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Importance of Sulfide, Polysulfides, and Elemental Sulfur for Abiotic and Biotic Redox Processes in Sulfur-Metal(Loid) Systems

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Importance of Sulfide, Polysulfides, and Elemental Sulfur for Abiotic and Biotic Redox Processes in Sulfur-Metal(Loid) Systems Importance of Sulfide, Polysulfides, and Elemental Sulfur for Abiotic and Biotic Redox Processes in Sulfur-Metal(loid) Systems Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften (Dr. rer. nat.) an der Graduiertenschule für Mathematik und Naturwissenschaften der Universität Bayreuth vorgelegt von Regina Lohmayer Bayreuth, Mai 2015 Die vorliegende Arbeit wurde in der Zeit von März 2011 bis Mai 2015 in Bayreuth am Lehrstuhl Umweltgeochemie unter Betreuung von Frau Professorin Dr. Britta Planer- Friedrich angefertigt. Vollständiger Abdruck der von der Bayreuther Graduiertenschule für Mathematik und Naturwissenschaften (BayNAT) der Universität Bayreuth genehmigten Dissertation zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.). Dissertation eingereicht am: 26.05.2015 Zulassung durch das Leitungsgremium: 19.06.2015 Wissenschaftliches Kolloquium: 30.10.2015 Amtierender Direktor: Prof. Dr. Stephan Kümmel Prüfungsausschuss: Prof. Dr. Britta Planer-Friedrich (Erstgutachterin) Prof. Dr. Ruben Kretzschmar (Zweitgutachter) Prof. Dr. Egbert Matzner (Vorsitz) Prof. Dr. Stefan Peiffer - III - ACKNOWLEDGEMENTS I would like to express my sincere thanks to all people, who supported me during my PhD. First of all, I would like to thank Prof. Dr. Britta Planer-Friedrich for her supervisorship and her constant and intense scientific support on the work in the laboratory or in the field and on the presentation of results of my research in publications and presentations. I am especially thankful for numerous productive discussions, critical comments, and valuable suggestions. I would like to thank Prof. Dr. Stefan Peiffer, Prof. Dr. Andreas Kappler, and all members of the DFG research group e-TraP for many valuable discussions. Thanks to Dr. Alexey Kamyshny for his helpfulness concerning questions regarding polysulfide chemistry and to Prof. Dr. Ralf Steudel and Dr. Joachim Weiss for valuable hints in the field of chromatographic analysis. My acknowledgements to Dr. Elvira Bura-Nakić for her help during sampling at Lake Rogoznica in Croatia and various instructive conversations about fundamental principles of chemistry. I would like to acknowledge the valuable scientific cooperation with all authors of the publications to which I contributed. For laboratory assistance on the analysis by HPLC in the early phase of my PhD I would like to thank Dr. Sasan Rabieh and Dr. Sophie Fortenfant. Thanks to Prof. Dr. Andreas Kappler and his Geomicrobiology Group at the University of Tübingen for laboratory training and helpful advice in the field of microbiology. My acknowledgements to Stefan Will and Dr. Frank Thomas for support in the analysis by IC-ICP-MS. Special thanks to all current and former members of the Environmental Geochemistry Group and especially to Sinikka Hinrichsen, Maria Ullrich, Julia Arndt, Judith Mehlhorn, Cornelia Härtig, Dr. Elke Süß, Dr. Frank Thomas, and Dr. Jörg Schaller for their helpfulness, their interest in my work, and numerous encouraging discussions. I would like to thank my supervised bachelor and master students Anja Schnell, Gloria Reithmaier, Axel Müller, and Carolin Kerl for the good cooperation. I would like to acknowledge financial support by the State of Bavaria for a 2.5-years PhD scholarship and by the University of Bayreuth Graduate School for a travel grant to the EuCheMS conference 2014 in Istanbul. Sincere thanks to my family and my partner for their unlimited support. - IV - ABSTRACT Sulfur, an ubiquitous element in the environment, occurs in different oxidation states from +6 to -2. Between the thermodynamically stable end members sulfate and sulfide, a variety of intermediate sulfur species exist, examples of which are sulfite, polythionates, thiosulfate, elemental sulfur, and polysulfides. Polysulfides are highly reducing and nucleophilic sulfur chains of the general structure 2- Sn (n ≥ 2). Due to their high reactivity and instability, inorganic polysulfide analysis is challenging. Currently, the most reliable analytical approach is derivatization of inorganic polysulfides to form more stable organic polysulfanes, which can be analyzed chromatographically. Intermediate sulfur species in general and polysulfides in particular are assumed to be decisive for a variety of redox transformation processes of metal(loid)s but are only rarely analyzed. The aim of the present study was to investigate the role of sulfide, elemental sulfur, and especially polysulfides for abiotic and biotic redox processes in sulfur-metal(loid) systems. Open questions resulting from previous investigations concerning the interaction of different sulfur species with iron, arsenic, and molybdenum were addressed with special focus on the sulfur speciation. Elemental sulfur disproportionation is among the oldest metabolic pathways in earth’s history and still raises many questions. Growth of microorganisms by elemental sulfur disproportionation was found to depend on the presence of a sulfide scavenger such as ferric iron. In the present study, growth of haloalkaliphilic bacteria by elemental sulfur disproportionation was shown for the first time and was observed both, in the presence of iron, which is in accordance to previous studies, but also in the absence of iron. This was possible due to substantial formation of polysulfides under anoxic and alkaline conditions, which decreased free sulfide concentrations in solution and consequently rendered elemental sulfur disproportionation thermodynamically favorable. The reaction of dissolved sulfide with ferric (oxyhydr)oxides can result in the formation of thermodynamically stable pyrite, the most commonly occurring sulfide-bearing mineral. In former studies, different reaction pathways of pyrite formation were determined to occur in the aqueous phase. In the present study, polysulfides were found at the mineral surface during sulfidation of ferric (oxyhydr)oxides. Concentrations of disulfide, the dominating polysulfide species, increased with the reactivity of the iron minerals, which is also positively correlated to the kinetics of pyrite formation. Overall, it was concluded that surface-associated polysulfides play a decisive role as pyrite precursors. The reductive dissolution of ferric (oxyhydr)oxides is crucial with regard to the release of adsorbed nutrients or contaminants. It can be mediated indirectly by sulfur-reducing bacteria. Previously, thiosulfate, elemental sulfur, or polysulfides were proposed to serve as electron shuttles between bacteria and ferric minerals. We found elemental sulfur, attached to the mineral surface, as predominant sulfur oxidation product. Besides thiosulfate, tetrathionate, sulfite, and sulfide, polysulfides could initiate the electron shuttling process but were of minor importance for the shuttling - V - Abstract process itself. Overall, the present study revealed a detailed insight into the role of different sulfur species during microbially mediated ferric mineral reduction. Soluble arsenic-sulfur species are crucial for the cycling of arsenic under sulfidic conditions. In former studies, trivalent thioarsenites were found to form by the reaction of arsenite with sulfide and to rapidly oxidize to pentavalent thioarsenates. The latter were suggested to form directly by the reaction of arsenite with polysulfides. In the present study, polysulfides were found to react with arsenite to form monothioarsenate. Moreover, the higher nucleophilicity of polysulfides in comparison to sulfide seemed to accelerate the formation of higher thiolated arsenates. The formation of polysulfides and monothioarsenate was also observed in biotic systems during growth of an anaerobic haloalkaliphile, which couples arsenate reduction with sulfide oxidation. Additionally, monothioarsenate was microbially disproportionated to arsenite and polysulfides. Confirming previous suggestions, polysulfides were found to play a crucial role for thioarsenate formation. Evidence for substantial microbial acceleration of thioarsenate transformation processes was found earlier. In the present study, monothioarsenate transformation was considerably faster in the presence of a hyperthermophile bacterium in comparison to abiotic conditions. Abiotically, monothioarsenate was determined to be desulfidized to form arsenate and sulfide, which in turn was oxidized to elemental sulfur and thiosulfate under high temperature and oxic conditions. The bacteria accelerated monothioarsenate transformation mainly by oxidizing the abiotically formed intermediate sulfur species to sulfate. In general, sulfur redox chemistry was found to be decisive for thioarsenate transformation processes. The formation of soluble thiomolybdate species was assumed to be crucial for molybdenum burial in sediments, an important indicator for reconstructing paleoredox conditions. However, up to now there is no evidence about thiomolybdate occurrence in the environment. In the laboratory, we found that rate and extent of thiomolybdate formation increased with increasing sulfide to molybdate excess and a pH of 7 was determined to be most favorable for the nucleophilic substitution reaction. Polysulfides did not have any influence on thiomolybdate formation. We optimized ion-pair chromatographic separation of thiomolybdates for coupling to an inductively coupled plasma-mass spectrometer to be able to analyze nanomolar thiomolybdate concentrations. Using this new method, spontaneous formation of thiomolybdates could be observed in euxinic marine waters after addition of
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