparation de l'échantillon, de séparation et de quantification du Hg dans les matrices biologiques, afin d'émettre des choix analytiques. Ainsi, les principaux composés mercuriels susceptibles d'être retrouvés dans les produits de la pêche (le méthylmercure et le mercure inorganique) ont été déterminés par couplage GC-ICP-MS et une quantification par dilution isotopique. La seconde partie des travaux a été consacrée à l'optimisation de la méthode de préparation des échantillons et de la technique de quantification. Ces travaux sur différents matériaux de référence certifiés ont montré que des modifications de la distribution naturelle de l'échantillon pouvaient survenir dès l'étape d'extraction, préconisant un marquage isotopique avant extraction solide-liquide par digiPREP des espèces mercurielles et dérivation par propylation par le tétrapropylborate de sodium et agitation rotative. Les résultats expérimentaux ont été traités par dilution isotopique simple et multiple. Les teneurs obtenues ont été similaires, pour l'ensemble des matrices analysées, montrant que peu ou pas de transformation inter-espèces surviennent au cours de la procédure analytique. Une quantification par double marquage isotopique et dilution isotopique simple a donc été conservée. L'évaluation des critères analytique a démontré que la méthode est validée pour la spéciation du mercure dans les produits de la pêche, selon les normes françaises AFNOR NF V03-110 de 1998 et de 2010. La dernière partie des travaux a porté sur l'application de la méthode validée à la spéciation du mercure dans des échantillons biologiques réels, ainsi qu'à la participation à plusieurs essais interlaboratoires d'aptitudes organisés par le CSL-FAPAS sur un échantillon de thon en conserve et par l'IRMM sur le matériau IMEP-109 de homard. / Mercury is a contaminant which is found in all compartments of the environment and to which human beings are directly exposed when eating food. Government agencies assess the safety of food products by using total mercury concentrations. However, its toxicity depends on the species absorbed (among which methylmercury is its most toxic form). Therefore, the analysis of speciation, i.e. detection and quantification of different chemical forms of this element, is of high interest. The main objective of this project was to develop and validate, under quality assurance, a sensitive and highly accurate method, based on the use of isotope dilution. This method will then be applied as a reference method by the agency for speciation analysis of mercury in seafood, in order to better assess risks to the consumer. The first part of this work focused on the biogeochemical cycle of mercury and the state of art of the various methods of sample preparation, separation and quantification of Hg in biological matrices in order to make analytical choices. Thus, mercury compounds (methyl mercury and inorganic mercury) were determined by gas chromatography (GC) coupled with an inductively coupled plasma mass spectrometer (ICP-MS) and quantified by isotope dilution. The second part of the work was dedicated to the optimization of the method of sample preparation and the quantification technique. The work was made on different certified reference materials and showed that changes of the natural distribution of the sample could occur during the extraction step. Therefore, isotopic tracers had been added to the sample before this step. Mercury species were extracted by a solid-liquid extraction by using a digiPREP and derivated by propylation using tétrapropylborate the sodium and a rotary agitation. Data were treated by simple and multiple isotope dilution. Achieved concentrations were similar for all analyzed matrices. Results showed that inter-species transformation hardly occurred during the analytical procedure. This was the reason why the use of two isotopic tracers for quantification by simple isotope dilution was kept. To end, the method was validated for the speciation of mercury in seafood, in respect with the French norms AFNOR NF V03-110 of 1998 and 2010. Finally, the work ended with the applicability of the validated method for mercury speciation analysis in real biological samples and our participation in several inter-laboratory proficiency tests organized by the CSL-FAPAS on a sample of tuna and by the IRMM on the material IMEP-109 (lobster).

L'environnement s'est considérablement transformé au cours des dernières décennies sous l'effet du développement économique. Ces transformations se sont accompagnées d'effets positifs, mais aussi négatifs car l'homme se trouve exposé à un grand nombre de substances chimiques dont certaines présentent des risques pour sa santé. La dégradation de l'environnement et ses conséquences néfastes sur la santé ont fait prendre conscience progressivement aux décideurs publics de la nécessité de s'engager dans un développement durable reposant sur un modèle de croissance économiquement soutenable. Dans ce contexte, l'élaboration de politiques de prévention en santé environnementale repose sur une approche globale mobilisant différentes disciplines scientifiques allant de la toxicologie aux sciences sociales en passant par les sciences de l?ingénieur et l'écologie environnementale. En France, les politiques publiques de prévention mobilisent encore peu l'approche économique comme outil d'aide à la décision. Or la contribution de cette approche est indéniable : elle peut, notamment, mesurer la réduction du bien-être social liée aux effets des expositions sur la santé. L'évaluation économique peut permettre, entre autres, de faire révéler aux agents leur consentement à payer pour éviter une réduction de leur état de santé ou de leur bien-être, en donnant une valeur monétaire à ces externalités. Outre le fait d'aider à la décision, elle apporte aussi des éléments utiles et nécessaires au débat public. Dans cette thèse, nous avons retenu l'Impact Pathway Analysis (IPA) comme méthode d?évaluation parce qu'elle analyse un risque environnemental donné en définissant précisément sa nature, son ampleur et les probabilités qui le caractérisent et elle intègre ensuite l'évaluation économique afin de mesurer l'impact monétaire de la réduction du risque sur la santé. Cette thèse s'appuie sur deux exemples des conséquences de la pollution environnementale sur la santé des enfants, les cas du plomb et du mercure, et cherche à mettre en évidence le bien-fondé de l'intégration de l'évaluation économique dans les processus de décision publique. L'exposition au plomb et l'exposition au mercure altèrent la santé des enfants et provoquent des effets indésirables graves, tels que des troubles cognitifs et comportementaux. L'impact économique de l'exposition de la population infantile française à ces deux polluants et de sa réduction a été évalué par l'Analyse Coût Bénéfice (ACB) qui permet de rapprocher l'objectif à atteindre de l'optimisation des coûts. Les premiers résultats de l'évaluation montrent que des politiques publiques axées sur la réduction de l'exposition à ces polluants permettraient de réaliser des bénéfices monétaires de plusieurs milliards d'Euros par année comme le montrent les deux articles présentés 1,2. Ces bénéfices incluent une réduction des dépenses médicales futures et de la charge d'une éducation spécialisée des enfants en bas âge, et surtout l'augmentation de la productivité de ces derniers au cours de leur vie d'adulte. L'évaluation des coûts d'investissements dans des programmes de réduction des émissions des polluants est utile au décideur public afin qu'il puisse mettre en balance les coûts des interventions et le bénéfice de cette réduction. Différentes interventions pour réduire les émissions et/ou les expositions sont possibles : "réglementation - permis d'émission - information" et ont des coûts et des efficacités différents. Un troisième papier fait apparaître des bénéfices nets négatifs dans le cas des changements des canalisations d'eau contenant du plomb. Dans un contexte d'allocation de ressources rares, la recherche de l'efficience d'une politique publique nécessite de s'interroger sur le retour sur investissements, ce que permet l'évaluation économique / The environment has changed considerably in recent decades due to economic development. These changes have been accompanied by positive effects but also negative because people are exposed to many chemicals, some of which pose health risks. The environmental degradation and its adverse health effects have gradually led policy makers to become aware of the need to engage in development based on an economically sustainable growth model. In this context, prevention policies in environmental health I should be based on a comprehensive approach mobilizing various scientific fields, from toxicology to social sciences through engineering and environmental ecology. In France, public policies hardly use the economic approach as a tool for decision support. Now, the contribution of this approach is undeniable: it may, in particular, measure the reduction of social welfare associated with the health effects of exposure. Economic evaluation can help economic agents disclose their willingness to pay in order to avoid a degradation of their health or welfare, by giving a monetary value on these externalities. In addition to helping decision, it also provides useful and necessary items for public discussion. In this thesis, we selected the Impact Pathway Analysis (IPA) as an assessment method because it precisely defines the nature, magnitude and probability of a given environmental hazard and integrates the economic assessment to measure the monetary impact of reducing risk. This thesis is based on two examples of the effects of environmental pollution on children's health, the cases of lead and mercury, and seeks to highlight the validity of integrating economic evaluation in the process of public decision. Exposure to lead and mercury affects the health of children and may cause serious side effects, such as cognitive and behavioral disorders. The objective of this thesis is to evaluate the economic impact of the exposure of the French child population to these pollutants, and to highlight the costs and benefits of measures that would reduce the risks. To do this, we selected the Cost Benefit Analysis (CBA), which encompasses a cost optimization assessment. The first results of the evaluation show that public policy focused on reducing exposure to these pollutants would achieve monetary benefits of several billion Euros per year as shown by the two first papers presented in the thesis1.2. These benefits include a reduction in future medical expenses and of the burden of special education of young children, and mainly increased productivity of the latter during their adult life. Assessing the costs of investments in programs to reduce emissions of pollutants is useful for public decision so that costs of intervention and the benefit of this reduction can be weighed. Different interventions are possible to reduce emissions and / or exposures: "regulation - emission permits - information" and have different costs and efficiencies. A third paper shows net negative benefits in the case of removal of water pipes containing lead. In a context of allocating scarce resources, the pursuit of efficiency in public policy requires to consider the return on investment, which is allowed by economic evaluation. Following the empirical work in the three articles, the general discussion comes back on contributions, limits and prospects of integration in the economic evaluation of prevention policies and environmental risks of their neurotoxic effects on the health of children

[pt] O objetivo, deste trabalho, foi avaliar as concentrações de mercúrio total (HgT) e metilmercúrio (MeHg) bem como a % MeHg no tecido muscular, no fígado e na gônada da corvina (Micropogonias furnieri; carnívora), do bagre (Bagre spp.; onívoro) e da tainha (Mugil liza; planctívora). Além de alguns parâmetros bióticos tais como: comprimento, peso, idade, maturidade sexual e o sexo. Foi possível estabelecer uma comparação entre as concentrações de HgT no tecido muscular da corvina e da tainha ao longo dos últimos treze anos. A concentração de HgT foi determinado através de EAA - vapor frio utilizando borohidreto de sódio como agente redutor. E a concentração MeHg foi determinada através de GC-DCE. Para o controle de qualidade analítica utilizaram-se amostras de padrões certificados IAEA MA-1 e Dolt-2. As concentrações de HgT e MeHg no tecido muscular dos carnívoros foram maiores que nos onívoros seguidos pelos planctívoros. O fígado de todas as espécies apresentaram as maiores concentrações de HgT. Enquanto, no músculo as maiores concentrações observadas foram de MeHg. A corvina apresentou a maior percentagem de MeHg no fígado comparada ao bagre e a tainha. Nas gônadas a % MeHg correspondeu a 100 %. Foi observada uma correlação significativa e positiva entre a concentração de HgT no tecido muscular do bagre e seu comprimento e peso. Utilizando-se o teste de Mann-Whitney foi observada uma diferença significativa entre as concentrações de HgT e o estágio de vida dos indivíduos, tanto para a corvina como para a tainha. Os resultados apresentaram uma diferença estatisticamente significativa entre as concentrações de HgT no músculo tanto das corvinas quanto das tainhas coletadas nos anos de 1999 e 2003. / [en] This study assesses the concentration of total mercury (THg), methylmercury (MeHg) and the % MeHg in muscle tissue, liver and gonad of three fish species (Micropogonias furnieri - Atlantic croaker; carnivorous fish, Bagre spp. - Catfish; omnivorous fish and Mugil liza - mullet; planktivorous fish). Furthermore, some other biotic parameters with: total length, weight, age, sexual maturity and sex. The mercury concentration along the last thirteen years in Atlantic croaker and mullet muscle tissue was assessed. THg concentrations were determined by cold vapour AAS with sodium borohydride as a reducing agent. The MeHg was made by CG-ECD. Theses analytical methodologies presented high precision and accuracy when tested with certified reference materials from IAEA - MA-1 and DOLT 2. The carnivorous fish showed higher THg and MeHg concentrations in its muscles than omnivorous and planktivorous fish. The liver of all fish species showed higher THg concentrations than the muscle tissues and gonad. Meanwhile, the MeHg concentrations were higher in the muscle. Atlantic croaker presented higher percentage of MeHg in liver than catfish and mullet. The fish species showed similar percentage of MeHg in their gonad. Significant and positive correlations were observed between THg concentration in catfish muscle and their total length and weight. Mann-Whitney test showed that the stage of the life of the individuals was one of the parameters that influenced THg concentration in the muscle for carnivorous fish planktivorous fish. The results presented a statistically significant difference between the THg in the muscle of the organisms of the Atlantic croaker and the mullet collected in the years 1999 and 2003.