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The ∼74 ka Toba eruption was one of the largest volcanic events of the Quaternary. There is much interest in determining the impact of such a large event, particularly on the climate and hominid populations at the time. Although the Toba eruption has been identified in both land and marine archives as the Youngest Toba Tuff, its precise place in the ice core record is ambiguous. Several volcanic sulfate signals have been identified in both Antarctic and Greenland ice cores and span the Toba eruption 40Ar/39Ar age uncertainty. Here, we measure sulfur isotope compositions in Antarctic ice samples from the Dome C (EDC) and Dronning Maud Land (EDML) ice cores at high temporal resolution across 11 of these potential Toba sulfate peaks to identify candidates with sulfur mass-independent fractionation (S-MIF), indicative of an eruption whose plume reached altitudes at or above the stratospheric ozone layer. Using this method, we identify several candidate sulfate peaks that contain stratospheric sulfur. We further narrow down potential candidates based on the isotope signatures by identifying sulfate peaks that are due to a volcanic event at tropical latitudes. In one of these sulfate peaks at 73.67 ka, we find the largest ever reported magnitude of S-MIF in volcanic sulfate in polar ice, with a Δ33S value of −4.75 ‰. As there is a positive correlation between the magnitude of the S-MIF signal recorded in ice cores and eruptive plume height, this could be a likely candidate for the Toba super-eruption, with a plume top height in excess of 45 km. These results support the 73.7±0.3 ka (1σ) 40Ar/39Ar age estimate for the eruption, with ice core ages of our candidates with the largest magnitude S-MIF at 73.67 and 73.74 ka. Finally, since these candidate eruptions occurred on the transition into Greenland Stadial 20, the relative timing suggests that Toba was not the trigger for the large Northern Hemisphere cooling at this time although we cannot rule out an amplifying effect.

This research was supported by NERC award NE/L002590/1 to the IAPETUS DTP, and by NERC Standard Grant NE/J023485/2 to A.L.Z. The initiation of Cu isotope analysis at the University of St Andrews was aided significantly by a Carnegie Trust Research Incentive Grant awarded to P.S.S. The rise of oxygenic photosynthesis arguably represents the most important evolutionary step in Earth history. Recent studies, however, suggest that Earth’s pre-oxidative atmosphere was also heavily influenced by biological feedbacks. Most notably, recent geochemical records propose the existence of a hydrocarbon haze which periodically formed in response to enhanced biospheric methane fluxes. Copper isotopes provide a potential proxy for biological methane cycling; Cu is a bioessential trace metal and a key element in the aerobic oxidation of methane to carbon dioxide (methanotrophy). In addition, Cu isotopes are fractionated during biological uptake. Here, we present a high-resolution Cu isotope record measured in a suite of shales and carbonates from core GKF01, through the ~2.6–2.5 Ga Campbellrand-Malmani carbonate platform. Our data show a 0.85‰ range in Cu isotope composition and a negative excursion that predates the onset of a haze event. We interpret this excursion as representing a period of enhanced aerobic methane oxidation before the onset of the Great Oxidation Event. This places valuable time constraints on the evolution of this metabolism and firmly establishing Cu isotopes as a biomarker in Late Archaean rocks. Postprint

On March 6, 2016 at 21:36:51 UT, extended areas of Upper Austria, Bavaria (Germany) and the southwestern part of the Czech Republic were illuminated by a very bright bolide. This bolide was recorded by instruments in the Czech part of the European Fireball Network and it enabled complex and precise description of this event including prediction of the impact area. So far six meteorites totaling 1473 g have been found in the predicted area. The first pieces were recovered on March 12, 2016 on a field close to the village of Stubenberg (Bavaria). Stubenberg is a weakly shocked (S3) fragmental breccia consisting of abundant highly recrystallized rock fragments embedded in a clastic matrix. The texture, the large grain size of plagioclase, and the homogeneous compositions of olivine (Fa31.4) and pyroxene (Fs25.4) clearly indicate that Stubenberg is an LL6 chondrite breccia. This is consistent with the data on O, Ti, and Cr isotopes. Stubenberg does not contain solar wind-implanted noble gases. Data on the bulk chemistry, IR spectroscopy, cosmogenic nuclides, and organic components also indicate similarities to other metamorphosed LL chondrites. Noble gas studies reveal that the meteorite has a cosmic ray exposure (CRE) age of 36 ± 3 Ma and that most of the cosmogenic gases were produced in a meteoroid with a radius of at least 35 cm. This is larger than the size of the meteoroid which entered the Earth's atmosphere, which is constrained to

We are grateful for funding for this work from UCLA and NASA Cosmochemistry (grant NNX13AD13G). The Ti isotope variations observed in hibonites represent some of the largest isotope anomalies observed in the solar system. Titanium isotope compositions have previously been reported for a wide variety of different early solar system materials, including calcium, aluminum rich inclusions (CAIs) and CM hibonite grains, some of the earliest materials to form in the solar system, and bulk meteorites which formed later. These data have the potential to allow mixing of material to be traced between many different regions of the early solar system. We have used independent component analysis to examine the mixing end-members required to produce the compositions observed in the different data sets. The independent component analysis yields results identical to a linear regression for the bulk meteorites. The components identified for hibonite suggest that most of the grains are consistent with binary mixing from one of three highly anomalous nucleosynthetic sources. Comparison of these end-members show that the sources which dominate the variation of compositions in the meteorite parent body forming regions was not present in the region in which the hibonites formed. This suggests that the source which dominates variation in Ti isotope anomalies between the bulk meteorites was not present when the hibonite grains were forming. One explanation is that the bulk meteorite source may not be a primary nucleosynthetic source but was created by mixing two or more of the hibonite sources. Alternatively, the hibonite sources may have been diluted during subsequent nebula processing and are not a dominant solar system signatures. Postprint

Dr. Coath is supported in this work by STFC grant ref. ST/F002734/1. This paper presents the mathematics of the systematic bias in the expected value of the ratio of two noise- corrected Poisson-distributed variables, such as ion counting measurements. Such bias can lead to the reporting of incorrect ratios and, in some cases, systematic correlations with other measurements which can impact the scientific interpretation. We describe a novel method of treating such measurements which results in a negligible, exponentially small bias. We also re-examine the conventional approach deriving an exact expression for the bias including the noise correction explicitly. Postprint

We present new, mass-independent, Ni isotope data for a range of bulk chondritic meteorites. The data are reported as e 60 Ni58/61, e 62 Ni58/61, and e 64 Ni58/61, or the parts per ten thousand deviations from a terrestrial reference, the NIST SRM 986 standard, of the 58 Ni/ 61 Ni internally normalized 60 Ni/ 61 Ni, 62 Ni/ 61 Ni, and 64 Ni/ 61 Ni ratios. The chondrites show a range of 0.15, 0.29, and 0.84 in e 60 Ni58/61, e 62 Ni58/61, and e 64 Ni58/61 relative to a typical sample precision of 0.03, 0.05, and 0.08 (2 s.e.), respectively. The carbonaceous chondrites show the largest positive anomalies, enstatite chondrites have approximately terrestrial ratios, though only EH match Earth’s composition within uncertainty, and ordinary chondrites show negative anomalies. The meteorite data show a strong positive correlation between e 62 Ni58/61 and e 64 Ni58/61, an extrapolation of which is within the error of the average of previous measurements of calcium-, aluminium-rich inclusions. Moreover, the slope of this bulk meteorite array is 3.003 ± 0.166 which is within the error of that expected for an anomaly solely on 58 Ni. We also determined to high precision (∼10 ppm per AMU) the mass-dependent fractionation of two meteorite samples which span the range of e 62 Ni58/61 and e 64 Ni58/61. These analyses show that “absolute” ratios of 58 Ni/ 61 Ni vary between these two samples whereas those of 62 Ni/ 61 Ni and 64 Ni/ 61 Ni do not. Thus, Ni isotopic differences seem most likely explained by variability in the neutron-poor 58 Ni, and not correlated anomalies in the neutron-rich isotopes, 62 Ni and 64 Ni. This contrasts with previous inferences from mass-independent measurements of Ni and other transition elements which invoked variable contributions of a neutron-rich component. We have examined different nucleosynthetic environments to determine the possible source of the anomalous material responsible for the isotopic variations observed in Ni and other transition elements within bulk samples. We find that the Ni isotopic variability of the solar system cannot be explained by mixing with a component of bulk stellar ejecta from either SN II, Wolf–Rayet or, an asymptotic giant branch source and is unlikely to result from bulk mixing of material from an SN Ia. However, variable admixture of material from the Si/S zone of an SN II can create all the characteristics of Ni isotope variations in solar system materials. Moreover, these characteristics can also be provided by an SN II with a range of masses from 15 to 40 M� , showing that input from SN II is a robust source for Ni isotope variations in the solar system. Correlations of Ni isotope anomalies with O, Cr, and Ti isotope ratios and Pb/Yb in bulk meteorites suggest that the heterogeneous distribution of isotopic anomalies in the early solar system likely resulted from nebular sorting of chemically or physically different materials bearing different amounts of isotopes synthesized proximally to the collapse of the protosolar nebula.