Methylmercury (MeHg) is the most toxic form of Hg to wildlife, partly because of its ability to biomagnify through the food chain. Previous studies have shown that river otter (Lutra canadensis) is particularly susceptible to increased exposure and body burdens of MeHg due to the piscivorous nature of its diet. The objectives of this study were to attempt to establish a relationship between MeHg concentrations in otter tissues and DNA fragmentation using single cell electrophoresis (comet assay) as well as evaluate the effectiveness of the comet assay as a tool in genotoxicity assessment in field samples. Results of preliminary experiments indicate that both time and storage temperature markedly influence the rate of spontaneous DNA degradation. Increased numbers of freeze/thaw cycling also appear to have a negative effect on DNA integrity. In addition, a cell culture experiment was set up to measure the effects of differing levels of MeHg on a neuroblastoma cell line.

L'utilisation du biote dans le suivi de la contamination métallique des milieux aquatiques est aujourd'hui une approche pertinente, car elle permet (i) de répondre aux difficultés analytiques liées à la présence des métaux à faible dose dans l'eau, (ii) d'intégrer la contamination dans le temps et (iii) de renseigner sur la biodisponibilité des métaux et leur potentiel toxique. Toutefois, l'interprétation des niveaux de contamination des organismes en termes de contamination biodisponible des milieux est difficile car elle dépend de facteurs confondants (physicochimiques et biologiques). Dans ce contexte, l'objectif de ce travail de thèse est d'étudier la variabilité des capacités de bioaccumulation des métaux par voie dissoute chez le gammare, en s'appuyant sur un modèle cinétique. Des expérimentations en laboratoire ont permis d'étudier l'influence de facteurs physicochimiques (cations majeurs de l'eau) et biologiques (histoire de vie) sur les constantes d'accumulation et d'élimination du modèle pour le Cd, le Cu, le Ni et le Pb. Les résultats de ces travaux ont montré l'importance de prendre en compte l'influence des teneurs calciques du milieu et la pré-exposition des gammares à certains métaux dans l'interprétation de la bioaccumulation. Des suivis de la contamination dans des gammares transplantés in situ à l'échelle de la France ont montré les limites du modèle pour relier la contamination du milieu à celle des organismes. Ainsi, pour une meilleure caractérisation de la contamination biodisponible des milieux, il est nécessaire d'approfondir les connaissances sur l'influence d'autres facteurs physicochimiques et sur l'importance de la voie trophique comme source de contamination biodisponible pour les gammares / The use of biota in order to monitor metallic contamination in freshwaters is a relevant tool to (i) overcome difficulties of measuring low concentrations in water, (ii) integrate metal fluctuations over time and, (iii) quantify the bioavailable fraction of metals, considered as potentially toxic. However, the interpretation of metal contents in aquatic organisms in terms of bioavailable contamination in freshwaters remains complex because it depends on confounding factors (physicochemical and biotic factors). In this context, the aim of this work was to study the variability of waterborne metal bioaccumulation abilities in gammarids, using the kinetic model. In the laboratory, the influence of water chemistry (major ions) and biological factors (local acclimation) on the accumulation and elimination rate constants of the kinetic model was assessed. The results showed that the consideration of calcium concentrations in water and the pre-exposure of gammarids to some metals were crucial for a reliable interpretation of bioaccumulation. Meanwhile, metal contamination was followed in transplanted gammarids at the national-scale (France) and showed the limits of kinetic modelling to link metal contamination in water to bioaccumulation. Therefore, to better characterize the bioavailable contamination in freshwaters, it is necessary to further study the influence of other physicochemical factors, such as temperature, and the importance of food as a source of bioavailable metals for gammarids

La contamination atmosphérique par les métaux/métalloïdes (As, Cd, Cu, Pb, Sb, Zn…) et par les composés azotés impacte durablement les écosystèmes. L’évaluation des dépôts atmosphériques responsables de ces effets néfastes reste éparse car complexe, en particulier dans les environnements éloignés des sources de contamination comme les massifs forestiers. La prospection et l’estimation des éléments traces et de l’azote apportés dans ces dépôts ont été réalisées à l’échelle nationale à travers deux approches de biosurveillance par les lichens et les mousses : la bioaccumulation et la bioindication. L’enregistrement des éléments traces par les organismes indique une forte pression lithogénique dans ces milieux éloignés des sources directes, qui s’inclut dans le bruit de fond géochimique (e. g. Al, As, Co, Cr, Fe, Ni et Ti). Des sources additionnelles issues des activités anthropiques plus locales complètent régionalement les cortèges des éléments chimiques enregistrés (Cd, Cu, Sb ou Zn). La comparaison des échantillons de lichens et de mousses avec des spécimens historiques d’herbiers nous permet de retrouver ce contexte régional durant les siècles passés, et notamment de conforter les signatures lithologiques à travers le temps grâce aux terres rares. Ainsi, l’utilisation du charbon fossile apparaît être la source de contamination métallique dominante durant la fin du XIX e siècle et le début du XX e siècle, et plus récemment, une source additionnelle comme le transport routier (cas de Pb) a pu être notée. En parallèle, des facteurs influençant la bioaccumulation des métaux ont été testés : l’espèce considérée joue sur la capture des particules atmosphériques à travers la morphologie du thalle, et l’écorce support ne présente que peu d’influence. En considérant les signatures des dépôts atmosphériques, la végétation au travers des pluviolessivats apparaît influencer davantage les mousses terricoles que les lichens corticoles, ces derniers étant plus représentatifs des dépôts totaux. Des expérimentations de sorption/désorption montrent un processus rapide d’accumulation (une semaine) pour Pb et Cd, mais ne montrent ni compétition entre les métaux bioaccumulés, ni influence du lessivage sur la bioaccumulation. De nouvelles données concernant la sensibilité des espèces lichéniques face aux polluants métalliques ont pu être obtenues à partir de relevés de bioindication couplés à des analyses statistiques multivariées. / The atmospheric contamination by metals/metalloids (As, Cd, Cu, Pb, Sb, Zn…) and by nitrogen compounds impact the ecosystems. The atmospheric deposition is responsible of these harmful effects and its evaluation is complex and missing, particularly in remote environments like forest areas. The monitoring of trace element and nitrogen deposition at the national scale is carried out through two different approaches of biomonitoring by lichens and mosses: bioaccumulation and bioindication. The metal bioaccumulation points out a strong lithogenic pressure in these remote areas that is included in the geochemical background (e. g. Al, As, Co, Cr, Fe, Ni and Ti). Additional sources from more local anthropogenic activities are responsible for the regional context by the accumulation of other chemical elements (Cd, Cu, Sb or Zn). The comparison of current samples with herbarium specimens allows us getting back to historical regional influence one and half century ago, including consolidating the lithological influence over the time by rare earth elements. The use of fossil coal appears as a dominant source of metallic contamination in the late 19th century and the beginning 20th century. In parallel, the factors influencing the bioaccumulation of metals were evaluated: the entrapment of atmospheric particles is influenced by the morphology of the thallus but not by the bark. Considering the atmospheric deposition signature, vegetation via throughfall was found to be more influent for terricolous mosses than for corticolous lichens. Additional experiments of sorption/desorption showed a quick accumulation process (one week) for Pb and Cd, but neither metal competition, nor leaching influence on bioaccumulation were highlighted. New data on lichen species sensitivity to metal pollutants have been compiled through multivariate statistical analysis

Les tensioactifs poly- et perfluoroalkylés (PFAS) sont des composés d’origine anthropique produits à partir des années 1950 et qui sont désormais considérés comme des polluants ubiquistes. La première partie de ce travail a consisté à optimiser et valider des procédures pour l’analyse ultra-trace des PFAS. Ces méthodes ont ensuite été utilisées afin d’apporter de nouveaux éléments de réponse sur l’occurrence et la dynamique des PFAS dans les environnements aquatiques. Une attention particulière a été accordée aux valeurs censurées (<LD). Dans les eaux de surface et les sédiments, à l’échelle nationale, le perfluorooctane sulfonate (PFOS) s’est avéré prédominant parmi les acides perfluoroalkylés (PFAA) considérés ; la fraction organique du sédiment est apparue un facteur de contrôle clé des teneurs sédimentaires. L’utilisation des cartes auto-organisatrices de Kohonen a facilité la synthèse des résultats et les comparaisons entre sites. A une échelle plus locale, ces travaux ont permis de cartographier la contamination sédimentaire d’un estuaire macrotidal et d’étudier les facteurs de contrôle de leur distribution. La dynamique spatio-temporelle des PFAS et leur transfert aux premiers maillons trophiques ont été évalués en milieu fluvial urbain (la Seine) et en milieu estuarien (la Gironde). La détermination des facteurs d’amplification trophique en estuaire de Gironde confirme le caractère bioamplifiable du PFOS et de certains PFAA à longue chaîne. Le dernier axe de ces travaux concernait la recherche de PFAS d’intérêt émergent zwittérioniques et cationiques ; des résultats préliminaires semblent dissiper les inquiétudes concernant leur potentiel de bioaccumulation. / Poly- and perfluoroalkyl surfactants (PFAS) are anthropogenic compounds that have been used sincethe 1950s in a variety of applications and that have emerged as ubiquitously distributed contaminants.The first aim of this work was to optimize and validate analytical procedures for the trace-leveldetermination of PFAS. These methods were then applied to various sets of environmental samples,providing new elements to document the occurrence and environmental fate of PFAS in aquaticecosystems. In terms of statistical analyses, a special care has been devoted to incorporate nondetects(data <LOD). In French surface waters and sediments, perfluorooctane sulfonate (PFOS) wasthe prevailing perfluoroalkylated acid (PFAA); sediment organic carbon fraction was a key controllingfactor of PFAS sedimentary levels. Kohonen self-organizing maps were used to highlight similaritiesand differences between sites, providing evidence for distinctive features, sometimes at watershedscale. A mapping of PFAS in sediments was established in a macrotidal estuary, along with theirpartitioning behavior in the water column. The spatio-temporal dynamics of PFAS and transfer to thefirst trophic levels were investigated in an urban freshwater hydrosystem (the Seine River) and in anestuarine environment (Gironde estuary). In the Gironde estuary, trophic magnification factors (TMF)were significantly >1 for PFOS and several long-chain PFAA, providing new evidence for theirbiomagnification. The last theme addressed in this work was the analysis of newly-identified cationicand zwitterionic PFAS ; preliminary evidence seem to dispel concerns about the bioaccumulationpotential of the latter.

No description available.

In recent decades, there has been a rapid expansion in the use of manufactured nanoparticles (MNPs). Experimental evidence and material flow models predict that MNPs enter wastewater treatment plants and partition to sewage sludge and majority of that sludge is land applied as biosolids. During wastewater treatment and after land application, MNPs undergo biogeochemical transformations (aging). The primary transformation process for silver MNPs (Ag-MNPs) is sulfidation, while zinc oxide MNPs (ZnO-MNPs) most likely undergo phosphatation and sulfidation. Our overall goal was to assess bioavailability and toxicogenomic impacts of both pristine, defined as-synthesized, and aged Ag- and ZnO-MNPs, as well as their respective ions, to a model organism, the soil nematode Caenorhabditis elegans. We first investigated the toxicity of pristine Ag-MNPs, sulfidized Ag-MNPs (sAg-MNPs), and AgNO3 to identify the most sensitive ecologically relevant endpoint in C. elegans. We identified reproduction as the most sensitive endpoint for all treatments with sAg-MNPs being about 10-fold less toxic than pristine Ag-MNPs. Using synchrotron x-ray microspectroscopy we demonstrated that AgNO3 and pristine Ag-MNPs had similar bioavailability while aged sAg-MNPs caused toxicity without being taken up by C. elegans. Comparisons of the genomic impacts of both MNPs revealed that Ag-MNPs and sAg-MNPs have transcriptomic profiles distinct from each other and from AgNO3. The toxicity mechanisms of sAg-MNPs are possibly associated with damaging effects to cuticle. We also investigated the effects pristine zinc oxide MNPs (ZnO-MNPs) and aged ZnO-MNPs, including phosphatated (pZnO-MNPs) and sulfidized (sZnO-MNPs), as well as ZnSO4 have on C. elegans using a toxicogenomic approach. Aging of ZnO-MNPs reduced toxicity nearly 10-fold. Toxicity of pristine ZnO-MNPs was similar to the toxicity caused by ZnSO4 but less than 30% of responding genes was shared between these two treatments. This suggests that some of the effects of pristine ZnO-MNPs are also particle-specific. The genomic results showed that based on Gene Ontology and induced biological pathways all MNP treatments shared more similarities than any MNP treatment did with ZnSO4. This dissertation demonstrates that the toxicity of Ag- and ZnO-MNPs to C. elegans is reduced and operates through different mechanisms after transformation during the wastewater treatment process.

Current concerns about inorganic contaminants in food products have raised consumer awareness of anthropogenic sources of heavy metal contamination in ecosystems and their potential threat to human health. Mining and exploration of mineralized zones is a major source of such contamination. Mining throughout the Patagonia Mountains, Arizona, has left a legacy of surface water contamination by acid mine drainage (AMD). This study assessed the impacts of AMD on soils and plants throughout the study area. Concentrations, transport, and loading of heavy metals (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, and Zn) in soils and plants was quantified using total concentrations, suggested toxic levels, and plant and soil pollution indices. Pollution indices were modified to include antimony and molybdenum. Pollution indices greater than 100 were found in areas disturbed by mining, remediation sites and beyond. Cattle grazing on grasses contaminated by metals were documented.

Two studies were designed to investigate the time course development of enlarged plasma volume and cholesterol pool size in copper (Cu)-deficient rats as well as influence of Cu deficiency on the lipid composition of lipoproteins. Rats were randomly assigned to three dietary Cu treatments (deficient, marginal, and adequate) in the Study I and two dietary Cu treatments (deficient and adequate) in Study II. Enlargement of plasma volume and cholesterol pool size were established prior to the increase in plasma cholesterol concentration. Cu concentration was decreased, whereas iron and zinc concentrations were increased in the organs of Cu-deficient and Cu-marginal rats. The plasma pool size of VLDL triglyceride was elevated 6-fold, protein and phospholipid were unaltered, and cholesterol was reduced 36%. The plasma pool size of lipid and protein components of HDL and LDL fractions were markedly elevated in Cu-deficient rats.

L’étude qui suit porte sur l’évaluation du risque écotoxicologique du cérium, l’élément le plus exploité de la famille des lanthanides. La présence grandissante de ce métal dans notre quotidien rend possible son relargage dans l’environnement. Il est donc primordial de comprendre l’impact qu’il aura sur les organismes vivant dans un système aquatique. Une approche centrée sur le modèle du ligand biotique a été utilisée pour évaluer adéquatement l’interaction entre le cérium et un ligand biotique à la surface de l’algue unicellulaire Chlamydomonas reinhardtii. Pour mener une étude sur le risque écotoxicologique d’un élément métallique il faut, avant tout, comprendre la spéciation (répartition sous ses différentes formes chimiques) de l’élément en question. Les premières sections du mémoire vont donc traiter des expériences qui ont été menées pour évaluer la spéciation du cérium dans les conditions expérimentales d’exposition à C. reinhardtii. Il sera question de faire la distinction entre la forme particulaire du métal et sa forme dissoute, de caractériser ces changements par spectroscopie ainsi que d’évaluer le pouvoir complexant de la matière organique naturelle. Les résultats montrent une importante déplétion du métal dissout en solution à pH neutre et basique et une forte interaction avec la matière organique naturelle, peu importe le pH de la solution. Ensuite, les expériences de bioaccumulation seront expliquéesen comparant l’effet du pH, de la présence d’un ion compétiteur et de la présence de matière organique naturelle sur les paramètres d’internalisation du cérium. Les résultats indiquent qu’à pH acide, le comportement du cérium est plus prévisible qu’à pH neutre. Néanmoins, en tenant compte de la complexité des milieux naturels, l’interaction du métal avec les molécules complexantes va diminuer son risque d’interaction avec un organisme vivant. / The following study is on the ecotoxicological risk evaluation of cerium, the most widely exploited element of the lanthanide family. The increasing presence of this element in our everyday lives renders possible its release in the environment. It is therefore of primary importance to understand the impact this metal will have on living organisms in aquatic environments. An approach centered on the biotic ligand model was used here to evaluate the interaction between cerium and a biotic ligand at the surface of the unicellular algae Chlamydomonas reinhardtii. To study the ecotoxicological risk of a metallic element one must understand the speciation (partitioning between its multiple chemical species) of the element in question. The first chapters of this thesis will discuss the experiments performed to evaluate cerium speciation under exposure conditions C. reinhardtii. The issue will be to distinguish between the particulate and dissolved species of the metal, to characterise these changes by spectroscopy, as well as to evaluate the complex formation capacity of the metal with natural organic matter. Results indicate an important depletion of dissolved metal in neutral and alkaline solutions as well as a strong interaction with natural organic matter, regardless of solution pH. Bioaccumulation experiments will then be explained and will compare the effects of pH, the presence of competing ions and the presence of natural organic matter on cerium uptake. Results show that cerium’s behaviour is more predictable under acidic pH conditions. Nonetheless, considering the complexity of the natural environment, the interaction of the metal with natural ligands will most likely reduce the risk of cerium’s interaction with living organisms.

Ett flertal vattendrag i Sverige är idag förorenade (till viss grad), däribland Dalälven. Östersjön är ett utsatt hav vad gäller näringstillförsel, där Dalälven är en bidragande del till detta. I takt med att kunskapsnivån stiger kring hur vattenkvalitén påverkar organismer och människor så kan specifika åtgärder tas fram för enskilda vattendrag, för att förbättra kvalitén. Rapporten handlar om fiskodlingar och hur dem påverkas av utsläpp från mänskliga aktiviteter, samt hur odlingen påverkar dess omgivande vattendrag. Fiskodlingar används främst för att odla fisk som livsmedel, men även fisk som är avsedd för utplantering till sjöar och hav. Utplantering av fisk görs främst för att minska trycket på den vilda fisken. Att bedriva en fiskodling innebär stort ansvar för verksamhetsutövaren, där lagar och krav som är fastställda av riksdagen måste uppfyllas. För att kontrollera lagar och krav har man regelbundna kontroller vid fiskodlingar från olika myndigheter. Större delen av dagens fiskodlingar ligger i kontakt med sjöar och hav, och kan därmed påverkas av yttre faktorer i form av mänkliga aktiviteter, men även från själva odlingen i sig. Påverkan som bygger på utsläpp från dessa kan både vara positivt och negativt för vattendraget beroende på hur förutsättningarna hos denna ser ut. Fiskodlingar kan även placeras på land, men är dock betydligt mer kostsamt i jämförelse med en odling placerad i vattendrag. Det finns vissa risker med att bedriva en fiskodling i vattendrag, med avseende på sjukdomar och rymning. Sjukdomar inom en fiskodling kan resultera i slakt, och denna kan även spridas till utomstående vattendrag. En rymning kan bidra till hybridisering och därav påverka det vilda beståndet av fisk, den kan även rubba näringsväven hos vattendraget i form av konkurrens med det vilda beståndet, men även via bioackumulation och biomagnifikation. Det finns vissa faktorer som avgör placeringen av en fiskodling, detta allt efter hur förutsättningarna ser ut och vilken fisk som odlas. Slotts Lax AB, som är en fiskodlingsverksamhet i Dalarna, har valt att odla sin fisk i vattendrag, detta främst för att minimera kostnaderna och nyttja den miljö som erbjuds, vid Dalälven och Siljan. Fisk kan även odlas på land, detta görs främst för  att minimera riskerna med rymning av fisk och spridning av sjukdomar. / Several rivers in Sweden, including Dalälven, are today contaminated  to certain degree. As the knowledge rises around how water quality affects the organisms and humans can specific measures be developed for water bodies, to improve the quality. This thesis focuses on fish farms and how they are affected by emissions from human activity, and how fish farming affects its surrounding water. Fish farms are mainly used to raise fish for human consumption, but also fish intended for planting out in lakes and seas. The planting of fish is mainly to reduce the pressure on wild fish. Conducting a fish farm involves great responsibility for the operator, where laws and requirements that are established by the parliament must be met. For that purpose the laws and requirements are regularly checked at farms from different agencies. Most of the fish farms are currently in contact with lakes and seas, and those can be affected by external factors such as human activities, but also from the culturing itself. Impact of emissions from fish farms can be both positive and negative for the watercourse, depending on the conditions of the area. Fish farms can also be placed on land, but this would be far more costly in comparison with fish farming in waterways. There are certain risks associated with conducting a fish in streams such as, diseases and fish escaping. Diseases in the fish farming can result in the slaughter, and this can also spread to outside watercourses. An escape can contribute to hybridization which therefore affect the wild population of fish, it can also disrupt the food chain of the stream in the form of competition with the wild population, but also through bioaccumulation and biomagnification. There are certain factors that determine the location of a fish farm, depending on how the conditions look likes and what kind of fish species that are being grown. Slotts Lax AB, which is a fish farming business in Dalarna, have chosen to grow their fish in streams, primarily in order to minimize costs and use the environment offered by the Dalälven River and Lake Siljan. Fish can also be grown on land, this is done primarily to minimize the risks of escape and the spread of diseases.