Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mercury (Hg) is a potent human toxin and a persistent global pollutant with unique properties and environmental behaviours which make it difficult to model and understand. While anthropogenic mercury sources are well understood along with the impacts on ecosystems and human populations, the processes and transformations which govern environmental cycling lack the same level of understanding. Concentrations in Arctic environments are a specific concern, along with cycling behaviours in regions spanning from temperate to Arctic climates. The objective of this experiment was the investigation and characterization of the mechanisms which promote elemental mercury (Hg^0) flux from soils in these environments during simulated seasonal cycling. A laboratory scale experiment was conducted which used a Dynamic Flux Chamber (DFC) to monitor Hg^0 flux from a naturally Hg enriched soil during temperature cycling relevant to cold environments. The results, which were split into freeze-thaw (FT) and sub-zero (SZ) cycles, showed that Hg^0 flux from frozen soils remains active during temperature cycling. During FT cycles, Hg^0 flux is controlled by soil temperature and energy entering the system, with a linear increase in flux for increases in energy. This response is produced from the entire soil column. During SZ cycles, Hg^0 flux is produced only in the thin soil surface layer and is controlled by the air temperature at the soil-air interface. A decrease in the DFC air temperature was observed to produce an increase in flux, with an inverse relationship controlled by a separate mechanism than the FT cycle response. Recommendations for modifications to the experimental set-up and methodology have been made to improve the accuracy of the results and confirm the behaviours characterized during this study. / Natural Sciences and Engineering Research Council of Canada (NSERC)

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

O metal mercúrio é conhecido pela sua grande toxidade apesar de seu emprego difundido. Desde a Antigüidade, se reconhece sua ação tóxica na exposição ocupacional. Em alguns ambientes laborais, os riscos são maiores, como é o caso de hospitais, que utilizam o mercúrio elementar em vários equipamentos, especialmente em termômetros de verificação da temperatura corporal, largamente empregados. Como na instituição objeto deste estudo foram quebrados 148 termômetros em uma Unidade de Terapia Intensiva no período de um ano, esta pesquisa objetivou a realização de uma avaliação de alguns indicadores ambientais neste espaço de trabalho e de alguns indicadores biológicos e psicológicos em uma amostra de trabalhadores desta unidade, que se dispuseram a participar da pesquisa. A avaliação de tais indicadores são recomendados como pertinentes pela literatura (ATSDR, 1989). Não se detectou em nenhuma das avaliações realizadas, índices acima das normas estabelecidas. Interpreta-se que a temperatura da unidade (20ºC) reduz a possibilidade do mercúrio se volatizar e intoxicar os trabalhadores. As regras de higiene, típicas do contexto hospitalar, e a rotina de rápido recolhimento dos resíduos dos termômetros quebrados e seu acondicionamento em recipientes com tampa são os principais fatores explicativos para os índices encontrados. / Mercury is known by its great toxity in spite of its wide use. Its toxic action in the occupational exposition has been known since ancient time. In some working places risks are great such as hospitals. Once mercury is used in a greater variety of equipments, especially in thermometers to check bodily temperature. In the institution where this study was carried out 148 thermometers were broken in the intensive care unit in a one-year period. This paper aims at assessing environmental e as well as some biologic and psycho logic rates in this area considering a group of employees of this unit, who were willing to take part in the study the rate assessment is recommended by literature (ATSDR 1989). In rates above normality have not been found in these assessments therefore, it is concluded that the unit temperature (20ºC) reduces in mercury the possibility to volatize and intoxicate employees. Hygiene rules, usual in the hospital routine, as well as quich collection of residues from the broken thermometers and their placement in containers with lids are the main reason for the found rates.

O metal mercúrio é conhecido pela sua grande toxidade apesar de seu emprego difundido. Desde a Antigüidade, se reconhece sua ação tóxica na exposição ocupacional. Em alguns ambientes laborais, os riscos são maiores, como é o caso de hospitais, que utilizam o mercúrio elementar em vários equipamentos, especialmente em termômetros de verificação da temperatura corporal, largamente empregados. Como na instituição objeto deste estudo foram quebrados 148 termômetros em uma Unidade de Terapia Intensiva no período de um ano, esta pesquisa objetivou a realização de uma avaliação de alguns indicadores ambientais neste espaço de trabalho e de alguns indicadores biológicos e psicológicos em uma amostra de trabalhadores desta unidade, que se dispuseram a participar da pesquisa. A avaliação de tais indicadores são recomendados como pertinentes pela literatura (ATSDR, 1989). Não se detectou em nenhuma das avaliações realizadas, índices acima das normas estabelecidas. Interpreta-se que a temperatura da unidade (20ºC) reduz a possibilidade do mercúrio se volatizar e intoxicar os trabalhadores. As regras de higiene, típicas do contexto hospitalar, e a rotina de rápido recolhimento dos resíduos dos termômetros quebrados e seu acondicionamento em recipientes com tampa são os principais fatores explicativos para os índices encontrados. / Mercury is known by its great toxity in spite of its wide use. Its toxic action in the occupational exposition has been known since ancient time. In some working places risks are great such as hospitals. Once mercury is used in a greater variety of equipments, especially in thermometers to check bodily temperature. In the institution where this study was carried out 148 thermometers were broken in the intensive care unit in a one-year period. This paper aims at assessing environmental e as well as some biologic and psycho logic rates in this area considering a group of employees of this unit, who were willing to take part in the study the rate assessment is recommended by literature (ATSDR 1989). In rates above normality have not been found in these assessments therefore, it is concluded that the unit temperature (20ºC) reduces in mercury the possibility to volatize and intoxicate employees. Hygiene rules, usual in the hospital routine, as well as quich collection of residues from the broken thermometers and their placement in containers with lids are the main reason for the found rates.

O metal mercúrio é conhecido pela sua grande toxidade apesar de seu emprego difundido. Desde a Antigüidade, se reconhece sua ação tóxica na exposição ocupacional. Em alguns ambientes laborais, os riscos são maiores, como é o caso de hospitais, que utilizam o mercúrio elementar em vários equipamentos, especialmente em termômetros de verificação da temperatura corporal, largamente empregados. Como na instituição objeto deste estudo foram quebrados 148 termômetros em uma Unidade de Terapia Intensiva no período de um ano, esta pesquisa objetivou a realização de uma avaliação de alguns indicadores ambientais neste espaço de trabalho e de alguns indicadores biológicos e psicológicos em uma amostra de trabalhadores desta unidade, que se dispuseram a participar da pesquisa. A avaliação de tais indicadores são recomendados como pertinentes pela literatura (ATSDR, 1989). Não se detectou em nenhuma das avaliações realizadas, índices acima das normas estabelecidas. Interpreta-se que a temperatura da unidade (20ºC) reduz a possibilidade do mercúrio se volatizar e intoxicar os trabalhadores. As regras de higiene, típicas do contexto hospitalar, e a rotina de rápido recolhimento dos resíduos dos termômetros quebrados e seu acondicionamento em recipientes com tampa são os principais fatores explicativos para os índices encontrados. / Mercury is known by its great toxity in spite of its wide use. Its toxic action in the occupational exposition has been known since ancient time. In some working places risks are great such as hospitals. Once mercury is used in a greater variety of equipments, especially in thermometers to check bodily temperature. In the institution where this study was carried out 148 thermometers were broken in the intensive care unit in a one-year period. This paper aims at assessing environmental e as well as some biologic and psycho logic rates in this area considering a group of employees of this unit, who were willing to take part in the study the rate assessment is recommended by literature (ATSDR 1989). In rates above normality have not been found in these assessments therefore, it is concluded that the unit temperature (20ºC) reduces in mercury the possibility to volatize and intoxicate employees. Hygiene rules, usual in the hospital routine, as well as quich collection of residues from the broken thermometers and their placement in containers with lids are the main reason for the found rates.

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Over the last decade our understanding of mercury cycling has dramatically changed. Evidence of rapid atmospheric oxidation has been observed in the Arctic, Antarctic, the MBL, coastal environments, saline lakes, and the upper troposphere/lower stratosphere. These results show that, Hg0, can undergo rapid gas-phase oxidation under standard atmospheric conditions. However, the mechanism and importance of this transformation is still unclear. The goal of this work was two-fold: to investigate of the kinetics of potential pathway for the gas phase oxidation of atmospheric mercury and to develop new laser based techniques, which can be employed for both laboratory and field studies of Hg(0) and the products of mercury oxidation. First and foremost, this work determined kinetic rate coefficients for the potentially important mercury reactions. Rate coefficients were determined using a Pulse Laser Photolysis - Laser Induced Fluorescence (PLP-LIF) technique monitoring one or more of the following species, Hg(0), Cl, Br, HgCl, and HgBr. The concentrations of these species were measured by LIF as the reaction occurred and a concentration vs. time profile was generated. From these profiles a rate coefficient for the reaction can be obtained. In the course of this work kinetic rate coefficients for the following mercury reactions were measured. Hg(0) + Cl + M --> HgCl + M Hg(0) + Br + M --> HgBr + M HgBr + M --> Hg(0) + Br + M HgBr + Br --> products HgCl + O2 --> products This work is the first direct measurement of a kinetic rate coefficient for these reactions, and the first work which employed one photon LIF to monitor the HgCl and HgBr products. The second aspect of this work was the development of new laser based techniques to detect atmospheric mercury and its oxidation products for both laboratory and field application. In this work a LIF technique was develop to detect HgCl and HgBr. In addition, a two photon LIF technique initially developed by Bauer et al., 2002 was verified and expanded. The two photon LIF technique was used to directly monitor Hg(0) atoms in-situ, to monitor Hg(0) evolving form a gold tube, and to monitor the Hg(0) evolving from the thermal decomposition of reactive gaseous mercury collected on a KCl coated or uncoated denuder. This work represents a significant advance in the development of a viable method the detect mercury and the mercury oxidation products in the laboratory and in the field and is the first study to observe clear differences in the characteristic desorption profiles of HgO and HgX2. This work has broad implications, it enhanced our current knowledge concerning the biogeochemical cycling of mercury, broadened our understanding of the mercury chemistry in high halogen environment, and provided new techniques which can be applied in future field and laboratory studies.