Manmade climate change has expressed a plethora of complex effects on Earth's biogeochemical compartments. Climate change may also affect the mobilisation of natural metal sources, with potential ecological consequences beyond mountains' geographical limits; however, this question has remained largely unexplored. We investigated this by analysing a number of key climatic factors in relationship with trace metal accumulation in the sediment core of a Pyrenean lake. The sediment metal contents showed increasing accumulation trend over time, and their levels varied in step with recent climate change. The findings further revealed that a rise in the elevation of freezing level, a general increase in the frequency of drier periods, changes in the frequency of winter freezing days and a reducing snow cover since the early 1980s, together are responsible for the observed variability and augmented accumulation of trace metals. Our results provide clear evidence of increased mobilisation of natural metal sources - an overlooked effect of climate change on the environment. With further alterations in climate equilibrium predicted over the ensuing decades, it is likely that mountain catchments in metamorphic areas may become significant sources of trace metals, with potentially harmful consequences for the wider environment.

This paper traces La Llorona’s evolution from ancient Aztec cosmology to Trace Elements of Random Tea Parties, a contemporary novel by Felicia Luna Lemus. I argue that the protagonist’s entrenchment in her own Llorona myth ultimately inhibits the development of a queer community in collaboration with the community of her birth. While Trace Elements of Random Tea Parties leaves the tension between familial duty and personal desire unresolved, the constant narrative oscillation between past tea parties with Leti’s grandmothers and present tea parties with Leti’s chosen lesbian familia opens a space for new kinship structures to emerge, remapping the contours of the Mexican-American family and a woman’s role within it. / text

This study shows how the composition of gases released from a single magmatic source may be modified during their ascending path. The main processes that influence the composition of the gases in these high temperature fumarolic environments, are: 1) interactions with wallrocks during gas ascent, which change the fugacities of the metal volatile species and affect the equilibrium between major species (fH2S/fSO2; fH2/fH2O); 2) mixing with meteoric water with consequent Cl adsorption, which may account for the Cl depletion of the gases; 3) remobilisation of previously formed sublimates and/or incrustation deposits. Comparison between the thermochemical models and the mineralogical composition of the silica tubes at Kudryavy and Satsuma-Iwojima volcanoes suggests that high fO2 due to the mixing of the gases with air during their injection into the atmosphere significantly reduces the volatility of several trace elements (As, Sb, Sn, Na, K, Tl, Te, Se and Cd). Comparisons between the enriched metals in aerosols and in the gases suggest that Mo, Pb, Bi, Na, K, Cu, Zn or Fe, which are enriched in the gases, are preferentially deposited in the gas conduits and vents whereas the highly volatile metals (Te, Tl, Sb, As and Se) and Cd condense in the plume. This study determines the reactions that may occur during the alteration of rocks in high temperature fumarolic environments. Three different processes of alteration prevail: (1) Acidic alteration which is characterized by the complete absence of clays, because the constant supply of gases to these systems allows for the pH values of the acidic fluids to be maintained low enough to prevent the precipitation of clay minerals. Complete leaching of all cations, except Si, from the primary silicates leads to important "silicification" of the wall rock. The primary mineral cations are leached in the following order: K, Na > Ca > Fe, Mg > Al > Si, Ti. The fluids enriched in these cations circulate in microcracks at different temperatures and different redox conditions and lead to the precipitation of secondary incrustations. At Kudryavy the incrustations are mainly sulfates. At Usu the lower sulfur/fluoride ratio of the gases allows the occurrence of aluminum fluoride incrustations. The order of primary minerals dissolution (olivine > plagioclase > pyroxene > matrix glass > Fe-Ti oxides) is established for both sites studied. (2) Alteration by an oxidized volcanic gas, resulting from mixing with the atmosphere (500 to 300°C). At Kudryavy, thermochemical modeling suggests that anhydrite and anhydrous sulfates, which occur at intermediate temperatures, are formed by interactions of the rock with oxidized gas. (3) The most important outcome of this work is the identification of the features of alteration by the volcanic gas that directly reacts with the rock at high temperatures (T > 500°C). The Kudryavy rocks show evidences for mineral transformations, which occur in the presence of the volcanic gas phase. Volcanic gas directly reacts with rocks at high temperatures (T > 500°C). The gas destabilizes the primary minerals, remobilizes the rock-bearing cations, and leads to the formation of second mineral assemblages. These transformations occur in situ, without significant mobility (gain or loss) of the cations. The high temperature secondary associations are characterized by the presence of andradite, hedenbergite, hercynite, tridymite/cristobalite. Anhydrite and anhydrous Al sulfate may occur within these mineral assemblages if the gas is oxidized.

The geochemistry, of groundwater collected from deep wells in the western section of the lower Santa Cruz basin of southeastern Arizona, was studied in order to determine the extent to which geochemica] analysis can be used to assess fluid flow and major and trace element migration patterns along hydrologic flowpaths in desert basins. Interaction between groundwater and enclosing sediments, and mixing between chemically distinct basin groundwater is found to exert a significant control on the chemical patterns that have evolved in the system. Activity-activity diagrams of the Na-Si-O-H system show that groundwater throughout the basin clusters near the three phase boundary between fluid, kaolinite, and montmorillonite and trends along the boundary to higher log (aNa⁺/aH⁺) values. A reaction model generated with computer program PHREEQE, that combines silicate weathering, kaolinite-Na-beidellite equilibrium, calcite equilibrium, and solution mixing, can simulate trends in groundwater composition along flowpaths in the basin. Trace metals introduced into the basin by the weathering of a buried porphyry copper deposit become spatially separated upon migration. Metal concentrations are found to be correlated to major cation concentrations. Cu is associated with high Na concentrations and a high ratio of Carbonate:Ca, whereas Zn is associated with high Ca concentration and a low ratio of Carbonate:Ca. Behavior of Cu and Zn during low-temperature transport can be controlled by the effects of mineral alteration on groundwater composition. Computer analysis of early basin diagenesis shows that changes in major solute composition that accompany weathering, constrained by equilibrium with clays and calcite, can produce the metal segregation pattern observed in the basin. Because the aquifer is strongly influenced by silicate and carbonate mineral equilibrium, the introduction of Central Arizona Project recharge, which is not in equilibrium with alluvial minerals, into the basin, requires a response by mineral reactions that attempt to restore the system to a state of equilibrium with kaolinite, montmorillonite, and calcite. A reaction model is developed to predict the consequent effects of outside recharge on groundwater quality.

Studying calcium carbonate (otoliths) and calcium phosphate (fins, scales, bones) hard structure chemistry has numerous applications in the fisheries field for both freshwater and marine environments. The overall thesis objectives were: 1.) to provide an integrated and multidisciplinary approach to understanding the incorporation of trace elements and isotopes into biomineralized hard structures, and 2.) to apply this multidisciplinary perspective in the examination of element marking, stock discrimination, and migration in teleost fish species found within the Canadian Polar North. Varying physiological mechanisms within fishes control the uptake of essential and non-essential trace elements and isotopes during biomineralization processes. Essential life elements such as zinc and magnesium are controlled by their own uptake regulation systems whereas non-essential elements such as strontium and barium are controlled primarily by calcium uptake at the gills driven by internal calcium homeostasis. Secondarily, environmental trace elements compete with calcium and with each other for uptake at the gills. The ability of certain hard structures such as bones, fins, and scales to remobilise calcium and associated calcium-like elements, plays a role in the prolonged high concentrations of strontium that were observed in otolith marking of Greenland Halibut, Reinhardtius hippoglossoides. High doses of strontium chloride resulted in a prolonged expulsion of excess strontium. Strong associations of Dolly Varden Char, Salvelinus malma malma, with groundwater allowed discrimination of populations among studied river systems using otolith strontium and barium, and strontium isotopes. Calculation of otolith strontium freshwater baselines allowed for a quantitative method to examine migration histories of Arctic Char, S. alpinus, in Canada and western Greenland. Migration seaward was related to ease of access to estuary and marine habitats. Easy access to estuaries resulted in migration at a young age and small size whereas longer rivers resulted in a delay of migration to older ages and larger sizes. Understanding the role of fish physiology in association with calcium homeostasis provided a stronger basis for understanding the incorporation and presence of trace elements and isotopes found within biomineralized hard structures. These studies underscore the utility of microchemical studies for elucidating biological phenomena, thus linking the aspects of biology, physiology, and geology. / February 2017

SUMMARY: Aim of this thesis is to provide, by using trace elements analysis and Pb isotopes analysis of archaeological findings from Roman era and following migration period, informations about basic bioarchaeological parameters of sites Abrahám, Rusovce II and Sládkovičovo (territory of present Slovakia) and Sopianae site (area of present Pécs city in Hugary). Analyses were performed on samples of 81 bones and 21 dental enamels. For purposes of this work most important concentrations are of Ca, P, Sr, Zn, Ba, Fe, Al, Mn and Pb (and its isotopes). They were consequently used for calculating Ca/P ratio in order to assess extent of after-burial diagenetic changes. For this purpose Al and Fe concentrations were taken into account too. Sr/Ca and Sr/Zn ratios were compared to assess prevailing type of diet. The Ba/Ca and Sr/Ca ratios were compared in order to asess supposable mobility of some individuals. By using of Pb concentrations and its isotopes contamination by this metal was assessed. During interpretations of individual conclusions useability of samples outgoing from assessment of extent of diagenetic alterations were always taken into account. Little changes in chemical composition of samples arise in case of Sopianae site, samples from other sites are greatly preserved. Using of paleodietary...

The Mokrsko-West deposit, situated about 20 km south from Prague, is one of the most important gold deposits in the Bohemian Massif. We can find hydrothermal quartz veins in two types of host rocks: tonalite in the Central Bohemian Plutonic Complex (CBPC) and amphibolite in the Jílové Belt (JB). A several generations of the quartz veins with different mineralization were found in the deposit. This study has several objectives. At first, it determines and compares the chemistry of quartz samples from different generations of hydrothermal veins. In addition, this work describes the distribution of the most important trace elements. Lastly, the work compares the potential differences in the chemistry of samples from the different host rocks (CBPC and JB). With the use of the LA-ICP-MS, 16 quartz samples from the Mokrsko-West deposit were analysed. Finally, 101 analyses were realized. From the analysed trace elements, the most important were Li, Mg, Al, Ca, Fe, Cu, Zn, As, Sb and Pb. Aluminium affects the concentration of the most of analysed trace elements. Positive correlation between Al and the other metals was also found. The samples with high Al content also showed high concentrations of other metals (Fe, Cu, Zn, Pb) and As. Samples with lower Al content showed lower concentration of other metal...

Les changements paléoenvironnementaux se produisant pendant le Sarmatien dans la Paratéthys Centrale ont été reconstitués par l’étude des foraminifères (36 espèces) et des ostracodes (28 espèces) de deux forages, combinée à une analyse géochimique de leurs squelettes calcitiques, des coquilles aragonitiques de gastéropodes et des dents phosphatiques de rongeurs.La composition de la microfaune indique que la connexion entre la Paratéthys et la Méditerranée est interrompue ou réduite à la base du Sarmatien mais qu’un bras de mer persiste entre Paratéthys Centrale et Paratéthys Orientale jusqu’à la fin du Sarmatien. Le Sarmatien inférieur est caractérisé par des eaux saumâtres peu profondes (maximum 80 m), bien ventilées, des températures stables (~ 15°C), un riche couvert végétal (algues et/ou phanérogames) et des efflorescences phytoplanctoniques périodiques. Un événement transgressif y est observé (TST de 3ème ordre; TB 2.6 du cycle global). Les changements faunistiques qui se produisent à la limite entre Sarmatien inférieur et moyen sont expliqués par un évènement de type HST accompagné de conditions dysoxiques. A la fin du Sarmatien moyen, une baisse du niveau marin relatif d’environ 50 m se produit et des eaux tempérées chaudes, plus saumâtres (17-23‰) et bien ventilées se mettent en place. Après un court épisode régressif, une connexion est rétablie entre la Paratéthys et la Méditerranée au début du Sarmatien supérieur. Des eaux chaudes (15-21° C), bien ventilées, correspondant à des lagunes marines et des marécages avec de fortes variations de la salinité (15-43 ‰) s’installent alors avant un isolement ultime de la Paratéthys qui se produit à la fin du Sarmatien. / Palaeoenvironmental changes in the Sarmatian Central Paratethys were reconstructed by studying foraminifers (36 species) and ostracods (28 species) from two boreholes coupled with geochemical analyses of their calcite skeletons and of aragonite gastropod shells and phosphate rodent teeth.The composition of the microfauna suggests that the connection between the Central Paratethys and the Mediterranean was interrupted or limited at the base of the Sarmatian, but that a seaway between the Eastern and Central Paratethys existed until the end of the Sarmatian. The early Sarmatian is characterized by brackish littoral seawater (maximum 80 m), well ventilated, stable temperatures (~ 15°C), with rich algae and/or seagrass vegetation and periodic phytoplankton blooms. A transgressive event can be observed as part of a 3rd order transgressive systems tract (TST) corresponding roughly to the TB 2.6 global cycle. The faunal changes occurring at the boundary between the lower and the middle Sarmatian can be explained by a sea-level highstand with dysoxic conditions. A relative sea-level fall with a maximum depth of about 50 m, and well ventilated, warm temperate and more brackish (17-23‰) conditions is documented at the end of the middle Sarmatian. After a short regressive event, a marine connection between the Paratethys and the Mediterranean was established at the beginning of the upper Sarmatian. Warm (15-21°C), well-ventilated, corresponding to marine shallow lagoon and marsh environments with high fluctuations in salinity (15-43 ‰) then prevailed before a final isolation of the Central Paratethys that occurred at the end of the Sarmatian.

This PhD thesis follows my master's thesis, which I focused on the problem of uranium determination and content in macrofungal fruit-bodies (the results have been published, Appendix 1). Macrofungi apparently do not accumulate uranium in fruit-bodies but as other studies suggested major roles of fungi in environmental geochemistry of uranium, I hypothesized possible accumulation of uranium and other elements in ectomycorrhizae. I therefore decided to continue the research and focus on investigation of trace elements in ectomycorrhizae. As I had opportunity to use a variety of analytical methods, I also participated in other studies in the field geomycology and the results are included in this thesis. In response to alarmist reports in Czech media, I focused on activity and distribution of radiocaesium in fruit-bodies of Boletus badius. As demonstrated in Appendix 2, the fruit- bodies of this species do not represent a health risk for mushroom consumers. Distribution of mycelium of saprotrophic Agaricus bernardii in a soil profile in Prague was investigated by use of molecular methods (PCR with specific primers). The results have shown that the mycelium reaches the depth of 30 cm. Lead isotopic composition of fruit- bodies suggests lead can be accumulated from soil depth of 13-17 cm (Appendix 3)....

Uma das maiores causas da alta taxa de mortalidade em todo o mundo está relacionada com a neoplasia em tecidos. Particularmente, o câncer de mama é o segundo tipo desta doença que mais atinge mulheres no Brasil. O diagnóstico precoce certamente pode diminuir o risco de morte de pessoas com este tipo de doença e o tratamento e a prevenção são certamente grandes desafios enfrentados pela medicina contemporânea. Atualmente, vem surgindo uma nova ferramenta de potencial diagnóstico, baseada no estudo de alguns elementos químicos que estão presentes em pequena quantidade no organismo, conhecidos como elementos traços. Estes elementos, responsáveis por algumas funções biológicas, podem apresentar-se em diferentes concentrações em tecidos normais e neoplásicos, o que pode indicar as mudanças histopatológicas dos tecidos e tornar possível a identificação de cada tipo de neoplasia. Desta forma, o estudo e determinação dos elementos traços em tecidos neoplásicos, que é o foco deste trabalho, apresenta uma nova área de interesse de investigação, principalmente pela possibilidade de oferecer informações diagnósticas, melhorando sua eficiência e em conseqüência, melhorando o prognóstico da paciente. Neste trabalho, utilizando a técnica de Fluorescência de Raios-X com feixes polienergéticos e monoenergéticos, determinamos as concentrações dos elementos traços em tecidos mamários normais e neoplásicos. Foram estudadas ao total 101 amostras de tecidos mamários normais, neoplásicos e tecidos normais adjacentes às neoplasias. As correções para os efeitos de matriz foram realizadas pelo método de padrão externo e pelo método de radiação espalhada para feixes polienergético e monoenergético respectivamente. Os resultados obtidos mostraram que todos os elementos analisados estão em níveis elevados nas espécies neoplásicas em relação às normais. Nas medidas com feixe polienergético foram verificadas diferenças significativas entre as concentrações dos elementos cobre e zinco entre tecidos normais e neoplásicos de amostras pareadas (p < 0,005) e não pareadas (p < 0,001). Com feixe monoenergético, foram obtidas diferenças significativas entre as concentrações de todos os elementos (Ca, Fe, Cu e Zn) em tecidos normais e neoplásicos de amostras pareadas e não pareadas (ambas com p < 0,001). Para as concentrações dos elementos cálcio e zinco foram observadas ainda diferenças significativas entre tecidos neoplásicos benignos e malignos (p < 0,001 e p < 0,002 respectivamente). A quantificação das concentrações dos elementos traços em tecidos normais e neoplásicos pode vir, portanto, auxiliar com precisão o diagnóstico das neoplasias de mama. / One of the major causes of the elevated rate of mortality in the whole world is related with the neoplasies in tissues. Particularly, the breast cancer is the second type of this disease that more reaches women in Brazil. Early diagnosis certainly can reduce the death risk in people with this type of disease and the treatment and prevention are certainly the great challenge found by medicine today. At present, it comes appearing a new diagnostic tool, based in the study of some chemical elements that are in small amount in the organism, known as trace elements. These elements, responsible for some biological functions, can be in different concentrations in healthy and neoplasics tissues that can indicate histopatological changes of breast cancer tissues, and become possible the identification of each type of neoplasies. In this way, the study and determination of trace elements in neoplastic tissues, the aim of this work, can be a new area of interest, mainly for the possibility to offer diagnostic information, improving its efficiency and in consequence, to improve the prognostic of the patient. In this work, using X-ray Fluorescence technique with polienergetic and monoenergetic beams, we determined the concentrations of the trace elements in healthy and neoplastic breast tissues. A total of 101 samples of healthy, neoplastic and adjacent normal tissues to neoplasies had been studied. The corrections for the matrix effect had been carried through by the method of external standard and by the method of scattered radiation for polienergetic and monoenergetic beams respectively. Results showed that all the analyzed elements are in raised levels in the neoplastic tissues in relation to the normal ones. In procedures with polienergetic beam significant differences between the concentrations of the elements copper and zinc had been verified between normal and neoplastic tissues of paired samples (p < 0,005) and independent samples (p < 0.001). With monoenergetic beam, concentrations of all elements (Ca, Fe, Cu and Zn) in healthy and neoplastic tissues of paired and independent samples showed significant differences (all with p < 0.001). For concentrations of the elements calcium and zinc significant differences between benign and malignant neoplastic tissues had been observed (0.001 p < and p < 0,002 respectively). The quantification of concentrations of trace elements in normal and neoplastic tissues can, therefore, support with precision the breast cancer diagnosis.