Grain-scale iron isotopic distribution of pyrite from Precambrian shallow marine carbonate revealed by a femtosecond laser ablation multicollector ICP-MS technique: Possible proxy for the redox state of ancient seawater

The redox state of Precambrian shallow seas has been linked with material cycle and evolution of the photosynthesis-based ecosystem. Iron is a redox-sensitive element and exists as a soluble Fe(II) species or insoluble Fe(III) species on Earth’s surface. Previous studies have shown that the iron isotopic ratio of marine sedimentary minerals is useful for understanding the ocean redox state, although the redox state of the Archean shallow sea is poorly known. This is partly because the conventional bulk isotope analytical technique has often been used, wherein the iron isotopic record may be dampened by the presence of isotopically different iron-bearing minerals within the same sample. Here we report a microscale iron isotopic ratio of individual pyrite grains in shallow marine stromatolitic carbonates over geological time using a newly developed, near-infrared femtosecond laser ablation multicollector ICP-MS technique (NIR-fs-LA-MC-ICP-MS).We have determined that the grain-scale iron isotopic distribution of pyrite from coeval samples shows a bimodal (2.7 and 2.3 Ga) or unimodal pattern (2.9, 2.6, and 0.7 Ga). In particular, pyrite from the 2.7 Ga Fortescue Group shows a unique bimodal distribution with highly positive (+1.0‰ defined as Type 1) and negative δ⁵⁶Fe values (−1.8‰ defined as Type 2). Type 1 and 2 pyrites occasionally occur within different siliceous layers in the same rock specimen. Layer-scale iron isotopic heterogeneity indicates that the iron isotopic ratios of the two types of pyrite are not homogenized by diagenesis after deposition. Some cubic pyrites have a core with a positive δ⁵⁶Fe value (1‰) and a rim with a crustal δ⁵⁶Fe value (0‰). The observed isotopic zoning suggests that the positive δ⁵⁶Fe value is a primary signature at the time of stromatolite formation, while secondary pyrite precipitated during diagenesis.The positive δ⁵⁶Fe value of Type 1 and the large iron isotopic difference between Type 1 and 2 (2.8‰.) suggest partial Fe(II) oxidation in the 2.7-Ga shallow sea, i.e., pyritization of ⁵⁶Fe-enriched ferric oxyhydroxide (Type 1) and ⁵⁶Fe depleted Fe²⁺aq in seawater (Type 2). Type 2 pyrite was probably not produced by microbial iron redox cycling during diagenesis because this scenario requires a higher abundance of pyrite with δ⁵⁶Fe of 0‰ than of −1.8‰. Consequently, the degree of Fe(II) oxidation in the 2.7-Ga shallow sea can be estimated by a Fe²⁺aq steady-state model. The model calculation shows that half the Fe²⁺aq influx was oxidized in the seawater. This implies that O₂ produced by photosynthesis would have been completely consumed by oxidation of the Fe²⁺aq influx. Grain-scale iron isotopic distribution of pyrite could be a useful index for reconstructing the redox state of the Archean shallow sea.     

Geochemistry of the oldest MORB and OIB in the Isua Supracrustal Belt, southern West Greenland: Implications for the composition and temperature of early Archean upper mantle

Abstract Recent geological investigations of the Isua Supracrustal Belt (3.8 Ga), southern West Greenland, have suggested that it is the oldest accretionary complex on earth, defined by an oceanic plate‐type stratigraphy and a duplex structure. Plate history from mid‐oceanic ridge through plume magmatism to subduction zone has been postulated from analysis of the reconstructed oceanic plate stratigraphy in the accretionary complex. Comparison between field occurrence of greenstones in modern and ancient accretionary complexes reveals that two types of tholeiitic basalt from different tectonic settings, mid‐oceanic ridge basalt (MORB) and oceanic island basalt (OIB), occur. This work presents major, trace and rare earth element (REE) compositions of greenstones derived from Isua MORB and OIB, and of extremely rare relict igneous clinopyroxene in Isua MORB. The Isua clinopyroxenes (Cpx) have compositional variations equivalent to those of Cpx in modern MORB; in particular, low TiO₂ and Na₂O contents. The Isua Cpx show slightly light (L)REE‐depleted REE patterns, and the calculated REE pattern of the host magma is in agreement with that of Isua MORB. Analyses of 49 least‐altered greenstones carefully selected from approximately 1200 samples indicate that Isua MORB are enriched in Al₂O₃, and depleted in TiO₂, FeO*, Y and Zr at the given MgO content, compared with Isua OIB. In addition, Isua MORB show an LREE‐depleted pattern, whereas Isua OIB forms a flat REE pattern. Such differences suggest that the Early Archean mantle had already become heterogeneous, depending on the tectonic environment. Isua MORB are enriched in FeO compared with modern MORB. Comparison of Isua MORB with recent melting experiments shows that the source mantle had 85–87 in Mg? and was enriched in FeO. Potential mantle temperature is estimated to be approximately 1480°C, indicating that the Early Archean mantle was hotter by at most approximately 150°C than the modern mantle.     

Anomalous content of chromium in a Cretaceous sandstone aquifer of the Bauru Basin,state of São Paulo,Brazil

Anomalous and natural concentrations of Cr⁶⁺, occasionally exceeding the permitted limit for human consumption (0.05 mg/L), have been detected in groundwater in the northwestern region of the state of São Paulo. As part of a water-rock interaction investigation, this article describes the chemical and mineralogical characterization of rock samples taken from boreholes in the municipality of Urânia, with the objective of identifying Cr-bearing minerals and determining how chromium is associated with these minerals. Rock sample analysis were performed using X-ray Fluorescence, X-ray Diffraction, Scanning Electron Microscopy, electron microprobe and sequential extraction techniques. Chemical analyses indicated that the quartzose sandstones show a geochemical anomaly of chromium, with an average content of 221 ppm, which is higher than the reported chromium content of generic sandstones (35 ppm). Diopside was identified as the primary Cr-bearing mineral potentially subject to weathering processes, with a chromium content of up to 1.2% as Cr₂O₃. Many of the diopside grains showed dissolution features, confirming the occurrence of weathering. Sequential extraction experiments indicated that 99.3% of the chromium in samples is tightly bonded to minerals, whereas 0.24% is weakly bonded via adsorption. Assuming hypothetically that all adsorbed chromium is released via desorption, the theoretical Cr concentration in water would be one order of magnitude higher than the concentrations of Cr⁶⁺ detected in groundwater.     

Internal structures and U–Pb ages of zircons from a tuff layer in the Meishucunian formation, Yunnan Province, South China

The Precambrian/Cambrian (PC/C) boundary is one of the most important intervals for the evolution of life, represented by prominent biological evolution from the first appearance of soft-bodied animals from the late Neoproterozoic to the sudden diversification of animals with mineralized skeletons in the Cambrian. In South China several areas contain many fossils and are well exposed, suitable for the investigation of PC/C boundary. However, geochronological relationships are still poorly known because of lack of combined detailed investigations of internal structures of zircons and in-situ U–Pb dating.We focus on the internal structure of zircons from a tuff layer within Bed 5 in the Meishucun section on which we undertook cathodoluminescence (CL) imaging and in-situ U–Pb dating with LA-ICP-MS and nano-SIMS. Over 600 zircons from the tuff layer were classified into three types based on their CL images: oscillatory rims, inherited cores and dull structures. U–Pb dating of the internal structure of the zircons by LA-ICP-MS clearly shows a distinct unimodal age population dependent on the structure: 531 ± 17 Ma for the oscillatory rims and 515 Ma for the dull structures. The clear oscillatory zonation, the prismatic morphology, and their occurrence indicate that the oscillatory rims were formed from felsic magmatism, and that the U–Pb nano-SIMS age of 536.5 ± 2.5 Ma records the depositional age of the tuff. Our results indicate that the PC/C boundary is situated below Bed 5, and therefore the bottom of Zone 1 (Marker A) is more appropriate for the PC/C boundary than is the top of Zone 1 (Marker B). The age of a positive anomaly (P2) in the early Cambrian is estimated to be ca. 536 Ma.     

Incorporation of U,Pb and Rare Earth Elements in Calcite through Crystallisation from Amorphous Calcium Carbonate: Simple Preparation of Reference Materials for Microanalysis

Uncertainty for elemental and isotopic measurements in calcite by LA‐ICP‐MS is largely controlled by the homogeneity of the reference materials (RMs) used for calibration and validation. In order to produce calcite RMs with homogeneous elemental and isotopic compositions, we incorporated elements including U, Pb and rare earth elements into calcite through heat‐ and pressure‐induced crystallisation from amorphous calcium carbonate that was precipitated from element‐doped reagent solution. X‐ray absorption spectra showed that U was present as U(VI) in the synthesised calcite, probably with a different local structure from that of aqueous uranyl ions. The uptake rate of U by our calcite was higher in comparison with synthetic calcite of previous studies. Variations of element mass fractions in the calcite were better than 12% 2RSD, mostly within 7%. The ²⁰⁷Pb/²⁰⁶Pb ratio in the calcite showed < 1% variations, while the ²³⁸U/²⁰⁶Pb ratio showed 3–24% variations depending on element mass fractions. Using the synthetic calcite as primary RMs, we could date a natural calcite RM, WC‐1, with analytical uncertainty as low as < 3%. The method presented can be useful to produce calcite with controlled and homogeneous element mass fractions and is a promising alternative to natural calcite RMs for U‐Pb geochronology.     

Global mapping of the degree of space weathering on asteroid 25143 Itokawa by Hayabusa/AMICA observations

Abstract— We obtained color images of near‐Earth asteroid 25143 Itokawa by the Hayabusa multiband imaging camera to characterize the regional color properties. Images were obtained for the whole disk from the gate position (GP) and home position (HP) at a spatial resolution of 0.8–3.7 m/pixel. Whole‐disk spectra are adjusted to the telescopic data obtained by the University of Hawai'i's 88‐inch telescope using the Eight Color Asteroid Survey (ECAS) system. The disk‐resolved measurements show large variations in the three visible channels. We present a map of an index related to the degree of space weathering, which has been newly developed based on laboratory measurements. We find large variations in the degree of space weathering on Itokawa. Fresh materials are observed in regions of steep slopes and craters, whereas mature materials are ubiquitously distributed. This result suggests that pristine ordinary chondrite‐like materials have been exposed through weathered layers by excavation. By also examining close‐up images obtained during touchdown rehearsal, we find that most rocks in Itokawa's rough terrains are weathered. Instead of a regolith blanket, the surface of this small asteroid is covered with weathered rocks and gravels.     

Rhenium and osmium systematics on iron and stony iron meteorites

Abstract— Re and Os abundances and ¹⁸⁷Os/¹⁸⁶Os isotopic ratios in 12 iron meteorites of various groups and five stony iron meteorites have been determined by an inductively coupled plasma mass spectrometry (ICP-MS). The series of iron meteorites studied have Re and Os concentrations ranging from 0.004 to 3.3 ppm and 0.03 to 41 ppm, respectively. The ¹⁸⁷Re/¹⁸⁶Os ratios in these meteorites fall between 3.0 and 6.1 and the ¹⁸⁷Os/¹⁸⁶Os between 1.0 and 1.2, giving an initial ¹⁸⁷Os/¹⁸⁶Os isotopic ratio of 0.790 and a Re-Os age of iron meteorites of 4.30 ± 0.28 Ga when employing the decay constant of 1.64 × 10^?11 yr^?1. The observed Re-Os age for iron meteorites appears somewhat younger than that for chondrites. The resultant younger age might be due either to a very slow cooling of the parental planetesimals or due to a secondary “shock” event. However, for definite conclusions about the Re-Os age, higher precisions of the Re and Os isotopic measurements and of the decay constant of ¹⁸⁷Re are required. Furthermore, the clear elucidation of the mechanisms for the fractionation of the Re/Os abundance ratios are related to the understanding of the meaning of the Re-Os age. The Re and Os abundances in pallasite stony iron meteorites are extremely low compared with those for most iron meteorites. On the other hand, the Re and Os abundances in mesosiderite stony iron meteorites show values comparable with those observed in most iron meteorites. The difference in Re and Os abundances in pallasite and mesosiderite stony iron meteorites strongly suggests that these stony iron meteorites are different in origin or history of chemical evolution. Re and Os abundances in the series of iron and stony iron meteorites were found to have a wide variation covering nearly four orders of magnitude, with a very high correlation coefficient (0.996), and a slope very slightly less than unity. The regression line observed here covers various groups of iron meteorites, stony iron meteorites and also chondrites. Masuda and Hirata (1991) suggested the possible direct mixing process of particles of most refractory metallic elements with gaseous clouds of less refractory matrix elements, since the Re and Os were predicted theoretically to be the first elements to condense as a solid phase from the high temperature solar nebula. The aims of this paper are to present a reliable technique for the Re-Os chronology and to study the cosmochemical sequences of the meteoritic metals.