Variations in the isotopic composition of Ni resulting from natural mass-dependent processes in terrestrial or extraterrestrial conditions, inhomogeneous distribution of nucleosynthetic components and/or ingrowth from radioactive parent nuclides, help us to further understand the early formation history of Solar System materials and the nature of the processes these materials subsequently experienced. In studies of Ni isotope systematics, mass-dependent variations in the isotopic composition of Ni are often bypassed because of the challenges associated with the sample preparation. At the level of natural variation studied, Ni isotope ratio measurements are extremely sensitive to spectral interference, artificial on-column isotope fractionation and possibly even to the mass bias correction model applied. To adequately address these complications, an isolation procedure and measurement protocol relying on multi-collector ICP-mass spectrometry (MC-ICP-MS) have been designed and validated in this work. The overall reproducibility obtained based on repeated measurement of a Sigma-Aldrich high-purity Ni standard is 0.036&, 0.049 parts per thousand, 0.078 parts per thousand and 0.53 parts per thousand for delta Ni-60/58, delta Ni-61/58, delta Ni-62/58 and delta Ni-64/58, respectively (n = 14; 2 SD). Nickel isotope ratio variations have been studied in a set of iron meteorites and geological reference materials, and the results obtained, except for those suffering from an elevated Zn-64 background, show good agreement with the available literature data. By using the flexible generalized power law with a variable discrimination exponent and the three-isotope method, the processes underlying natural mass fractionation of Ni for terrestrial reference materials were found to have a mixed equilibrium/kinetic nature. Mass-dependent Ni fractionation was observed between sample fractions of the Canyon Diablo iron meteorite, and the extracted fractionation factor beta corresponds to isotope partitioning following the power law
The Cretaceous-Paleogene (K-Pg) mass extinction is marked globally by elevated concentrations of iridium, emplaced by a hypervelocity impact event 66 million years ago. Here, we report new data from four independent laboratories that reveal a positive iridium anomaly within the peak-ring sequence of the Chicxulub impact structure, in drill core recovered by IODP-ICDP Expedition 364. The highest concentration of ultrafine meteoritic matter occurs in the post-impact sediments that cover the crater peak ring, just below the lowermost Danian pelagic limestone. Within years to decades after the impact event, this part of the Chicxulub impact basin returned to a relatively low-energy depositional environment, recording in unprecedented detail the recovery of life during the succeeding millennia. The iridium layer provides a key temporal horizon precisely linking Chicxulub to K-Pg boundary sections worldwide.
Main group pallasite meteorites are samples of a single early magmatic planetesimal, dominated by metal and olivine but containing accessory chromite, sulfide, phosphide, phosphates, and rare phosphoran olivine. They represent mixtures of core and mantle materials, but the environment of formation is poorly understood, with a quiescent core–mantle boundary, violent core–mantle mixture, or surface mixture all recently suggested. Here, we review main group pallasite data sets and petrologic characteristics, and present new observations on the low‐MnO pallasite Brahin that contains abundant fragmental olivine, but also rounded and angular olivine and potential evidence of sulfide–phosphide liquid immiscibility. A reassessment of the literature shows that low‐MnO and high‐FeO subgroups preferentially host rounded olivine and low‐temperature P2O5‐rich phases such as the Mg‐phosphate farringtonite and phosphoran olivine. These phases form after metal and silicate reservoirs back‐react during decreasing temperature after initial separation, resulting in oxidation of phosphorus and chromium. Farringtonite and phosphoran olivine have not been found in the common subgroup PMG, which are mechanical mixtures of olivine, chromite with moderate Al2O3 contents, primitive solid metal, and evolved liquid metal. Lower concentrations of Mn in olivine of the low‐MnO PMG subgroup, and high concentrations of Mn in low‐Al2O3 chromites, trace the development and escape of sulfide‐rich melt in pallasites and the partially chalcophile behavior for Mn in this environment. Pallasites with rounded olivine indicate that the core–mantle boundary of their planetesimal may not be a simple interface but rather a volume in which interactions between metal, silicate, and other components occur.
This work presents an evaluation of various methods for in situ high‐precision Sr and Pb isotopic determination in archaeological glass (containing 100–500 μg g−1 target element) by nanosecond laser ablation multi‐collector‐inductively coupled plasma‐mass spectrometry (ns‐LA‐MC‐ICP‐MS). A set of four soda‐lime silicate glasses, Corning A–D, mimicking the composition of archaeological glass and produced by the Corning Museum of Glass (Corning, New York, USA), were investigated as candidates for matrix‐matched reference materials for use in the analysis of archaeological glass. Common geological reference materials with known isotopic compositions (USGS basalt glasses BHVO‐2G, GSE‐1G and NKT‐1G, soda‐lime silicate glass NIST SRM 610 and several archaeological glass samples with known Sr isotopic composition) were used to evaluate the ns‐LA‐MC‐ICP‐MS analytical procedures. When available, ns‐LA‐MC‐ICP‐MS results for the Corning glasses are reported. These were found to be in good agreement with results obtained via pneumatic nebulisation (pn) MC‐ICP‐MS after digestion of the glass matrix and target element isolation. The presence of potential spectral interference from doubly charged rare earth element (REE) ions affecting Sr isotopic determination was investigated by admixing Er and Yb aerosols by means of pneumatic nebulisation into the gas flow from the laser ablation system. It was shown that doubly charged REE ions affect the Sr isotope ratios, but that this could be circumvented by operating the instrument at higher mass resolution. Multiple strategies to correct for instrumental mass discrimination in ns‐LA‐MC‐ICP‐MS and the effects of relevant interferences were evaluated. Application of common glass reference materials with basaltic matrices for correction of ns‐LA‐MC‐ICP‐MS isotope data of archaeological glasses results in inaccurate Pb isotope ratios, rendering application of matrix‐matched reference materials indispensable. Correction for instrumental mass discrimination using the exponential law, with the application of Tl as an internal isotopic standard element introduced by pneumatic nebulisation and Corning D as bracketing isotopic calibrator, provided the most accurate results for Pb isotope ratio measurements in archaeological glass. Mass bias correction relying on the power law, combined with intra‐element internal correction, assuming a constant 88Sr/86Sr ratio, yielded the most accurate results for 87Sr/86Sr determination in archaeological glasses
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