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The Toarcian Oceanic Anoxic Event (T-OAE; ~183 Mya) was a globally significant carbon-cycle perturbation linked to widespread deposition of organic-rich sediments, massive volcanic CO2 release, marine faunal extinction, sea-level rise, a crisis in carbonate production related to ocean acidification, and elevated seawater temperatures. Despite recognition of the T-OAE as a potential analog for future ocean deoxygenation, current knowledge on the severity of global ocean anoxia is limited largely to studies of the trace element and isotopic composition of black shales, which are commonly affected by local processes. Here, we present the first carbonate-based uranium isotope (δ238U) record of the T-OAE from open marine platform limestones of the southeastern Tethys Ocean as a proxy for global seawater redox conditions. A significant negative δ238U excursion (~0.4‰) is recorded just prior to the onset of the negative carbon isotope excursion comprised within the T-OAE, followed by a long-lived recovery of δ238U values, thus confirming that the T-OAE represents a global expansion of marine anoxia. Using a Bayesian inverse isotopic mass balance model, we estimate that anoxic waters covered ~6 to 8% of the global seafloor during the peak of the T-OAE, which represents 28 to 38 times the extent of anoxia in the modern ocean. These data, combined with δ238U-based estimates of seafloor anoxic area for other CO2-driven Phanerozoic OAEs, suggest a common response of ocean anoxia to carbon release, thus improving prediction of future anthropogenically induced ocean deoxygenation. [ABSTRACT FROM AUTHOR]

As the field of zirconium (Zr) stable isotopes is rapidly expanding from the study of mass-independent to that of mass-dependent isotope effects, a variety of Zr standards have appeared in the literature. While several of these standards have been proposed as the ideal isotope reference material (iRM) against which all data should be reported, none of them have been shown to meet the compositional and/or conflict-of-interest-free distribution requirements put forth by the community. To remedy this situation, we report on a community-led effort to develop and calibrate a scale defining iRM for Zr isotopes: NIST RM 8299. Developed in partnership with the National Institute of Standards and Technology (NIST) from the widely used SRM 3169 Zirconium Standard Solution (certified for mass fraction), the candidate RM 8299 was calibrated through an inter-laboratory study involving three laboratories. Our data show that candidate RM 8299 meets all requirements of an ideal iRM. It is an isotopically homogeneous, high-purity reference material, that is free of isotope anomalies, and whose composition is identical to that of a major geological reservoir (Ocean Island Basalts). Furthermore, RM 8299 will be curated and distributed by NIST, a neutral, conflict-of-interest free organization, and was produced in sufficient quantities to last multiple decades. We recommend that all Zr isotope data be reported against RM 8299. Our results also show that SRM 3169 lots #130920 and #071226 have indistinguishable composition compared to candidate RM 8299. Therefore, using RM 8299 as the scale defining iRM will enable direct comparison of all future data with the vast majority of the existing literature data, both for mass-independent and mass-dependent isotope effects. To facilitate conversion of δ94/90Zr values reported against other Zr standards, we provide high-precision conversion factors to the RM 8299 scale obtained using the double-spike method. [ABSTRACT FROM AUTHOR]

Mass-independent tungsten isotope variations provide critical insights into the timing and nature of processes that occurred in the early Solar System and during planetary differentiation. However, W isotope analyses are often compromised by an analytical artifact manifesting itself as an apparent deficit in 183W, whose origin and nature have remained enigmatic. Here, by evaluating previously published high-precision W isotope data for a large and diverse set of terrestrial samples, we demonstrate that this artifact occurs independent of the type of mass spectrometer and confirm that it can be attributed to mass-independent fractionation of 183W. Contrary to previous proposals, we find that this 'analytical183W effect' cannot be explained by a nuclear field shift, but may instead reflect a magnetic isotope effect. Regardless of its exact origin, our investigation reveals that this artifact is induced during the chemical separation of W, and that the specific combination of chromatographic purification and dry-down procedure determines its overall magnitude. Within a given analytical protocol, however, its size is strongly controlled by the amount of W that is processed, where the 183W effect increases with decreasing amount of W. Therefore, this work resolves apparent inconsistencies between previous studies regarding the occurrence and magnitude of the 183W effect, and provides directions for its mitigation and reliable correction. This in turn is crucial for the accurate interpretation of W isotope data with respect to radiogenic and nucleosynthetic anomalies for both terrestrial and meteoritic materials. [ABSTRACT FROM AUTHOR]

Paqueite (Ca3TiSi2[Al,Ti,Si]3O14; IMA 2013‐053) and burnettite (CaVAlSiO6; IMA 2013‐054) are new refractory minerals, occurring as euhedral to subhedral crystals within aluminous melilite in A‐WP1, a type A Ca‐Al‐rich inclusion, and CGft‐12, a compact type A (CTA) from the Allende CV3 carbonaceous chondrite. Type paqueite from A‐WP1 has an empirical formula of (Ca2.91Na0.11)Ti4+Si2(Al1.64Ti4+0.90Si0.24V3+0.12Sc0.07Mg0.03)O14, with a trigonal structure in space group P321 and cell parameters a = 7.943 Å, c = 4.930 Å, V = 269.37 Å3, and Z = 1. Paqueite's general formula is Ca3TiSi2(Al,Ti,Si)3O14 and the endmember formula is Ca3TiSi2(Al2Ti)O14. Type burnettite from CGft‐12 has an empirical formula of Ca1.01(V3+0.56Al0.25Mg0.18)(Si1.19Al0.81)O6. It assumes a diopside‐type C2/c structure with a = 9.80 Å, b = 8.85 Å, c = 5.36 Å, β = 105.6°, V = 447.7 Å3, and Z = 4. Burnettite's general formula is Ca(V,Al,Mg)AlSiO6 and the endmember formula is CaVAlSiO6. Paqueite and burnettite likely originated as condensates, but the observed grains may have crystallized from local V‐rich melts produced during a later thermal event. For CGft‐12, the compositions of paqueite, clinopyroxene, and perovskite suggest that type As drew from two distinct populations of grains. Hibonite grains drew from multiple populations, but these were well mixed and not equilibrated prior to incorporation into type A host melilite. [ABSTRACT FROM AUTHOR]

Owing to the challengingly small amounts of uranium (U) they contain, the isotopic composition (238U/235U) of single zircon grains has never been measured. Leveraging methods we designed for analysis of small sample amounts and modern MC-ICPMS instruments, we show that precise (±0.04 to ±0.25‰) single-zircon 238U/235U measurements are now possible. We report data for 31 single grains from the Jack Hills conglomerate, and 3 reference zircon localities (FC-1, R33 and Temora). Consistent with the reducing conditions implied by the small Ce anomalies of many Hadean zircon, Jack Hills grains display only small δ238U variations (from −0.60 to −0.12‰). The distribution is centered on the average chondritic and bulk continental crust value, arguing against the widespread existence of Oklo-type reactors in the early Earth. The subtle δ238U variations in Jack Hills zircons are more plausibly explained by a small (∼0.10%) mass-dependent equilibrium isotope fractionation between at least one U-bearing accessory mineral and silicate melts, during magmatic differentiation under reducing conditions. In contrast, the large δ238U difference between pooled titanite and pooled zircon fractions from the Fish Canyon Tuff sample suggests larger isotope effects during igneous fractional crystallization under oxidizing conditions (∼QFM+2), with preferential removal of 235U from the melt and into zircon, and/or other accessory phases. We estimate that ∼50% of zircon dated by the CA-ID-TIMS method would be amenable to single-grain U isotope measurements, making this method widely applicable to future studies. This would enable (i) improvements in precision and accuracy of U–Pb and Pb–Pb dates, (ii) accurate investigation of U-series disequilibrium contribution to U–Pb discordance, and (iii) accurate re-evaluation of U decay constants. [ABSTRACT FROM AUTHOR]

The article focuses on understanding the difference in iodine/plutonium ratios between different mantle reservoirs of Earth and its implications for Earth's accretion history. It mentions using molecular dynamics simulations, the researchers quantify the metal-silicate partition coefficients of iodine and plutonium during core formation and demonstrate that core formation alone cannot explain the observed iodine/plutonium difference.

Paqueite (Ca3TiSi2[Al,Ti,Si]3O14; IMA 2013‐053) and burnettite (CaVAlSiO6; IMA 2013‐054) are new refractory minerals, occurring as euhedral to subhedral crystals within aluminous melilite in A‐WP1, a type A Ca‐Al‐rich inclusion, and CGft‐12, a compact type A (CTA) from the Allende CV3 carbonaceous chondrite. Type paqueite from A‐WP1 has an empirical formula of (Ca2.91Na0.11)Ti4+Si2(Al1.64Ti4+0.90Si0.24V3+0.12Sc0.07Mg0.03)O14, with a trigonal structure in space group P321 and cell parameters a = 7.943 Å, c = 4.930 Å, V = 269.37 Å3, and Z = 1. Paqueite's general formula is Ca3TiSi2(Al,Ti,Si)3O14 and the endmember formula is Ca3TiSi2(Al2Ti)O14. Type burnettite from CGft‐12 has an empirical formula of Ca1.01(V3+0.56Al0.25Mg0.18)(Si1.19Al0.81)O6. It assumes a diopside‐type C2/c structure with a = 9.80 Å, b = 8.85 Å, c = 5.36 Å, β = 105.6°, V = 447.7 Å3, and Z = 4. Burnettite's general formula is Ca(V,Al,Mg)AlSiO6 and the endmember formula is CaVAlSiO6. Paqueite and burnettite likely originated as condensates, but the observed grains may have crystallized from local V‐rich melts produced during a later thermal event. For CGft‐12, the compositions of paqueite, clinopyroxene, and perovskite suggest that type As drew from two distinct populations of grains. Hibonite grains drew from multiple populations, but these were well mixed and not equilibrated prior to incorporation into type A host melilite. [ABSTRACT FROM AUTHOR]

Protein phosphatase 2A (PP2A), a serine/threonine phosphatase involved in the regulation of apoptosis, proliferation, and DNA-damage response, is overexpressed in many cancers, including small cell lung cancer (SCLC). Here we report that LB100, a small molecule inhibitor of PP2A, when combined with platinum-based chemotherapy, synergistically elicited an antitumor response both in vitro and in vivo with no apparent toxicity. Using inductively coupled plasma mass spectrometry, we determined quantitatively that sensitization via LB100 was mediated by increased uptake of carboplatin in SCLC cells. Treatment with LB100 alone or in combination resulted in inhibition of cell viability in two-dimensional culture and three-dimensional spheroid models of SCLC, reduced glucose uptake, and attenuated mitochondrial and glycolytic ATP production. Combining LB100 with atezolizumab increased the capacity of T cells to infiltrate and kill tumor spheroids, and combining LB100 with carboplatin caused hyperphosphorylation of the DNA repair marker γH2AX and enhanced apoptosis while attenuating MET signaling and invasion through an endothelial cell monolayer. Taken together, these data highlight the translational potential of inhibiting PP2A with LB100 in combination with platinum-based chemotherapy and immunotherapy in SCLC., (©2021 The Authors; Published by the American Association for Cancer Research.)