Post-depositional diagenetic alteration makes the accurate interpretation of key precipitation processes in ancient sediments, such as Precambrian banded iron formations (BIFs), difficult. While microorganisms are proposed as key contributors to BIF deposition, the diagenetic transformation of precursor Fe(III) minerals associated with microbial biomass had not been experimentally tested. We incubated mixtures of ferrihydrite (proxy for biogenic ferric oxyhydroxide minerals) and glucose (proxy for microbial biomass) in gold capsules at 1.2 kbar and 170°C. Both wet chemical analysis and mineralogical methods (microscopy, X-ray diffraction and Mössbauer spectroscopy) were used to analyze the reaction products. Under these conditions, ferrihydrite (Fe III(OH)3) transforms to hematite (Fe2IIIO3), magnetite (FeIIFe2IIIO4), and siderite (FeIICO3). Silica-coated ferrihydrite prepared at conservative Si:Fe ratios (as predicted for the Precambrian oceans) and mixed with glucose yielded hematite and siderite, whereas magnetite could not be identified microscopically. Our results show that electron transfer from organic carbon to Fe(III) minerals during temperature/pressure diagenesis can drive the production of key BIF minerals. Our results also demonstrate that the post-depositional mineralogy of BIF does not directly archive the oceanic or atmospheric conditions present on Earth during their lithification. As a consequence, atmospheric composition regarding concentrations of methane and CO2 during the time of BIF mineral deposition cannot be directly inferred from BIF mineralogical data alone
During deposition of Precambrian iron formation, the combined sedimentation of ferrihydrite and phytoplankton biomass should have facilitated Fe(III) reduction during diagenesis. However, the only evidence for this reaction in iron formations is the iron and carbon isotope values preserved in the authigenic ferrous iron-containing minerals. Here we show experimentally that spheroidal siderite, which is preserved in many iron formation and could have been precursor to rhombohedral or massive siderite, forms by reacting ferrihydrite with glucose (a proxy for microbial biomass) at pressure and temperature conditions typical of diagenesis (170°C and 1.2 kbar). Depending on the abundance of siderite, we found that it is also possible to draw conclusions about the Fe(III):C ratio of the initial ferrihydrite-biomass sediment. Our results suggest that spherical to rhombohedral siderite structures in deepwater, Fe-oxide iron formation can be used as a biosignature for photoferrotrophy, whereas massive siderite reflects high cyanobacterial biomass loading in highly productive shallowwaters.
Past orbital parameters of the Moon are difficult to reconstruct from geological records because relevant data sets of tidal strata are scarce or incomplete. The sole Archean data point is from the Moodies Group (ca 3.22 Ga) of the Barberton Greenstone Belt, South Africa. From the time‐series analysis of tidal bundles from a well‐exposed subaqueous sand wave of this unit, Eriksson and Simpson (Geology, 28, 831) suggested that the Moon’s anomalistic month at 3.2 Ga was closer to 20 days than the present 27.5 days. This is in apparent accordance with models of orbital mechanics which place the Archean Moon in a closer orbit with a shorter period, resulting in stronger tidal action. Although this study’s detailed geological mapping and section measuring of the site confirmed that the sandstone bed in question is likely a migrating dune, the presence of angular mud clasts, channel‐margin slumps, laterally aggrading channel fills and bidirectional paleocurrents in overlying and underlying beds suggests that this bedform was likely located in a nearshore channel near lower‐intertidal flats and subtidal estuarine bars; it thus carries risk of incomplete preservation. Repeated measurements of foreset thicknesses along the published traverse, measured perpendicular to bedding, failed to show consistent spectral peaks. Larger data sets acquired along traverses measured parallel to bedding along the 20.5 m wide exposure are affected by minor faulting, uneven outcrop weathering, changing illumination, weather, observer bias and show a low reproducibility. The most robust measurements herein confirm the periodicity peak of approximately 14 in the original data of Eriksson and Simpson (Geology, 28, 831). Because laminae may have been eroded, the measurements may represent a lower bound of about 28 lunar days per synodic month. This estimate agrees well with Earth–Moon dynamic models which consider the conservation of angular momentum and place the Archaean Moon in a lower orbit around a faster‐spinning Earth.
Biogeochemistry investigates chemical cycles which influence or are influenced by biological activity. Astrobiology studies the origin, evolution and distribution of life in the universe. The biogeochemical Fe cycle has controlled major nutrient cycles such as the C cycle throughout geological time. Iron sulfide minerals may have provided energy and surfaces for the first pioneer organisms on Earth. Banded iron formations document the evolution of oxygenic photosynthesis. To assess the potential habitability of planets other than Earth one looks for water, an energy source and a C source. On Mars, for example, Fe minerals have provided evidence for the past presence of liquid water on its surface and would provide a viable energy source. Here we present Mössbauer spectroscopy investigations of Fe and C cycle interactions in both ancient and modern environments. Experiments to simulate the diagenesis of banded iron formations indicate that the formation of ferrous minerals depends on the amount of biomass buried with ferric precursors rather than on the atmospheric composition at the time of deposition. Mössbauer spectra further reveal the mutual stabilisation of Fe-organic matter complexes against mineral transformation and decay of organic matter into CO2. This corresponds to observation of a ‘rusty carbon sink’ observed in modern sediments. The stabilisation of Fe-organic matter may also aid transport of particulate Fe in the water column while having on adverse effect on the bioavailability of Fe. In the modern oxic ocean, Fe is insoluble and particulate Fe represents an important source. Collecting that particulate Fe yields small sample sizes that would pose a challenge for conventional Mössbauer experiments. We demonstrate that the unique properties of the beam used in synchrotron-based Mössbauer applications can be utilized for studying such samples effectively. Reactive Fe species often occur in amorphous or nanoparticulate form in the environment and are therefore difficult to study with standard mineralogical tools. Sequential extraction techniques are commonly used as proxies. We provide an example where Mössbauer spectroscopy can replace sequential extraction techniques where mineralogical information is sought. Where mineral separation is needed, for example in the investigation of Fe or S isotope fractionation, Mössbauer spectroscopy can help to optimize sequential extraction procedures. This can be employed in large number of investigations of soils and sediments, potentially even for mineral separation to study Fe and S isotope fractionation in samples returned from Mars, which might reveal signatures of biological activity. When looking for the possibility of life outside Earth, Jupiter’s icy moon Europa is one of the most exciting places. It may be just in reach for a Mössbauer spectrometer deployed by a future lander to study the red streak mineral deposits on its surface to look for clues about the composition of the ocean hidden under the moon’s icy surface
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