The Structure of CaSO4 Nanorods: The Precursor of Gypsum

© 2019 American Chemical Society. Understanding the gypsum (CaSO4·2H2O) formation pathway from aqueous solution has been the subject of intensive research in the past years. This interest stems from the fact that gypsum appears to fall into a broader category of crystalline materials whose formation does not follow classical nucleation and growth theories. The pathways involve transitory precursor cluster species, yet the actual structural properties of such clusters are not very well understood. Here, we show how in situ high-energy X-ray diffraction experiments and molecular dynamics (MD) simulations can be combined to derive the structure of small CaSO4 clusters, which are precursors of crystalline gypsum. We fitted several plausible structures to the derived pair distribution functions and explored their dynamic properties using unbiased MD simulations based on both rigid ion and polarizable force fields. Determination of the structure and (meta)stability of the primary species is important from both a fundamental and applied perspective; for example, this will allow for an improved design of additives for greater control of the nucleation pathway

Authigenic minerals reflect microbial control on pore waters in a ferruginous analogue

Ferruginous conditions prevailed in the oceans through much of Earth's history. However, minerals recording these conditions remain difficult to interpret in terms of biogeochemical processes prior to lithification. In Lake Towuti, Indonesia, ferruginous sediments are deposited under anoxic sulfate-poor conditions similar to the Proterozoic oceans, allowing the study of mineralogical (trans)formations during microbial diagenesis. Comprehensive pore water geochemistry, high resolution geochemical core profiles, and electron microscopy of authigenic minerals revealed in situ formation of magnetite, millerite, and abundant siderite and vivianite along a 100 m long sequence. Framboidal magnetites represent primary pelagic precipitates, whereas millerite, a sulfide mineral often overlooked under sulfate-poor conditions, shows acicular aggregates entangled with siderite and vivianite resulting from saturated pore waters and continuous growth during burial. These phases act as biosignatures of microbial iron and sulfate reduction, fermentation and methanogenesis, processes clearly traceable in pore water profiles. Variability in metal and organic substrates attests to environment driven processes, differentially sustaining microbial processes along the stratigraphy. Geochemical profiles resulting from microbial activity over 200 kyr after deposition provide constraints on the depth and age of mineral formation within ferruginous records

Bacterially mediated removal of phosphorus and cycling of nitrate and sulfate in the waste stream of a "zero-discharge" recirculating mariculture system

Simultaneous removal of nitrogen and phosphorus by microbial biofilters has been used in a variety of water treatment systems including treatment systems in aquaculture. In this study, phosphorus, nitrate and sulfate cycling in the anaerobic loop of a zero-discharge, recirculating mariculture system was investigated using detailed geochemical measurements in the sludge layer of the digestion basin. High concentrations of nitrate and sulfate, circulating in the overlying water (~15 mM), were removed by microbial respiration in the sludge resulting in a sulfide accumulation of up to 3 mM. Modelling of the observed S and O isotopic ratios in the surface sludge suggested that, with time, major respiration processes shifted from heterotrophic nitrate and sulfate reduction to autotrophic nitrate reduction. The much higher inorganic P content of the sludge relative to the fish feces is attributed to conversion of organic P to authigenic apatite. This conclusion is supported by: (a) X-ray diffraction analyses, which pointed to an accumulation of a calcium phosphate mineral phase that was different from P phases found in the feces, (b) the calculation that the pore waters of the sludge were highly oversaturated with respect to hydroxyapatite (saturation index = 4.87) and (c) there was a decrease in phosphate (and in the Ca/Na molar ratio) in the pore waters simultaneous with an increase in ammonia showing there had to be an additional P removal process at the same time as the heterotrophic breakdown of organic matter

Glacier algae accelerate melt rates on the western Greenland Ice Sheet

Melting of the Greenland Ice Sheet (GrIS) is the largest single contributor to eustatic sea level and is amplified by the growth of pigmented algae on the ice surface that increase solar radiation absorption. This biological albedo reducing effect and its impact upon sea level rise has not previously been quantified. Here, we combine field spectroscopy with a novel radiative transfer model, supervised classification of UAV and satellite remote sensing data and runoff modelling to calculate biologically-driven ice surface ablation and compare it to the albedo reducing effects of local mineral dust. We demonstrate that algal growth led to an additional 5.5–8.0 Gt of runoff from the western sector of the GrIS in summer 2016, representing 6–9 % of the total. Our analysis confirms the importance of the biological albedo feedback and that its omission from predictive models leads to the systematic underestimation of Greenland’s future sea level contribution, especially because both the bare ice zones available for algal colonization and the length of the active growth season are set to expand in the future

<i>In-situ</i> grown silica sinters in Icelandic geothermal areas

Field in-situ sinter growth studies have been carried out in five geochemically very different Icelandic geothermal areas with the aim to quantify the effects of water chemistry, (e.g. silica content (250 to 695 p.p.m. SiO2), salinity (meteoric to seawater), pH (7.5 to 10)), temperature (42-96°C) and microbial abundance (prevalence, density) on the growth rates, textures and structures of sinters forming within and around geothermal waters. At each location, sinter growth was monitored over time periods between 30 min and 25 months using glass slides that acted as precipitation substrates from which sinter growth rates were derived. In geothermal areas like Svartsengi and Reykjanes, subaqueous sinters developed rapidly with growth rates of 10 and 304 kg year−1 m−2, respectively, and this was attributed primarily to the near neutral pH, high salinity and medium to high silica content within these geothermal waters. The porous and homogeneous precipitates that formed at these sites were dominated by aggregates of amorphous silica and they contained few if any microorganisms. At Hveragerdi and Geysir, the geothermal waters were characterized by slightly alkaline pH, low salinity and moderate silica contents, resulting in substantially lower rates of sinter growth (0.2-1.4 kg year−1 m−2). At these sites sinter formation was restricted to the vicinity of the air-water interface (AWI) where evaporation and condensation processes predominated, with sinter textures being governed by the formation of dense and heterogeneous crusts with well-defined spicules and silica terraces. In contrast, the subaqueous sinters at these sites were characterized by extensive biofilms, which, with time, became fully silicified and thus well preserved within the sinter edifices. Finally, at Krafla, the geothermal waters exhibited high sinter growth rates (19.5 kg year−1 m−2) despite being considerably undersaturated with respect to amorphous silica. However, the bulk of the sinter textures and structure were made up of thick silicified biofilms and this indicated that silica precipitation, i.e. sinter growth, was aided by the surfaces provided by the thick biofilms. These results further suggest that the interplay between purely abiotic processes and the ubiquitous presence of mesophilic and thermophilic microorganisms in modern silica rich terrestrial hydrothermal settings provides an excellent analogue for processes in Earth's and possibly Mars's ancient past