Search

The sulfate-methane transition zone (SMTZ) serves as an important geochemical transition especially during early diagenesis. Organoclastic sulfate reduction (OSR), sulfate-driven anaerobic oxidation of methane (SD-AOM), fermentation, and methanogenesis, the dominant diagenetic processes near the SMTZ, play key roles in marine sulfur and carbon cycling. However, the paleo-SMTZ has rarely been identified in the geologic record because of equivocal evidence. The presence of barite-calcite-pyrite assemblages (abundant nodules and pyritic laminae) concentrated over a 1-m thick interval of the Silurian Longmaxi Formation, Yangtze Block, South China, provide a unique opportunity to investigate possible vertical movements of the paleo-SMTZ in ancient sediments. The inferred paleo-SMTZ comprises nodules made up of barite (BaSO 4), calcium carbonate (CaCO 3), and pyrite (FeS 2), and pyritic laminae. Strong 34S enrichment of barite (50 to 62.1‰ VCDT) and modestly 13C-depleted calcite (−11.4‰ to −5.3 VPDB) of the nodules associated with positive δ34S values of pyritic laminae (4 to 6.2‰ VCDT) suggest precipitation of these minerals sourced by mixed carbon and sulfur sources close to and/or within the paleo-SMTZ. Nodules from center to edge display mineral zonation that may reflect the effects of depth fluctuations of the paleo-SMTZ. Initial (stage 1) barite mineralization in nodule centers appears to have occurred within the base of the sulfate reduction zone (SRZ). By the time if stage 2 mineralization, the stratigraphic locus of precipitation had migrated closer to highly alkaline SMTZ resulting in barite dissolution and calcium carbonate precipitation. Higher proportions of calcium carbonate exhibiting some enrichment of 12C associated with cubic pyrite crystals in nodule centers are consistent with the occurrence of SD-AOM within the SMTZ. Stage 3 acicular barite mineralization along nodule edges likely took place near at the base of SRZ immediately above the SMTZ, whereas the replacement of barite by calcite during stage 4 mineralization occurred again within the SMTZ. Vertical movement of paleo-SMTZs suggested by the occurrences of barite-calcite-pyrite assemblages in the Longmaxi Formation across Yangtze Block, are likely the consequence of the complex interplay of varying sedimentation rate, organic matter quality, methane flux, and perhaps seawater sulfate concentration. • Barite-calcite-pyrite assemblages of the Longmaxi Formation were formed near the sulfate–methane transition zone (SMTZ). • Nodule growth occurs concentrically so that changes in mineralization plausibly record vertical movements of SMTZ. • Multiple factors controlled the spatial distribution of SMTZ in the Longmaxi Formation across Yangtze Block. [ABSTRACT FROM AUTHOR]

The Llandovery epoch (Early Silurian) was marked by the interruption of widespread oceanic anoxia and associated oxygenation of seawater. The first oxygenation event appears to occur near the Rhuddanian–Aeronian stages boundary. However, ventilation of the marine environments is a dynamic process, differing in timing and magnitude from place to place, basic variations in the nature of marine circulation; e.g., open shelf versus restricted shelf. The correlation of oxygenation events from open to restricted shelf environments is of significance to enhancing our understanding of marine ventilation processes. Here, we describle nodular barite that accumulated in the open marine environment near the boundary at the northern margin of the Yangtze Block, South China, emphasizing its origin and environmental implications. Petrographic evidence suggests that the nodular barite is early diagenetic. Barium was likely derived from the dissolution of biogenic barite as suggested by the 87Sr/86Sr values of the diagenetic barite. The REE + Y pattern, low Y/Ho and high Ce*/Ce values of the barite nodules demonstrate that microbial degradation of organic matter in association with Ce oxidation controlled REE composition of the nodules. PAAS-normalized positive Eu anomalies of the studied barite, however, suggest an anoxic porewater environment perhaps related to bacterial sulfate reduction or the anaerobic oxidation of methane focused within the sulfate-methane transition zone (SMTZ) as also indicated by the minor contribution of radiogenic terrigenous Sr isotopes. We infer that high marine productivity and the associated transport of biogenic barite to the sea floor was critical to the formation of the studied barite nodules. Diagenetic barite formation and preservation in Aeronian stage deposits may indicate that circulation of open marine water masses had been much ameliorated. Our results are consistent with earlier suggestions that the restricted shelf experienced a transition from anoxic or even euxinic conditions to a more oxygenated (probably suboxic) condition during the early Aeronian. The approximately contemporaneous nature of this transition and global cooling associated with the glacial pulses indicate the critical role that global climate change near the Rhuddanian–Aeronian (R-A) boundary played in the redox evolution of the Yangtze Block, South China. • A diagenetic model for Llandovery nodular barite formation was established. • The different style of barite formed at a fluctuating sulfate methane transition zone. • Diagenetic barite precipitation implicates Llandovery paleoenvironmental changes. • Global climate had an important role in the Llandovery Yangtze Block redox evolution. [ABSTRACT FROM AUTHOR]