Iron Reduction Along an Inundation Gradient in a Tidal Sedge (<Emphasis Type="Italic">Cyperus malaccensis</Emphasis>) Marsh: the Rates,Pathways, and Contributions to Anaerobic Organic Matter Mineralization

Incubation experiments were adopted to characterize the rates and pathways of iron reduction and the contributions to anaerobic organic matter mineralization in the upper 0–5 cm of sediments along a landscape-scale inundation gradient in tidal marsh sediments in the Min River Estuary, Southeast China. Similar sediment characteristics, single-species vegetation, varied biomass and bioturbation, distinct porewater pH, redox potential, and electrical conductivity values have resulted in a unique ecogeochemical zonation along the inundation gradient. Decreases in solid-phase Fe(III) and increases in nonsulfidic Fe(II) and iron sulfide were observed in a seaward direction. Porewater Fe²⁺ was only detected in the upland area. High rates of iron reduction were observed in incubation jars, with significant accumulations of nonsulfidic Fe(II), moderate accumulations of iron sulfides, and negligible accumulations of porewater Fe²⁺. Most of the iron reduction was microbially mediated rather than coupled to reduced sulfides. Microbial iron reduction accounted for 20–89 % of the anaerobic organic matter mineralization along the inundation gradient. The rate and dominance of microbial iron reduction generally decreased in a seaward direction. The contributions of microbial iron reduction to anaerobic organic matter mineralization depended on the concentrations of bioavailable Fe(III), the spatial distribution of which was significantly related to tidal inundation. Our results clearly showed that microbial iron reduction in the upper sediments along the gradient is highly dependent on spatial scales controlled primarily by tidal inundation.     

Theoretical calculation of equilibrium Mg isotope fractionation between silicate melt and its vapor

Isotope fractionation during the evaporation of silicate melt and condensation of vapor has been widely used to explain various isotope signals observed in lunar soils, cosmic spherules, calcium–aluminum-rich inclusions, and bulk compositions of planetary materials. During evaporation and condensation, the equilibrium isotope fractionation factor (α) between high-temperature silicate melt and vapor is a fundamental parameter that can constrain the melt’s isotopic compositions. However, equilibrium α is difficult to calibrate experimentally. Here we used Mg as an example and calculated equilibrium Mg isotope fractionation in MgSiO₃ and Mg₂SiO₄ melt–vapor systems based on first-principles molecular dynamics and the high-temperature approximation of the Bigeleisen–Mayer equation. We found that, at 2500 K, δ²⁵Mg values in the MgSiO₃ and Mg₂SiO₄ melts were 0.141?±?0.004 and 0.143?±?0.003‰ more positive than in their respective vapors. The corresponding δ²⁶Mg values were 0.270?±?0.008 and 0.274?±?0.006‰ more positive than in vapors, respectively. The general \(\alpha - T\) equations describing the equilibrium Mg α in MgSiO₃ and Mg₂SiO₄ melt–vapor systems were: \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.264 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\) and \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.340 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\), respectively, where m is the mass of light isotope ²⁴Mg and m′ is the mass of the heavier isotope, ²⁵Mg or ²⁶Mg. These results offer a necessary parameter for mechanistic understanding of Mg isotope fractionation during evaporation and condensation that commonly occurs during the early stages of planetary formation and evolution.     

U–Pb zircon age of the base of the Ediacaran System at the southern margin of the Qinling Orogen

Global abrupt climate change from Marinoan snowball Earth to greenhouse Earth, recorded as cap carbonate overlain on diamictite, had shed the first light on Cambrian bio-radiation. The most documented cap carbonate sections are typical with comprehensive δ¹³C negative values and ubiquitous sedimentary structures, such as tepee-like, sheet-crack etc., which are associated with successive glacial eustatic variation caused by isostatic rebound in shallow-water facies. Here we report a deep-water basinal cap carbonate section with strong negative δ¹³C values in the southern margin of the Qinling Orogen, Heyu, Chengkou County, Chongqing in China, which consists of massive dolostone with abundant carbonaceous laminae. However, it lacks the sedimentary structure as mentioned above and is overlain by thin-bedded silicious shales and cherts. A K-bentonite bed was discovered within the base of cap carbonates, about 0.7 m above the top of the Marinoan diamictite. Magmatic zircons that were separated from the K-bentonite bed yield a SIMS concordia U–Pb age of 634.1 ± 1.9 Ma (1σ, MSWD_CE = 0.31, Probability_CE = 1.000, n = 20). The age is in good agreement with previously reported TIMS U–Pb ages for the termination of Marinoan glaciation and provides a geochronological constraint for the Ediacaran successions in the Qinling Orogen.     

Effects of a proline solution cover on the geochemical and mineralogical characteristics of high-sulfur coal gangue

Batch experiments were conducted to comparatively evaluate the inhibition effects and mechanisms of a low-concentration (1%) proline solution cover on the release of pollutants from high-sulfur coal gangue. High-sulfur coal gangue was continuously immersed in a proline solution and in deionized water (as a control treatment) for 540 days. The results showed that the coal gangue in the control treatment was oxidized and generated leachate with poor water qualities, i.e., the leachate exhibited lower pH values, higher redox potential values, higher pollutant concentrations (SO₄^2?, Fe, Mn, Cu, and Zn), and high levels of acidophilic sulfur-oxidizing bacteria. However, compared to the control treatment, the addition of the proline solution (1%) significantly improved the water quality of the leachate by significantly reducing the Eh values, the pollutant concentrations (SO₄^2?, Fe²⁺, Fe, Mn, Cu, and Zn), and the activity of acidophilic sulfur-oxidizing bacteria and by significantly increasing the pH value to neutral. The proline treatment significantly inhibited the oxidation of coal gangue and the release of pollutants, mainly by inhibiting the activity of acidophilic sulfur-oxidizing bacteria and by altering the heavy metal fractions and the mineralogical characteristics. Therefore, in engineering practice, workers should consider using an environmental friendly aqueous proline solution cover to achieve the in-situ control of pollutant releases from coal gangue dumps.