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The effects of 1 min 4 hr exposures to mercuric chloride (HgCl2), methyl mercuric chloride (CH3HgCl), p-chloromercuribenzoate (p-CMB) and ethylmercurithiosalicylate (TMS) on cell viability and kinetics of cell death, microtubules, F-actin, CD3 receptor expression, protein tyrosine phosphorylation (PTyr-P), intracellular calcium [Ca2+]i and responses to polarized signals in YAC-1 lymphoma cells were investigated. We hypothesized that immunotoxic effects of HgCl2 (Hg2+) are initiated by global receptor triggering, accompanied by increased protein tyrosine phosphorylation (PTyr-P) and down-regulation of the T-cell receptor (TCR). As a polychloride anion with poor lipid solubility, inorganic Hg2+ may produce effects at the outer cell membrane before significant intracellular accumulation, loss of microtubule integrity (a sensitive target) and activation of cell death through apoptotic pathways. The organomercurial compound p-CMB is likewise thought to penetrate membranes slowly as a result of ionization. In contrast, the highly lipid-soluble organomercurial compounds CH3HgCl and TMS were expected to reduce responses to polarized stimuli only in conjunction with and not prior to loss of microtubule integrity and the onset of necrotic cell death. <p>Two general patterns of effects were observed. In HgCl2-treated YAC-1 cells, inhibition of responses to polarized stimuli preceded loss of microtubules and onset of cell death. Effects on polarized stimuli were preceded by a transient Ca2+ signal; however, this Ca2+ signal appeared abortive, accompanied by a paradoxic decrease in PTyr-P and partial down-regulation of CD3 receptors. Responses to polarised stimuli were inhibited prior to extensive loss of microtubule staining, indicating effects preceded cytosolic Hg2+ accumulation. HgCl2 exposure was followed rapidly by necrotic cell death. <p>Similarly, p-CMB-treated YAC-1 cells failed to respond to polarized stimuli before effects on microtubules or loss of viability, and proceeded rapidly to late apoptosis; however, a transient Ca2+ signal and progressive loss of F-actin preceded effects in all other assays and may account for loss of polarized responses. <p>In CH3HgCl- and TMS-treated YAC-1 cells, CD3 receptor expression, [Ca2+] and PTyr-P were increased immediately, along with loss of microtubules. These reductions preceded inhibition of polarized signaling responses and seemed to indicate a general loss of cellular homeostasis not seen in HgCl2- and p-CMB-treated cells; loss of homeostasis did not necessarily produce simultaneous loss of viability, as TMS-treated cells remained viable for 30 min while CH3HgCl-treated cells became apoptotic within 1 min. Nonetheless, the YAC-1 cells proceeded to cell death more slowly, remaining early apoptotic after 4 hr, when almost all HgCl2- and p-CMB-treated cells were necrotic. These findings indicate the two groups of mercury compounds may alter responses to polarized stimuli and induce cell death by distinct pathways, one involving an apparently abortive signal and the other mediated by much more profound disruption of cellular homeostasis. Within the larger patterns there are further differences between the effects produced by each Hg compound, likely reflecting the combined influence of pharmacokinetic and dynamic factors governing access to and interactions with different cellular targets leading to cell death. These distinct targets may in turn be reflected in the different immune effects produced by these compounds <i>in vivo</i>.

The effects of 1 min 4 hr exposures to mercuric chloride (HgCl2), methyl mercuric chloride (CH3HgCl), p-chloromercuribenzoate (p-CMB) and ethylmercurithiosalicylate (TMS) on cell viability and kinetics of cell death, microtubules, F-actin, CD3 receptor expression, protein tyrosine phosphorylation (PTyr-P), intracellular calcium [Ca2+]i and responses to polarized signals in YAC-1 lymphoma cells were investigated. We hypothesized that immunotoxic effects of HgCl2 (Hg2+) are initiated by global receptor triggering, accompanied by increased protein tyrosine phosphorylation (PTyr-P) and down-regulation of the T-cell receptor (TCR). As a polychloride anion with poor lipid solubility, inorganic Hg2+ may produce effects at the outer cell membrane before significant intracellular accumulation, loss of microtubule integrity (a sensitive target) and activation of cell death through apoptotic pathways. The organomercurial compound p-CMB is likewise thought to penetrate membranes slowly as a result of ionization. In contrast, the highly lipid-soluble organomercurial compounds CH3HgCl and TMS were expected to reduce responses to polarized stimuli only in conjunction with and not prior to loss of microtubule integrity and the onset of necrotic cell death. <p>Two general patterns of effects were observed. In HgCl2-treated YAC-1 cells, inhibition of responses to polarized stimuli preceded loss of microtubules and onset of cell death. Effects on polarized stimuli were preceded by a transient Ca2+ signal; however, this Ca2+ signal appeared abortive, accompanied by a paradoxic decrease in PTyr-P and partial down-regulation of CD3 receptors. Responses to polarised stimuli were inhibited prior to extensive loss of microtubule staining, indicating effects preceded cytosolic Hg2+ accumulation. HgCl2 exposure was followed rapidly by necrotic cell death. <p>Similarly, p-CMB-treated YAC-1 cells failed to respond to polarized stimuli before effects on microtubules or loss of viability, and proceeded rapidly to late apoptosis; however, a transient Ca2+ signal and progressive loss of F-actin preceded effects in all other assays and may account for loss of polarized responses. <p>In CH3HgCl- and TMS-treated YAC-1 cells, CD3 receptor expression, [Ca2+] and PTyr-P were increased immediately, along with loss of microtubules. These reductions preceded inhibition of polarized signaling responses and seemed to indicate a general loss of cellular homeostasis not seen in HgCl2- and p-CMB-treated cells; loss of homeostasis did not necessarily produce simultaneous loss of viability, as TMS-treated cells remained viable for 30 min while CH3HgCl-treated cells became apoptotic within 1 min. Nonetheless, the YAC-1 cells proceeded to cell death more slowly, remaining early apoptotic after 4 hr, when almost all HgCl2- and p-CMB-treated cells were necrotic. These findings indicate the two groups of mercury compounds may alter responses to polarized stimuli and induce cell death by distinct pathways, one involving an apparently abortive signal and the other mediated by much more profound disruption of cellular homeostasis. Within the larger patterns there are further differences between the effects produced by each Hg compound, likely reflecting the combined influence of pharmacokinetic and dynamic factors governing access to and interactions with different cellular targets leading to cell death. These distinct targets may in turn be reflected in the different immune effects produced by these compounds <i>in vivo</i>.

In this thesis mercury concentrations in biota of the upper South Saskatchewan River Basin are assessed in three non-industrialized systems. Mercury levels in large sport fish (northern pike, walleye, lake trout) frequently exceeded the consumption limit of 0.5ppm. Goldeye and mooneye of the Oldman River and lake whitefish of Waterton Lakes were below 0.5ppm total mercury. Agricultural and urban effluents constituted no sources of significant mercury loadings to the Oldman River. A doubling of mercury biomagnification factors between longnose dace and their food suggests bioenergetic heterogeneity of these fish along the river gradient. Basin-specific mercury levels were detected for the upper and middle basins in Waterton Lakes, and are associated with food web characteristics, and fish bioenergetics. High mercury levels in a new reservoir were in part attributed to increased loadings from flooded soils, as is commonly observed, but also to bioenergetic constraints and growth inefficiency as a result of non-piscivory of this population. / xiii, 130 leaves : ill. ; 29 cm. --

In this master thesis, during 2009, 2010 and 2011, has been done measurement of total content of mercury in ambient air and soil air in urban and rural locations agglomeration of České Budějovice. The goal was to develop suitable method in order to provide sampling of air to evaluate rate of contamination from chosen locations. The aquaristic compressor was used for admission of air, thus collected air could pass through external amalgamator, which secured pre-concentration of mercury from air. Consecutively, captured mercury has been determined in laboratory by atomic absorption spectrometer AMA-254. In urban background locations has been found total average concentration of mercury in rate 4,01 +/- 3,5 ng.m-3 and urban locations influenced by traffic in rate 29,5 +/- 50,07 ng.m-3. The concentration of mercury in soil air taken from filter bed of constructed wetland (CW) was 16 +/- 9,44 ng.m-3 with average mercury flux 14,5 +/- 8,3 ng.m-2.h-1. In rural compared location has been concentration of mercury in rate 15,4 +/- 7,83 ng.m-3 and mercury flux in soil air was 16 +/- 9,3 ng.m-2.h-1 at this location. Significant differences in contamination of mercury among partial locations have not been ascertained to the exception. The statutory limit for amount of mercury in atmosphere is 50 ng.m-3, whose value has not been mostly reached in any of measured locations. Thus, it has been proved that air contamination is low at selected locations.

Le sol possède un capital naturel qui lui confère la capacité à produire des services écosystémiques aussi bien culturel que de régulation ou d’approvisionnement, il est indispensable à la Vie telle que nous la connaissons et au développement des activités humaines. Cependant les activités anthropiques et les pollutions, notamment par les éléments traces métalliques (ETMs) tel que le mercure (Hg), perturbent les sols et modifient en profondeur l’organisation des écosystèmes. Face à ces enjeux, des projets de remédiation et de gestion des sites et sols pollués se sont multipliés durant les dernières décennies en vue de futures ré-exploitations de ces sols. Cette thèse s’inscrit dans le cadre des projets ANR-BIOFILTREE et EC2CO FREIDI-Hg gérés par le laboratoire Chrono-Environnement. Mes travaux ont permis l’exploration de la diversité des communautés de microorganismes associées à une plantation de peuplier sur un site contaminé par le Hg et géré par phytomanagement, via les approches combinées de séquençage à très haut débit et par l’approche culture dépendante. Ces méthodes combinées ont permis de révéler i) la diversité des communautés bactériennes et fongiques de la peupleraie ; ii) les groupes de microorganismes particulièrement résistant au Hg (Trichoderma et Pseudomonas) ; et iii) des bactéries promotrices de croissance des plantes (PGPB). Par ailleurs, la compréhension des mécanismes cellulaires liés à l’accumulation de Hg par les microorganismes a été un de mes sujets d’étude en partenariat avec le LIEC (Université de Lorraine). Les modèles eucaryotes Saccharomyces cerevisiae et Podospora anserina ont été utilisés pour tester le rôle potentiel de certains transporteurs d’ions dans l’entrée du Hg dans les cellules fongiques. Les résultats ont montré que le transporteur de magnésium Alr1 situé sur la membrane plasmique pourrait participer au transport du Hg. En outre, une approche de transcriptomique chez Saccharomyces cerevisiae après une courte exposition au Hg des souches mutantes et sauvages a été mise en œuvre. Pour conclure, ce travail de thèse ambitionne d’être un travail de référence pour les futurs projets de phytomanagement en milieux contaminé par le Hg, qui met en avant les communautés de microorganismes et leurs rôles fondamentaux. / Soil has a natural capital that gives it the capacity to produce ecosystem services, cultural as well as regulation or supply, it is essential to the Life as we know it and the development of human activities. However, anthropogenic activities and pollution, in particular by trace elements (ETs) such as mercury (Hg), disrupt the soil and modify in depth the organization of ecosystems. Facing these challenges, remediation and management projects for polluted sites and soils have emerged during the last decades with a view to future re-exploitation of these soils. This thesis is part of the ANR-BIOFILTREE and EC2CO FREIDI-Hg projects managed by the Chrono-Environnement laboratory. My Ph-D work explored the diversity of microorganism communities associated with a poplar plantation at a Hg-contaminated site managed by phytomanagement, combining approaches such as very high-throughput sequencing and conventional culture-based techniques. These combined methods revealed i) the diversity of the bacterial and fungal communities of the poplar plantation; ii) the groups of microorganisms particularly resistant to Hg (Trichoderma and Pseudomonas); and iii) plant growth promoting bacteria (PGPB). In addition, understanding the cellular mechanisms related to the accumulation of Hg by microorganisms was one of my objectives carried out in collaboration with the LIEC (University of Lorraine). The eukaryotic models Saccharomyces cerevisiae and Podospora anserina were used to test the potential role of some ion transporters in the entry of Hg into fungal cells. The results showed that the magnesium transporter Alr1 located on the plasma membrane could participate in the transport of Hg. In addition, a transcriptomic approach in Saccharomyces cerevisiae after a short exposure to Hg of mutant and wild strains has been implemented. To conclude, this work aims to be a reference work for future phytomanagement projects in Hg-contaminated environments, which highlights micro-organism communities and their fundamental roles.

This study examined mercury and methylmercury concentrations in shark species in order to determine differences between shark species and between locations. Stable isotope ratios were determined to see if interaction existed between approximate trophic level and mercury concentrations. Sharks were sampled from Florida Bay where muscle tissue biopsies and blood samples were extracted upon capture. Stable isotope ratios for carbon-13 (δ13C) and nitrogen-15 (δ15N) from freezedried blood samples were compared with levels of organic and inorganic mercury species from tissue samples in seven different shark species, focusing on blacknose, blacktip, bull, and lemon sharks. Pre-caudal length (PCL) was strongly correlated to mercury concentration and δ13C but not with δ15N. Ratios of δ15N between shark species were in agreement with observed trophic-level behavior of blacktip sharks feeding on blacknose sharks, indicated by greater values for δ15N ratios in blacktip sharks. Calculated length-normalized stable isotope ratio values correlated strongly to values for mercury concentrations in blacktip sharks, indicating a potential method for forecasting inorganic or organic mercury concentrations without the use of more expensive mercury tests. This calculation also provided validity for a new metric involving the use of stable carbon isotope ratio divided by length (PCL) to be compared with other metrics. Correlations between δ15N values and mercury values indicate some level of interaction between trophic level and quantity of mercury contaminants in shark muscle tissue.

Thesis (M. Sc. Agriculture (Animal Production)) -- University of Limpopo, 2021 / The study was carried out to determine the concentration levels of mercury (Hg), lead (Pb), cadmium (Cd), chromium (Cr), nickel (Ni) and zinc (Zn) in water, soil, witbuffels grass and meat of goats reared along the river banks of Middle Olifants (Mogalatsana village) and Mogalakwena (Papegaai village) rivers. The samples were collected from the river water, soils along the river banks, grass grown along the river banks and male Pedi goats reared in Mogalatsana and Papegaai villages. The samples were analysed for the selected heavy metals with an inductively coupled plasma mass spectroscopy (ICP-MS). Data was analysed as in a complete randomised design. The results of selected heavy metals in water of both rivers ranged from 0.00 mg/litre of water (Ni and Cr) to 0.04 mg/litre of water (Hg). The concentration levels of selected heavy metals in water were similar (P>0.05) for Middle Olifants and Mogalakwena rivers. The concentration levels of selected heavy metals in the soils along the banks of Middle Olifants and Mogalakwena rivers ranged from 0.00 mg/kg DM soil (Hg and Cd) to 63.70 mg/kg DM soil (Cr). There were similar (P>0.05) concentration levels of selected heavy metals in the soils along the banks of Middle Olifants and Mogalakwena rivers. Heavy metal concentration levels in the witbuffels grass grown along the banks of Middle Olifants and Mogalakwena rivers ranged from 0.00 mg/kg DM of grass (Hg and Cd) to 5.05 mg/kg DM of grass (Zn). Similar (P>0.05) concentrations of selected heavy metals were observed in witbuffels grass grown along the banks of Middle Olifants and Mogalakwena rivers. However, the concentration levels of Zn, Pb and Cd in water from both sites were above internationally maximum permissible levels, indicating that the water from these rivers was not safe for drinking by humans and animals. The concentration levels of Ni and Pb in soils from both sites were above internationally recommended maximum permissible limits. Similarly, chromium concentration levels in witbuffels grass from both sites were above the recommended maximum permissible limits for livestock, indicating that the grass was not safe for consumption by livestock. It is recommended that further studies be conducted to ascertain these findings. Blood, liver, kidney and meat samples of yearling male Pedi goats grazing along the banks of Middle Olifants river (Mogalatsana village) had similar (P>0.05) Cr, Cd, Hg, Ni and Pb concentration levels, respectively. However, goat liver samples had higher (P<0.05) Zn concentrations than meat, kidney and blood samples. Samples of goat v meat contained higher (P<0.05) Zn concentrations than those of kidneys and blood. Similarly, goat kidney samples contained more (P<0.05) Zn than blood samples. Blood, liver, kidney and meat samples of Pedi goats grazing along the banks of Mogalakwena river (Papegaai village) contained similar (P>0.05) concentration levels of Cr, Cd, Hg, Ni and Pb, respectively. However, goat meat samples contained higher (P<0.05) Zn concentrations than liver, kidney and blood samples. Samples of goat liver contained higher (P<0.05) Zn concentration levels than kidney and blood samples. Similarly, goat kidney samples contained more (P<0.05) Zn than blood samples. Meat, blood, liver and kidney samples of male Pedi goats raised in Mogalatsana and Papegaai villages had similar (P>0.05) chromium, cadmium, mercury, nickel and lead concentrations, respectively. However, liver and kidney samples of goats from Mogalatsana village had higher (P<0.05) zinc levels than those from Papegaai village. Blood and meat samples of goats from Papegaai village had higher (P<0.05) zinc levels than those from Mogalatsana village. The concentration levels of Zn, Ni, Pb, Cr and Cd in the blood, liver, kidney and meat samples of male Pedi goats reared along the banks of Middle Olifants and Mogalakwena rivers were within the maximum permissible levels for human consumption. Mercury concentration levels in liver, kidney and meat samples of the goats were within the maximum permissible levels for human consumption. However, mercury concentration levels in the blood of goats grazing along the banks of Middle Olifants and Mogalakwena rivers were above the maximum permissible limit of 0.2 mg/litre of blood. It was concluded that meat, livers and kidneys of the goats were fit for human consumption. However, blood from these goats was not fit for human consumption.

The aim of this master thesis is a study of nitrogen post-discharge by mercury vapours titration. The nitrogen post-discharge is investigated for many years theoretically as well as for a practical use. The object of this master thesis is a study of kinetic processes ongoing at titrations of mercury vapours during the nitrogen post-discharge at different pressures and applied powers. All experimental data were obtained from an optical emission spectroscopy of nitrogen post-discharge. DC discharge in flowing regime was chosen for measurements. The first part of experiments was carried out at the constant discharge current (100 mA), voltage (1300 V) and wall temperature (300 K). The total gas pressure was varied in range of 500-3000 Pa at nitrogen flow in range of 0.12-0.68 l/min. Nitrogen flow values were arranged to obtain constant nitrogen flow velocity for all gas pressures. The second set of experiments studied power dependencies. The current was varied in the range of 50-200 mA for constant voltage 1300 V. The total gas pressure in this case was 1000 Pa. Mercury vapours were introduced into the system by titration tube at different post-discharge time. The nitrogen pink afterglow effect was well visible at all experimental conditions. This effect corresponds to the maximum intensity of light emission, which expresses as considerable growth of characteristic pink radiation in the post-discharge time. Optical emission spectra of post-discharge were taken in the range of 320-780 nm. Besides three nitrogen spectral systems (first and second positive and first negative), the mercury line at 254 nm was recorded in the second order spectrum at 508 nm under these conditions if mercury was added. This spectral line is excited under post-discharge conditions by collisionally induced resonance energy transfer from nitrogen highly vibrationally excited ground state metastables and it opens an unique technique for their monitoring. The dependence of relative intensities on decay time for mercury spectral line and selected nitrogen spectral systems at different titration positions were measured. The relative intensities of nitrogen bands decrease with increasing of mercury line relative intensity for all total gas pressures. The pink afterglow phenomenon shifts to the later decay times with the increasing of total gas pressure. In the case of experiments at different power, it can be seen that with decreasing power mercury spectral line intensity decreases in post-discharge time. The first detailed tests of the unique detection for highly excited of nitrogen metastables were completed. However this master thesis is concentrated on the basic research which supports better indication of kinetic processes and reactions leading to transformation of excitation energy, this new knowledge should be applied in future also in technologies based on the long-lived metastable induced reactions.

Doctor of Philosophy / Department of Chemical Engineering / Jennifer L. Anthony / Zeolites and zeolite-like materials have well-ordered structures and pores creating varying capacities for molecules based upon size, functional groups, polarity, and intermolecular forces making the materials useful for molecular sensing as well for molecules that are considered hazardous at very low concentrations with reproducible results because of these properties. This study will identify and characterize applications for zeolite and zeolite-like materials in gas and liquid phases based upon the dominating physical and chemical properties of the materials. The properties of interest include liquid phase ion exchange capacities, selectivities, gas/vapor phase adsorption capacity, and initial adsorption uptake rate. Zincosilicates have similar framework structures to aluminosilicate zeolites; however, they have distinct advantages over traditional zeolites. Zincosilicates typically have a higher ion density, lack “cages” in their structure which leads to all the cations being accessible for ion exchange, and have the ability to form three-membered rings which lead to large void spaces in their structure. These features lead to high capture capacities for divalent heavy metal mercury ions. In this work, the potential to use zincosilicates as ion exchangers such as VPI-7, VPI-9 and VPI-10 is presented. Results have shown that zincosilicates have capture capacities greater than traditional zeolites, even greater than those that have been synthesized with functional groups intended to increase metal sorption capacities. The selectivity coefficients in a binary ion exchange system were successfully modeled using the Gibbs-Donnan selectivity model. The selectivities for the zincosilicates were Pb>Na>Hg>K>Ca. Zeolites are also able to adsorb chemical species and therefore can be used as the recognition element in sensing devices. The sorption capacity of 2-chloroethyl ethyl sulfide, dimethyl methanephosphonate, ethanol, and n-butanethiol were examined with zeolites 13X, 4A, MCM-41, VPI-7, VPI-9, and ZSM-5. The zeolites selected provided very different framework composition, countercation, and surface area features for determining the most significant properties in adsorption. Zeolite 13X had the highest equilibrium and initial uptake rate for most compounds tested, whereas the low surface area zincosilicates, VPI-7 and VPI-9, had the lowest capacity. Based on these results, a piezoelectric device with an array of zeolites can be successfully employed as a sensor.