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Geochemical Study: Sediments as a Source and/or Trap of Mercury Contaminatin.
Májska, Milada ; Amouroux, David (oponent) ; Zdeňka, Svobodová (oponent) ; Dočekalová, Hana (vedoucí práce)
Mercury is naturally occurring toxic element; however global mercury emissions are dominated by anthropogenic sources. The global cycle of mercury has seen an increase in mercury deposition, especially in aquatic ecosystems, since the beginning of the industrial revolution. The sediment in aquatic systems may acts as the ultimate sink, where mercury in its various complexes is deposited. The mercury in sediments can then be converted to its more toxic organic form, methylmercury (MeHg), by the transformation processes controlled by various physical, chemical and biological factors. More over remobilization of mercury species from sediments is possible due to diffusion and resuspension and so sediments may act as potential source of mercury for aquatic biota. Bioaccumulation and biomagnifications can then continue up the food chain where humans, among other animals, consume the organic mercury. It is clear that determination of total mercury is not sufficient to understand its fate in the environment; determination of MeHg provides very useful additional information. The sensitive and precise analytical method for MeHg determination is necessary. The methodological part of the thesis deal with the methods for determination of mercury species in sediments. The method for methylmercury determination in sediments using automated Headspace sampler equipped with Trap and coupled with Gas Chromatography and Atomic Fluorescence Detector was developed and is define. The special attention is also given to the necessity of clean sampling procedures and the proper storage and pre-treatment of the samples and the field study of Hg distribution in sediments. The mercury contamination of sediments from the South Moravia and Northern France are compared. The mercury species and other elements (Fe, Mn, S) were analysed in sediments and/or pore water and/or surface water collected from the sampling sites in the Dele and Lys River (France) and Jihlava and Morava River (Czech Republic). In order to better assess the mercury contamination of aquatic ecosystem, the pore water concentration could be evaluated to understand the availability of mercury from sediment. The use of diffusive gradient in thin film (DGT) technique is applied to measure pore water mercury concentration in river sediments. Till 2005 the development of DGT for measuring mercury has been limited. But the recent progress of the availability of ion exchange resins capable of adsorbing mercury enables the use of DGT technique for mercury measurement. Different resins gels for mercury determination are used: Spheron-Thiol, Duolite GT-73 and TiO2. River Dele act as a sink for enormous anthropogenic Hg from the industrial activities and is considered as a potential significant source of methylmercury to the surrounding environment. The last part of thesis deal with the application of well-established isotope experiments to study methylation/demethylation processes in sediments of Dele River. For this purpose, species-specific isotopically enriched tracers in the form of inorganic mercury IHg (199Hg) and MeHg (201MeHg) have been added to the sediment slurries. Mercury labelled species were used as the tracers to follow their chemical fate and calculate the extent of the transformation reaction yield occurring during the 24 hours experiment.
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Geochemical Study: Sediments as a Source and/or Trap of Mercury Contaminatin.
Májska, Milada ; Amouroux, David (oponent) ; Zdeňka, Svobodová (oponent) ; Dočekalová, Hana (vedoucí práce)
Mercury is naturally occurring toxic element; however global mercury emissions are dominated by anthropogenic sources. The global cycle of mercury has seen an increase in mercury deposition, especially in aquatic ecosystems, since the beginning of the industrial revolution. The sediment in aquatic systems may acts as the ultimate sink, where mercury in its various complexes is deposited. The mercury in sediments can then be converted to its more toxic organic form, methylmercury (MeHg), by the transformation processes controlled by various physical, chemical and biological factors. More over remobilization of mercury species from sediments is possible due to diffusion and resuspension and so sediments may act as potential source of mercury for aquatic biota. Bioaccumulation and biomagnifications can then continue up the food chain where humans, among other animals, consume the organic mercury. It is clear that determination of total mercury is not sufficient to understand its fate in the environment; determination of MeHg provides very useful additional information. The sensitive and precise analytical method for MeHg determination is necessary. The methodological part of the thesis deal with the methods for determination of mercury species in sediments. The method for methylmercury determination in sediments using automated Headspace sampler equipped with Trap and coupled with Gas Chromatography and Atomic Fluorescence Detector was developed and is define. The special attention is also given to the necessity of clean sampling procedures and the proper storage and pre-treatment of the samples and the field study of Hg distribution in sediments. The mercury contamination of sediments from the South Moravia and Northern France are compared. The mercury species and other elements (Fe, Mn, S) were analysed in sediments and/or pore water and/or surface water collected from the sampling sites in the Dele and Lys River (France) and Jihlava and Morava River (Czech Republic). In order to better assess the mercury contamination of aquatic ecosystem, the pore water concentration could be evaluated to understand the availability of mercury from sediment. The use of diffusive gradient in thin film (DGT) technique is applied to measure pore water mercury concentration in river sediments. Till 2005 the development of DGT for measuring mercury has been limited. But the recent progress of the availability of ion exchange resins capable of adsorbing mercury enables the use of DGT technique for mercury measurement. Different resins gels for mercury determination are used: Spheron-Thiol, Duolite GT-73 and TiO2. River Dele act as a sink for enormous anthropogenic Hg from the industrial activities and is considered as a potential significant source of methylmercury to the surrounding environment. The last part of thesis deal with the application of well-established isotope experiments to study methylation/demethylation processes in sediments of Dele River. For this purpose, species-specific isotopically enriched tracers in the form of inorganic mercury IHg (199Hg) and MeHg (201MeHg) have been added to the sediment slurries. Mercury labelled species were used as the tracers to follow their chemical fate and calculate the extent of the transformation reaction yield occurring during the 24 hours experiment.
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