(Table 1) Sulfur isotopes and description of anhydrite in DSDP Holes 70-504B and 83-504B

Anhydrite occurs in veins in hydrothermally altered basalts recovered from Hole 504B during Leg 83 of the Deep Sea Drilling Project. Sulfur isotopic data indicate that the anhydrites formed from fluids with sulfur isotopic compositions similar to seawater sulfate. Anhydrite probably formed as a pulse of relatively unreacted seawater was heated when it entered a relatively hot hydrothermal system containing evolved fluids. Reheating and continued evolution of the system followed anhydrite deposition. Preservation of anhydrite in Hole 504B was probably favored by the high temperatures and by the low permeability that resulted from the sealing of cracks with secondary minerals. Evidence also indicates that anhydrite was partly replaced by laumontite and prehnite at relatively high temperatures, and possibly by calcite at lower temperatures.

The Early Diagenetic Formation of Organic Sulfur in the Sediments of Mangrove Lake, Bermuda

Due to a low mineral content, the sapropelic sediments depositing in Mangrove Lake, Bermuda, provide an excellent opportunity to explore for possible additions of sulfur to organic matter during the early stages of diagenesis. We evaluated early diagenetic organic sulfur transformations by monitoring the concentrations and stable isotopic compositions of a number of inorganic and organic sulfur pools, thereby accounting for all of the sulfur in the sediments. We have identified and quantified the following sulfur pools: porewater sulfate, porewater sulfide, elemental sulfur, pyrite sulfur, hydrolyzable organic sulfur (HYOS), chromium-reducible organic sulfur (CROS), and nonchromium-reducible organic sulfur (Non-CROS). Of the organic sulfur pools, the Non-CROS pool is by far the largest, followed by CROS, and finally HYOS. By 60 cm depth these pools contribute, respectively, to 85, 7.9, and 3.6% of the total solid phase sulfur. The HYOS pool is probably of biological origin and shows no interaction with the sulfur compounds produced during diagenesis. By contrast, CROS is produced, most likely, from the diagenetic addition of polysulfides to functionalized lipids in the upper, H2S-poor, elemental sulfur-rich, region of the sediment. A portion of this sulfur pool is unstable and decomposes on contact with the H2S-rich porewaters. The portion of CROS that remains in the sulfidic waters appears to readily exchange sulfur isotopes with H2S. While some of the Non-CROS pool is of biological origin, some is also formed by the diagenetic addition of sulfur to organic compounds in the upper H2S-poor region of the sediment. By contrast with CROS, Non-CROS is not diagenetically active in the H2S-rich porewaters. Overall, somewhere between 27 and 53 % of the organic sulfur buried in Mangrove Lake sediments is of diagenetic origin, with the remaining organic sulfur derived from biosynthesis. We extrapolate our Mangrove Lake results and calculate that in typical coastal marine sediments between 11 and 29 μmol g−1 of organic sulfur will form during early diagenesis, of which 2–5 μmol g−1 will be chromium reducible.

Using sulfur isotope fractionation to understand the atmospheric oxidation of SO 2

Sulfate aerosol plays an important but uncertain role in cloud formation and radiative forcing of the climate, and is also important for acid deposition and human health. The oxidation of SO2 to sulfate is a key reaction in determining the impact of sulfate in the environment through its effect on aerosol size distribution and composition. This thesis presents a laboratory investigation of sulfur isotope fractionation during SO2 oxidation by the most important gas-phase and heterogeneous pathways occurring in the atmosphere. The fractionation factors are then used to examine the role of sulfate formation in cloud processing of aerosol particles during the HCCT campaign in Thuringia, central Germany. The fractionation factor for the oxidation of SO2 by ·OH radicals was measured by reacting SO2 gas, with a known initial isotopic composition, with ·OH radicals generated from the photolysis of water at -25, 0, 19 and 40°C (Chapter 2). The product sulfate and the residual SO2 were collected as BaSO4 and the sulfur isotopic compositions measured with the Cameca NanoSIMS 50. The measured fractionation factor for 34S/32S during gas phase oxidation is αOH = (1.0089 ± 0.0007) − ((4 ± 5) × 10−5 )T (°C). Fractionation during oxidation by major aqueous pathways was measured by bubbling the SO2 gas through a solution of H2 O2

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.

Multiple sulfur isotope fractionations in inorganic aqueous systems

New constraints on isotope fractionation factors in inorganic aqueous sulfur systems based on theoretical and experimental techniques relevant to studies of the sulfur cycle in modern environments and the geologic rock record are presented in this dissertation. These include theoretical estimations of equilibrium isotope fractionation factors utilizing quantum mechanical software and a water cluster model approach for aqueous sulfur compounds that span the entire range of oxidation state for sulfur. These theoretical calculations generally reproduce the available experimental determinations from the literature and provide new constraints where no others are available. These theoretical calculations illustrate in detail the relationship between sulfur bonding environment and the mass dependence associated with equilibrium isotope exchange reactions involving all four isotopes of sulfur. I additionally highlight the effect of isomers of protonated compounds (compounds with the same chemical formula but different structure, where protons are bound to either sulfur or oxygen atoms) on isotope partitioning in the sulfite (S4+) and sulfoxylate (S2+) systems, both of which are key intermediates in oxidation-reduction processes in the sulfur cycle. I demonstrate that isomers containing the highest degree of coordination around sulfur (where protonation occurs on the sulfur atom) have a strong influence on isotopic fractionation factors, and argue that isomerization phenomenon should be considered in models of the sulfur cycle. Additionally, experimental results of the reaction rates and isotope fractionations associated with the chemical oxidation of aqueous sulfide are presented. Sulfide oxidation is a major process in the global sulfur cycle due largely to the sulfide-producing activity of anaerobic microorganisms in organic-rich marine sediments. These experiments reveal relationships between isotope fractionations and reaction rate as a function of both temperature and trace metal (ferrous iron) catalysis that I interpret in the context of the complex mechanism of sulfide oxidation. I also demonstrate that sulfide oxidation is a process associated with a mass dependence that can be described as not conforming to the mass dependence typically associated with equilibrium isotope exchange. This observation has implications for the inclusion of oxidative processes in environmental- and global-scale models of the sulfur cycle based on the mass balance of all four isotopes of sulfur. The contents of this dissertation provide key reference information on isotopic fractionation factors in aqueous sulfur systems that will have far-reaching applicability to studies of the sulfur cycle in a wide variety of natural settings.

阿尔泰南缘侧向增生过程中的VMS矿床：地质、地球化学特征与成矿机制

The Chinese Altai is one of the most important volcanogenic massive sulfide (VMS) deposit districts in China. All orebodies were lenticular or bedded and stratabounded by a suite of early Devonian volcanic-sedimentary rocks. Hydrothermal feeder zones developed under some of the orebodies. All the ores are massive or laminated, and show typical characteristics of VMS deposit. Based on the mineralizing time and the metal assembles, we divide 3 metallogenic stages: 1, Fe orefroming stage associated with basaltic and sedimentary rocks during very early Devonian; 2, Cu-Pb-Zn oreforming stage associated with rhyolitic and sedimentary rocks during early Devonian; 3， Cu-Zn oreforming stage in the dacitic and basaltic rocks during mid. Devonian. The hosting rocks for all orebodies are different, but they show very similar geochemical and isotopic characteristics. All the felsic rocks show enriched lighted rare earth elements (REE) patterns (La/Yb>5), and with an obvious Eu negative anomalies (Eu/Eu*<0.6). In the meanwhile, all the mafic rocks show flat REE pattern and no Eu anomalies. The Ashele basalt show an apparent Ce negative anomalies (Ce/Ce* <0.76), All the volcanic roks in Chinese Altai show the decoupled property between the high field strength elements (HFSE) and large ion lithophile elements (LILE). The negative Nb, Ta characteristics with respect to adjacent elements indicate that subduction-modified source. The Nd(t) of the hosting rocks for all orebodies changed in a small range (-1.5~5), and the (87Sr/86Sr)i change in a big range. The initial Sr value of the hosting rocks in Mengku and Tiemuerte are obviously affected by the seawater (0.705~0.710), and initial Sr values of hosting rocks Ashele change in a small range (0.704~0.706). All Sr-Nd isotopes of ores have the same range with the hosting rocks, indicating that both the ores and volcanic rocks have the same island arc source. The mean sulfur isotopes of sulfides from Ashele and Mengku are 6.2‰ and 3.4‰, respectively, indicating a deep magmatic source. However, the sulfur isotopes of sulfides from Keketale, Tiemuerte and Keyinbulake changed in -15.8‰~9.9‰, -23.5‰~1.87‰, -8.3‰~1.6‰, respectively. And the big sulfur isotope range indicated that the sulfur of the ores was a combination biogenic and magmatic source. All volcanic rocks from the VMS deposits in the southern Chinese Altai show a typical subduction related environments. Based on the regional and locally geological evidence, here we propose that the southern Chinese Altai is an island arc system, and all VMS deposits formed during the lateral accretion process. No VMS deposit formed during the formation of the island arc during Silurian; Fe VMS deposit formed during the beginning of the opening of the backarc basin in very early Devonian; Cu-Pb-Zn VMS deposits formed during the mature stage of the backarc basin in early Devonian; at last the Cu-Zn VMS deposit formed during the rifted stage of the island arc itself.

Isotopic imprints of mountaintop mining contaminants.

Mountaintop mining (MTM) is the primary procedure for surface coal exploration within the central Appalachian region of the eastern United States, and it is known to contaminate streams in local watersheds. In this study, we measured the chemical and isotopic compositions of water samples from MTM-impacted tributaries and streams in the Mud River watershed in West Virginia. We systematically document the isotopic compositions of three major constituents: sulfur isotopes in sulfate (δ(34)SSO4), carbon isotopes in dissolved inorganic carbon (δ(13)CDIC), and strontium isotopes ((87)Sr/(86)Sr). The data show that δ(34)SSO4, δ(13)CDIC, Sr/Ca, and (87)Sr/(86)Sr measured in saline- and selenium-rich MTM impacted tributaries are distinguishable from those of the surface water upstream of mining impacts. These tracers can therefore be used to delineate and quantify the impact of MTM in watersheds. High Sr/Ca and low (87)Sr/(86)Sr characterize tributaries that originated from active MTM areas, while tributaries from reclaimed MTM areas had low Sr/Ca and high (87)Sr/(86)Sr. Leaching experiments of rocks from the watershed show that pyrite oxidation and carbonate dissolution control the solute chemistry with distinct (87)Sr/(86)Sr ratios characterizing different rock sources. We propose that MTM operations that access the deeper Kanawha Formation generate residual mined rocks in valley fills from which effluents with distinctive (87)Sr/(86)Sr and Sr/Ca imprints affect the quality of the Appalachian watersheds.