Genesis of carbonate-hosted Zn-Pb deposits in the Late Indosinian thrust and fold systems: An example of the newly discovered giant Zhugongtang deposit, South China
Wei ChenZhilong HuangLin YeYusi HuM. SantoshTao WuLiang-Lun HeJiawei ZhangZhiwei HeZhenzhong XiangDa ChenChuanwei ZhuZhongguo Jin
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Devonian
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Sulfur Cycle
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Abstract In Austria the Devonian crops out south of the alpindinaric fault located in the southern part of Carinthia, north of the Yugoslavian border. It forms the base of the Mesozoic of the Southern Alps, the Carnic Alps and the Karawanken Mountains. North of this probable pre-Palaeozoic or Palaeozoic lineament Devonian rocks are found only in the region of the Upper Eastalpine nappe. There, fossiliferous Devonian sequences appear only in the central part of Carinthia, in the Palaeozoic of Graz and of the Burgenland, and at the base of the Mesozoic of the northern Limestone alps in the northern Greywacke-zone near Eisenerz (Styria) and Schwaz (Tyrol). Strong variscan and alpine movements disturbed the original connection of these Palaeozoic regions. In addition to the thick reef facies with hercynic faunal elements, particularly well-developed in the Carnic Alps and the Devonian of Eisenerz, the Devonian sequence appears also in a platform limestone facies and a basin shale facies.
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The Paleoproterozoic metasedimentary rocks of the Zaonega Formation (Onega Basin, NW Russia) are important archives of inferred global environmental change following the initial oxygenation of the Earth's atmosphere and oceans. However, the geochemical signals preserved in these exceptionally organic-and pyrite-rich metasedimentary rocks and their environmental meaning remain contested. In particular, the Zaonega Formation's unusually high pyrite sulfur isotope ratios (δ34S) have been explained by either global or local forcings acting on sulfur cycling processes. We tested former interpretations of the Zaonega Formation's sedimentary pyrite record by integrating bulk and micro-scale δ34S analysis to discriminate the isotopic signatures of different generations of pyrite and determine the underlying mechanisms contributing to δ34S variability. We show that the prolonged genesis of pyrite occurred via multiple stages and included precipitation from early diagenetic fluids, organic matter pyritization, and late-stage alteration fluids. Our results demonstrate that early-stage pyrite typically carries more variable and lower δ34S values than late-stage pyrite. Although the early pyrite captures pore water S isotope signatures least evolved from the seawater, their contribution to the bulk δ34S results can be dwarfed by the greater volume of late-stage coarse pyrite. Consequently, determining the sequence of pyrite precipitation and δ34S characteristics of individual generations in any given sample are fundamental to interpreting bulk δ34S records. Our micro-scale results suggest that previous estimates based on bulk pyrite data (ca. 6 to 18‰) should not be related to the original seawater sulfate's isotopic composition. These results demonstrate that a thorough understanding of the geological context and mechanisms associated with S-cycling, and pyrite formation is necessary to interpret bulk δ34S records accurately.
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The Howard's Pass district of sedimentary exhalative (SEDEX) Zn-Pb deposits is located in Yukon Territory and comprises 14 Zn-Pb deposits that contain an estimated 400.7 Mt of sulfide mineralization grading 4.5 % Zn and 1.5 % Pb. Mineralization is hosted in carbonaceous and calcareous and, to a lesser extent, siliceous mudstones. Pyrite is a minor but ubiquitous mineral in the host rocks stratigraphically above, within, and below mineralization. Petrographic analyses reveal that pyrite has a complex and protracted growth history, preserving multiple generations of pyrite within single grains. Sulfur isotope analysis of paragenetically complex pyrite by secondary ion mass spectrometry (SIMS) reveals that sulfur isotope compositions vary with textural zonation. Within the Zn-Pb deposits, framboidal pyrite is the earliest pyrite generation recognized, and this exclusively has negative δ34S values (mean = −16.6 ± 4.1 ‰; n = 55), whereas paragenetically later pyrite and galena possess positive δ34S values (mean = 29.1 ± 7.5 and 22.4 ± 3.0 ‰, n = 13 and 13, respectively). Previous studies found that sphalerite and galena mineral separates have exclusively positive δ34S values (mean = 16.8 ± 3.3 and 12.7 ± 2.8 ‰, respectively; Goodfellow and Jonasson 1986). These distinct sulfur isotope values are interpreted to reflect varying contributions of bacterially reduced seawater sulfate (negative; framboidal pyrite) and thermochemically reduced seawater sulfate and/or hydrothermal sulfate (positive; galena, sphalerite, later forms of pyrite). Textural evidence indicates that framboidal pyrite predates galena and sphalerite deposition. Collectively, the in situ and bulk sulfur isotope data are much more complex than δ34S values permitted by prevailing genetic models that invoke only biogenically reduced sulfur and coeval deposition of galena, sphalerite, and framboidal pyrite within a euxinic water column, and we present several lines of evidence that argue against this model. Indeed, the new data indicate that much of the base metal sulfide mineralization was emplaced below the sediment-water interface within sulfidic muds under reducing conditions during early diagenesis. Furthermore, thermochemical sulfate reduction provided most of the reduced sulfur within the Zn-Pb deposits.
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