Organo-mineral associations in chert of the 3.5 Ga Mount Ada Basalt raise questions about the origin of organic matter in Paleoarchean hydrothermally influenced sediments.

Hydrothermal and metamorphic processes could have abiotically produced organo-mineral associations displaying morphological and isotopic characteristics similar to those of fossilized microorganisms in ancient rocks, thereby leaving false-positive evidence for early life in the geological record. Recent studies revealed that geologically-induced alteration processes do not always completely obliterate all molecular information about the original organic precursors of ancient microfossils. Here, we report the molecular, geochemical, and mineralogical composition of organo-mineral associations in a chert sample from the ca. 3.47 billion-year-old (Ga) Mount Ada Basalt, in the Pilbara Craton, Western Australia. Our observations indicate that the molecular characteristics of carbonaceous matter are consistent with hydrothermally altered biological organics, although significantly distinct from that of organic microfossils discovered in a chert sample from the ca. 3.43 Ga Strelley Pool Formation in the same area. Alternatively, the presence of native metal alloys in the chert, previously believed to be unstable in such hydrothermally influenced environments, indicates strongly reducing conditions that were favorable for the abiotic formation of organic matter. Drawing definitive conclusions about the origin of most Paleoarchean organo-mineral associations therefore requires further characterization of a range of natural samples together with experimental simulations to constrain the molecular composition and geological fate of hydrothermally-generated condensed organics.

The interfacial reactivity of arsenic species with green rust sulfate (GRSO4).

Arsenic (As) contamination in groundwater is a significant health and environmental concern worldwide because of its wide distribution and toxicity. The fate and mobility of As is greatly influenced by its interaction with redox-active mineral phases, among which green rust (GR), an FeII-FeIII layered double hydroxide mineral, plays a crucial role. However, the controlling parameters of As uptake by GR are not yet fully understood. To fill this gap, we determined the interfacial reactions between GR sulfate (GRSO4) and aqueous inorganic As(III) and As(V) through batch adsorption experiments, under environmentally-relevant groundwater conditions. Our data showed that, under anoxic conditions, GRSO4 is a stable and effective mineral adsorbent for the removal of As(III) and As(V). At an initial concentration of 10 mg L-1, As(III) removal was higher at alkaline pH conditions (~95% removal at pH 9) while As(V) was more efficiently removed at near-neutral conditions (>99% at pH 7). The calculated maximum As adsorption capacities on GRSO4 were 160 mg g-1 (pH 8-9) for As(III) and 105 mg g-1 (pH 7) for As(V). The presence of other common groundwater ions such as Mg2+ and PO43- reduces the efficiency of As removal, especially at high ionic strengths. Long-term batch adsorption experiments (up to 90 days) revealed that As-interacted GRSO4 remained stable, with no mineral transformation or release of adsorbed As species. Overall, our work shows that GRSO4 is one of the most effective As adsorbents among iron (oxyhydr)oxide phases.

Magnesium Stable Isotope Fractionation on a Cellular Level Explored by Cyanobacteria and Black Fungi with Implications for Higher Plants.

In a controlled growth experiment we found that the cyanobacterium Nostoc punctiforme has a bulk cell 26Mg/24Mg ratio (expressed as δ26Mg) that is -0.27‰ lower than the growth solution at a pH of ca. 5.9. This contrasts with a recently published δ26Mg value that was 0.65‰ higher than growth solution for the black fungus Knufia petricola at similar laboratory conditions, interpreted to reflect loss of 24Mg during cell growth. By a mass balance model constrained by δ26Mg in chlorophyll extract we inferred the δ26 Mg value of the main Mg compartments in a cyanobacteria cell: free cytosolic Mg (-2.64‰), chlorophyll (1.85‰), and the nonchlorophyll-bonded Mg compartments like ATP and ribosomes (-0.64‰). The lower δ26Mg found in Nostoc punctiforme would thus result from the absence of significant Mg efflux during cell growth in combination with either (a) discrimination against 26Mg during uptake by desolvation of Mg or transport across protein channels or (b) discrimination against 24Mg in the membrane transporter during efflux. The model predicts the preferential incorporation of 26Mg in cells and plant organs low in Mg and the absence of isotope fractionation in those high in Mg, corroborated by a compilation of Mg isotope ratios from fungi, bacteria, and higher plants.

Mg Isotope Fractionation during Uptake by a Rock-Inhabiting, Model Microcolonial Fungus Knufia petricola at Acidic and Neutral pH.

The model rock-inhabiting microcolonial fungus Knufia petricola fractionates stable Mg isotopes in a time- and pH-dependent manner. During growth, the increase of 26Mg/24Mg in the fungal cells relative to the growth media amounted to 0.65 ± 0.14‰ at pH 6 and 1.11 ± 0.35‰ at pH 3. We suggest a constant equilibrium fractionation factor during incorporation of Mg into ribosomes and ATP as a cause of enrichment of 26Mg in the cells. We suggest too that the proton gradient across the cell wall and cytoplasmic membrane controls Mg2+ transport into the fungal cell. As the strength of this gradient is a function of extracellular solution pH, the pH-dependence on Mg isotope fractionation is thus due to differences in fungal cell mass fluxes. Through a mass balance model we show that Mg uptake into the fungal cell is not associated with a unique Mg isotope fractionation factor. This Mg isotope fractionation dependence on pH might also be observed in any organism with cells that follow similar Mg uptake and metabolic pathways and serves to reveal Mg cycling in ecosystems.

Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the µg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous stable isotope measurement and chemical composition analysis LASS-ICP-MS in combination with MC-ICP-MS is the method of choice.