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Unlike modern Mn(IV)-dominated manganese nodules, ancient manganese deposits primarily contain Mn(II) (manganous) mineral phases. The general assumption is that these manganous minerals formed post-depositionally from a Mn(IV) precursor phase during diagenesis and metamorphism. However, recent studies have shown that aqueous Mn(II) may combine with either CO 3 2– (aq) or H 4 SiO 4(aq) to nucleate and precipitate as primary manganous phases within anoxic waters. These findings thus make it difficult to assess what comprised the primary mineral assemblage of ancient Mn deposits, which in turn, has implications for understanding the redox fabric of the past marine water column. Here, we investigate the paragenesis and oxidation state of various Mn minerals (oxides, carbonates, and silicates) from the late Devonian Xialei and middle to late Permian Zunyi manganese deposits in South China. Through characterization of the micro-scale distribution, composition, and speciation of different Mn-bearing mineral phases, we provide evidence to support an oxidative mechanism during Mn cycling at the time of deposition. We document the presence of a residual oxide phase (hausmannite; Mn 3 O 4) that represents a primary to early formed Mn(III)-bearing oxide preserved in Mn(II)-carbonate nodules. Additionally, we observe spherulitic textures comprised of mixed-valence Mn(II,III,IV)-silicates enclosed in diagenetic Mn(II)-carbonate laminations. Our results allow for the construction of a paragenetic model for these deposits beginning with the reduction of a primary Mn(IV) phase and the subsequent precipitation of intermediate Mn(III)-oxide or -silicate mineral phases. Following continued exposure to reducing conditions during early diagenesis, Mn(III)-oxides were then replaced by Mn(II)-carbonates. Similarly, Mn(III)-silicates were transformed into various Mn(II)-silicates during late-stage diagenesis and metamorphism. This model suggests that the accumulation of various divalent Mn mineral phases in ancient sediments may, therefore, be indicative of deposition under a water column with a sufficient oxidizing potential to induce Mn(II) oxidation. [ABSTRACT FROM AUTHOR]

Travertines are potential archives of continental paleoclimate. Records of stable carbon and oxygen isotopic composition (δ 13 C and δ 18 O) in laminated travertine deposits from endogene spring waters show regular cyclic patterns which may be due to seasonal change in climate determinants such as temperature and rainfall. In this study, δ 13 C and δ 18 O measurements of three travertine specimens that grew naturally over the eight years, 2004–2011, at upstream, middle and downstream sites in a canal at Baishuitai, SW China, are presented. They exhibit clear seasonal variations that generally correlate with biannual laminations. Specifically, δ 13 C and δ 18 O values show significant positive correlation with each other for the three travertine specimens, with the correlation coefficients increasing downstream along the canal. To reveal the factors governing the seasonal and spatial variations in δ 13 C and δ 18 O values, newly formed travertines precipitated on Plexiglas substrates are also examined. Both δ 13 C and δ 18 O of the substrate travertines are low in the summer/rainy season and high in the winter/dry season, showing a great consistency with the patterns in the natural travertines. Spatially, isotope values increase downstream in both seasons, with higher increase rates in winter that are related to removal of larger fractions of dissolved inorganic carbon (DIC) from the solution and stronger kinetic isotopic fractionation in winter. Due to in-stream physicochemical processes, including CaCO 3 precipitation and the associated degassing of CO 2 , seasonal changes in δ 13 C and δ 18 O in the travertines are amplified by two times between the upstream and downstream sites: this is opposite to trends for epigene (meteogene) tufas whose seasonal changes in stable isotope compositions are reduced downstream. We suggest in-stream physicochemical processes are a potential reason for underestimation of annual temperature ranges that are inferred from epigene tufa δ 18 O data. [ABSTRACT FROM AUTHOR]