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[pt] Este estudo pretende avaliar as influências do tráfego de rotina e da construção de um novo trecho da BR-040, entre Duque de Caxias e Petrópolis, na emissão e composição do material particulado (MP) da região. As obras foram iniciadas em 2014 e interrompidas em junho de 2016. Foram realizados o monitoramento tradicional de MP e biomonitoramento com Tillandsia usneoides e Tillandsia stricta transplantadas em seis locais de amostragem ao longo da rodovia. O Laboratório de Estudos de Poluição Atmosférica (LEPA) forneceu filtros contendo partículas totais em suspensão (PTS), coletadas entre 2014 e 2016. A espectrometria de massas com plasma indutivamente acoplado (ICP-MS) e a cromatografia iônica (CI) foram utilizadas para a caracterização química das PTS. Em 2014 foram observadas as maiores concentrações médias de PTS nos pontos próximos ao pedágio. Em 2016 não houve diferença nas concentrações de PTS entre períodos com obras e em sua ausência. O elemento majoritário nas PTS foi Fe e os maiores fatores de enriquecimento (FE) foram obtidos para Cu, Cd e Ni. Os íons em maior concentração foram NO3-e SO4-2, associados a emissões veiculares. O biomonitoramento, realizado em 2018, revelou enriquecimento de Mn, Zn e Cd na maioria dos locais. A T. stricta apresentou maiores FE, que pode estar relacionado com os locais de origem ou fisiologia das plantas. Uma análise prévia de biomarcadores de estresse oxidativo revelou correlações entre metalotioneína e Fe, Mn, Co, Cu, Ni e Zn, indicando concentrações maiores que as fisiológicas para esses metais. As concentrações de outros biomarcadores como glutationa reduzida e H2O2 também foram avaliadas. / [en] This study aims to evaluate the influence of daily traffic and road construction of a new stretch of BR-040, between Duque de Caxias and Petrópolis, in the emission and composition of the particulate matter (PM) of the region. The construction works started in 2014 and were interrupted in June 2016. The traditional monitoring of PM and biomonitoring with transplanted Tillandsia usneoides and Tillandsia stricta were conducted at six sampling sites along the highway. The Laboratory of Atmospheric Pollution Studies (LEPA) provided filters containing total suspended particulates (TSP), collected between 2014 and 2016. inductively coupled plasma mass spectrometry (ICPMS) and ion chromatography (IC) were used to the chemical characterization of TSP. In 2014, the highest average concentrations of TSP were observed at points close to the toll. In 2016 there was no difference in TSP concentrations between periods with works and in their absence. The major element in the PTS was Fe and the greatest enrichment factors (FE) were obtained for Cu, Cd and Ni. The ions in higher concentrations were NO3 -and SO4-2 , associated with vehicular emissions. Biomonitoring, conducted in 2018, showed enrichment of Mn, Zn and Cd in most sites. T. stricta presented higher FE, which may be related to the sites of origin or physiology of the plants. A previous analysis of oxidative stress biomarkers revealed correlations between metallothionein and Fe, Mn, Co, Cu, Ni and Zn, indicating higher concentrations than the physiological ones for these metals. Concentrations of other biomarkers reduced glutathione and H2O2 were also evaluated.

An increase in public environmental awareness and a decrease in resources within government regulatory agencies have led to a larger interest in volunteer biomonitoring programs. Government agencies are currently using volunteer data for official purposes with increasing frequency, but questions have been raised about the validity of the data collected by volunteers who have only limited training and experience. Therefore, we conducted a detailed study to assess, modify, and validate the Virginia Save-Our-Streams (SOS) program, which is a volunteer organization collecting macroinvertebrate data. Sites were sampled using professional methods concurrently with volunteers who utilized the SOS protocol. The volunteer samples were retained for further laboratory analysis. In addition, numerous sites previously sampled by volunteers were re-sampled using professional methods. The data were statistically analyzed to determine if the results of volunteers and professional aquatic biologists were correlated and if they arrived at the same conclusions about ecological condition. It was determined that the Virginia SOS method, and probably other similar volunteer methods, consistently overrate ecological condition. This means that streams impaired by pollution could go unreported, if they are monitored exclusively by volunteers. The cause of this overestimation was determined to be the overly simplistic SOS metric, which is based solely on the presence or absence of taxa. The SOS protocol for data analysis was made more quantitative by developing a multimetric index that is appropriate for use by volunteers. The SOS sampling protocol was modified slightly to obtain actual counts of the different kinds of macroinvertebrates, which allowed for calculation of metrics. Sorting effort and taxonomic level of identification were not changed so that currently participating volunteers would not be excluded because of the need for expensive equipment or advanced technical training. The modified SOS protocol was evaluated by a different set of concurrent samples taken by volunteers and professionals, but using the same statistical techniques. The modified SOS protocol proved to be feasible for volunteers. The new SOS multimetric index correlated well with a professional multimetric index. The conclusions about ecological condition derived from the volunteer multimetric index agreed very closely with those made by professional aquatic biologists. This study demonstrated that volunteer biomonitoring programs can provide reliable data, but every volunteer program needs to be thoroughly validated by statistical comparisons to the professional methods being used in that area. / Master of Science

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Le bisphénol A (BPA), ubiquitaire dans l'environnement, est reconnu comme étant un perturbateur endocrinien (PE). La forte réactivité du BPA avec le chlore entraine la formation de dérivés chlorés du BPA (ClxBPA), possédant une activité perturbatrice endocrinienne supérieure au BPA. En santé environnementale, l'évaluation du risque chez l'homme implique notamment la mise en place d'études de biomonitoring et de toxicocinétique nécessitant l'analyse des micropolluants environnementaux dans les milieux biologiques.Afin d'estimer l'exposition des populations au BPA et ClxBPA, une méthode d'analyse par LC-MS/MS du BPA et des ClxBPA non conjugués a été validée dans l'urine. Cette méthode a ensuite été modifiée afin d'améliorer la rapidité et la sensibilité du dosage, et a été appliquée à la mesure de l'exposition aux PE dans une cohorte de femmes enceintes.L'étude de la toxicocinétique du BPA montre la formation de dérivés conjugués, éliminés par voie urinaire. Classiquement, pour la mesure des dérivés conjugués, des méthodes indirectes utilisant la déconjugaison enzymatique sont proposées. Dans ce cadre, nous avons développé une méthode originale permettant de valider l'efficacité de la déconjugaison. Si la mesure indirecte des métabolites après déconjugaison semble plus aisée, il reste néanmoins plus rationnel de doser directement l'analyte recherché. C'est pourquoi, après synthèse des substances étalons, nous avons pu développer, pour la 1ère fois, une méthode de dosage des dérivés glucuronides et sulfates du BPA et du Cl2BPA dans l'urine.Ce travail propose, à travers notamment le développement de méthodes d'analyse, des outils fiables pour la mesure de l'exposition aux PE. / Bisphenol A (BPA), a well-known endocrine disruptor (ED), is ubiquitously found in the environment. The high reactivity of BPA with chlorine results in the formation of chlorinated derivatives of BPA (ClxBPA), having a higher endocrine disrupting activity than BPA. In the field of environmental health sciences, human risk assessment implies, in particular, to perform biomonitoring and toxicokinetic studies requiring the analysis of environmental micropollutants in biological matrices. To estimate population exposure to BPA and ClxBPA, a LC-MS/MS method to assay BPA and ClxBPA was validated in urine. This method was then modified to improve the speed and sensitivity of the assay, and was applied to the measurement of ED exposure in a cohort of pregnant women.Toxicokinetic studies of BPA report the formation of conjugates, excreted in urine. Conventionally, for the measurement of conjugated derivatives, indirect methods using enzymatic deconjugation are proposed. In this context, we have developed an original method for validating the deconjugation efficiency.If the indirect measurement of metabolites after deconjugation appears easier, it is more rationale to assay directly the metabolite. Therefore, after synthesis of analytical standards, we were able to develop, for the first time, a method for assaying glucuronides and sulfates BPA and Cl2BPA derivatives in urine.This work offers, especially through the development of analytical methods, reliable tools for assessing human exposure to ED.

L'exposition humaine au bisphénol A et aux nonylphénols constitue un problème majeur de santé publique, en conséquence du caractère ubiquitaire de ces molécules et de leur toxicité en tant que perturbateur endocrinien. Leurs dérivés chlorés, formés par chloration lors de l'étape de désinfection de l'eau potable, présentent un effet perturbateur endocrinien jusqu'à 100 fois plus important que les composés parents. Au cours de ce travail nous avons développé des méthodes de dosage sensibles et reproductibles par LC-MS/MS de ces polluants dans l'eau. Le choix de l'isomère 353NP a été discuté et retenu comme substance de référence des nonylphénols. Le bisphénol A et le 353NP ont été retrouvés dans l'eau de surface (en entrée) et dans l'eau traitée (en sortie) de 8 usines de traitement d'eau potable, à des concentrations comprises entre 2,0 et 29,7 ng.L-1 et entre <4,1 et 124,9 ng.L-1 respectivement. Par ailleurs, aucun dérivé chloré n'a été détecté. Des dosages du bisphénol A et de ses dérivés chlorés réalisés dans 14 eaux du robinet et 4 eaux embouteillées ont montré leur présence dans ces eaux de boisson. Pour évaluer l'imprégnation de la population au bisphénol A et ses dérivés chlorés, nous avons mis au point un dosage ultrasensible de ces molécules par SPE-UPLC-MS/MS dans le lait maternel, validé selon les recommandations internationales. Ces composés ont été retrouvés dans le colostrum de 21 mères avec des concentrations comprises entre <0,40 et 6,12 ng.mL-1. Ces résultats prouvent qu'il existe une origine hydrique de la contamination chez l'homme par le bisphénol A, comme pour ses dérivés chlorés. / Bisphenol A and nonylphenols are widespread industrial chemicals which over the past decade have demonstrated their toxicity as endocrine disruptors. Residual chlorine present in drinking water may react with these compounds to form chlorinated derivatives, which have demonstrated a heightened level of estrogenic activity. In this work, we have comprehensively validated accurate and reproducible methods of quantification measuring these target compounds in water using LC-MS/MS. We have discussed and selected 353NP as the reference material for the analysis of nonylphenols. Bisphenol A and 353NP were found in both surface and treated water samples extracted from eight French drinking water treatment plants, at a level ranging from 2.0 to 29.7 ng.L-1 and from <4.1 to 124.9 ng.L-1, respectively. Neither chlorinated BPA nor chlorinated 353NP was detected. Quantification of bisphenol A and its chlorinated derivatives in 14 tap water samples and 4 bottled water samples showed that those pollutants are present in drinking water. Exposure to bisphenol A and its chlorinated derivatives in the population was investigated through breast milk. We developed a method using on-line SPE-UPLC-MS/MS to quantify these chemicals in breast milk according to internationally accepted guidelines. The target compounds were found in the colostrum of 21 women at concentrations ranging from <0.40 to 6.12 ng.mL-1. Drinking water may consequently constitute a source of human exposure to bisphenol A and its chlorinated derivatives.

L'évaluation de la contamination des cours d'eau par les agents parasites protozoaires est fondamentale puisqu'on estime qu'une personne sur deux dans le monde est ou a été infectée par une zoonose d'origine parasitaire. Les trois principaux parasites responsables d'épidémies hydriques sont Cryptosporidium parvum, Giardia duodenalis et Toxoplasma gondii. Actuellement, seule la matrice eau est utilisée pour analyser la présence de ces parasites dans l'environnement aquatique. Peu reproductible et chronophage, cette méthode ne permet pas de mettre en place une surveillance de routine. Le projet de thèse propose l'utilisation de la moule zébrée, Dreissena polymorpha, comme un nouvel outil complémentaire pour évaluer la qualité biologique des milieux d'eau douce. Au travers d'expérimentations combinant différentes approches in vivo, ex vivo et in situ, le potentiel de la dreissène à accumuler les parasites protozoaires ainsi que leurs cinétiques d'accumulation dans les tissus ont été déterminés. Utilisée comme espèce sentinelle des contaminations chimiques, l'effet d'un stress biologique dû aux protozoaires a été évalué au laboratoire sur les cellules clefs de l'immunité des bivalves, les hémocytes. Ainsi, le projet permet de placer l'organisme Dreissena polymorpha dans une double stratégie de biosurveillance : une biosurveillance sanitaire liée à l'utilisation de la dreissène en tant que vecteur de parasites considérés comme enjeux de santé publique et une biosurveillance environnementale liée à la compréhension des facteurs de confusion avec les réponses biologiques utilisées comme biomarqueurs. / Assessment of the water biological contamination by protozoa is crucial since one in two person of the world population is or has been infected by a parasitic zoonosis. The main protozoa responsible of waterborne outbreaks are Cryptosporidium parvum, Giardia duodenalis and Toxoplasma gondii. Currently, protozoa detection is only based on water analysis. Irrelevant and time consuming, water analysis do not permit accurate biomonitoring. These project aims to use the freshwater mussel, Dreissena polymorpha, as a new complementary tool for biological quality analysis of freshwater. Through in vivo, ex vivo and in situ experiments, we determine the utility of zebra mussel for protozoa accumulation and their accumulation pattern within mussel tissues. Already use as a sentinel specie for chemical contamination, biological stress caused by protozoa has been determined in laboratory experiments on key cells of bivalve immunity, the hemocytes. Hence, Dreissena polymorpha could be involved in a twofold biomonitoring tactics: sanitary biomonitoring related to the use of zebra mussel as vector to protozoa with public health issue and environmental biomonitoring on understanding of the confounding factors in biological responses used as biomarkers.

A avaliação da qualidade da água do rio Piracicaba foi realizada utilizando diferentes metodologias e organismos teste, e para tanto, de fevereiro de 2011 a janeiro de 2012 amostras de água foram coletadas em seis locais de amostragens ao longo do rio Piracicaba. Parâmetros físicos e químicos da água foram mensurados e de acordo com a condutividade elétrica e demanda bioquímica de oxigênio, baixa qualidade foi observada em locais próximos a Americana e Piracicaba. Efeitos sobre a reprodução de Ceriodaphnia dubia e Ceriodaphnia silvestrii foram observados em fevereiro e março de 2011 e janeiro de 2012, e ocorreram em amostras coletadas próximas às cidades de Americana e Piracicaba. A avaliação das brânquias do peixe Danio rerio mostrou que para todos os meses, exceto fevereiro, setembro e outubro para alguns pontos, as alterações não foram significativas. Amostras de água coletada em todos os locais, assim como em todos os meses apresentaram valores de clorofila a abaixo do estabelecido pela legislação ambiental brasileira. A água coletada nos meses de outubro e novembro e aquelas amostradas à montante e à jusante de Piracicaba apresentaram maiores valores de índice de estado trófico comparado aos outros pontos e meses do ano, no entanto, não foram classificadas como eutrofizadas. Concentrações dos herbicidas atrazina e ametrina também foram determinadas na água do rio Piracicaba e variaram de 0,11 a 1,92 \'mü\'g L-1 e 0,25 a 1,44 \'mü\'g L-1, respectivamente, e mostraram ter potencial mutagênico e genotóxico para D. rerio. Um estudo avaliando a toxicidade da vinhaça antes e após a correção do pH também foi realizado já que o rio Piracicaba está localizado em uma região influenciada por plantações de cana-de-açúcar. Os resultados apresentados confirmam que a vinhaça possui alta toxicidade aguda para organismos aquáticos, no entanto, esta pode ser reduzida através da correção do seu pH para 6,5 / An assessment of water quality of the Piracicaba River was performed using different methodologies and organisms, and therefore, from February 2011 to January 2012 water samples were collected at six sampling sites along the Piracicaba River. Physical chemical parameters of the water were measured and demonstred low water quality according to the conductivity and biochemical oxygen in places close to Americana and Piracicaba. Effects on the reproduction of Ceriodaphinia dubia and Ceriodaphnia silvestrii were observed in February and March 2011, and January 2012 and occurred in samples collected close to Americana and Piracicaba cities. Evaluation of the gills of Danio rerio showed no significant difference during all months, except in February, September and October for some locations. During the study period, water samples collected in all sampling sites and months presented values of chlorophyll a below the limit set by the Brazilian environmental law. Water collected in October and November and those sampled upstream and downstream of Piracicaba presented higher values of throfic state index than the other sites and months, however, were not classified as euthrofic. Concentrations of atrazine and ametrine during the sampling period were also measured and ranged from 0.11 to 1.92 \'mü\'g L-1 and from 0.25 to 1.44 \'mü\'g L-1, respectively, and showed genotoxic and mutagenic potentials to D. rerio. A study evaluating the acute toxicity of vinasse before and after the pH correction was conducted due to the influence of sugar cane cultures on the Piracicaba River area. The results confirmed the high acute toxicity of vinasse to aquatic organisms, however, this can be reduced by correcting its pH to 6.5