Neoproterozoic to early Phanerozoic rise in island arc redox state due to deep ocean oxygenation and increased marine sulfate levels

A rise in atmospheric O_2 levels between 800 and 400 Ma is thought to have oxygenated the deep oceans, ushered in modern biogeochemical cycles, and led to the diversification of animals. Over the same time interval, marine sulfate concentrations are also thought to have increased to near-modern levels. We present compiled data that indicate Phanerozoic island arc igneous rocks are more oxidized (Fe^(3+)/ΣFe ratios are elevated by 0.12) vs. Precambrian equivalents. We propose this elevation is due to increases in deep-ocean O_2 and marine sulfate concentrations between 800 and 400 Ma, which oxidized oceanic crust on the seafloor. Once subducted, this material oxidized the subarc mantle, increasing the redox state of island arc parental melts, and thus igneous island arc rocks. We test this using independently compiled V/Sc ratios, which are also an igneous oxybarometer. Average V/Sc ratios of Phanerozoic island arc rocks are elevated (by +1.1) compared with Precambrian equivalents, consistent with our proposal for an increase in the redox state of the subarc mantle between 800 and 400 Ma based on Fe^(3+)/ΣFe ratios. This work provides evidence that the more oxidized nature of island arc vs. midocean-ridge basalts is related to the subduction of material oxidized at the Earth’s surface to the subarc mantle. It also indicates that the rise of atmospheric O_2 and marine sulfate to near-modern levels by the late Paleozoic influenced not only surface biogeochemical cycles and animal diversification but also influenced the redox state of island arc rocks, which are building blocks of continental crust

Multidimensional shielding analysis of the JASPER in-vessel fuel storage experiments

The In-Vessel Fuel Storage (IVFS) experiments analyzed in this report were conducted at the Oak Ridge National Laboratory`s Tower Shielding Reactor (TSR) as part of the Japanese-American Shielding Program for Experimental Research (JASPER). These IVFS experiments were designed to study source multiplication and three-dimensional effects related to in-vessel storage of spent fuel elements in liquid metal reactor (LMR) systems. The present report describes the 2-D and 3-D models, analyses, and calculated results corresponding to a limited subset of those IVFS experiments in which the US LMR program has a particular interest

Sulfur isotope behavior during metamorphism and anatexis of Archean sedimentary rocks: A case study from the Ghost Lake batholith, Ontario, Canada

Recycling of surface-derived sulfur into the deep earth can impart distinct sulfur isotope signatures to magmas. The details of sulfur transfer from sedimentary rocks to magmas (and ultimately igneous rocks) through metamorphism and devolatilization and/or partial melting, however, is difficult to trace. To understand this process in detail we studied multiple-sulfur isotope compositions of sulfides in the Archean (c. 2685 Ma) Ghost Lake batholith (GLB) and its surrounding host metasedimentary rocks of the Superior Craton (Ontario, Canada) by high spatial resolution secondary ion mass spectrometry, complemented by high-precision gas source isotope ratio mass spectrometry measurements. The GLB comprises strongly peraluminous biotite+cordierite, biotite+muscovite, and muscovite+garnet+tourmaline granites to leucogranites, which are thought to represent the partial melts of surrounding metagreywackes and metapelites. The metasedimentary rocks display a range of metamorphic grades increasing from biotite-chlorite (280-380 °C) at ∼5 km away from the GLB to sillimanite-K-feldspar grade (∼660 °C) immediately adjacent to the batholith, thus providing a natural experiment to understand sulfur isotope variations from low- to high-grade Archean sedimentary rocks, as well as granites representative of their partial melts. We find that metasedimentary sulfide δ³⁴S values increase with progressive metamorphism at most 2-3‰ (from −1‰ up to +1 to +2‰). An increase in δ³⁴S values in pyrrhotite during prograde metamorphism can be explained through Rayleigh fractionation during pyrite desulfidation reactions. Pyrite from all but one of the granite samples preserve δ³⁴S values similar to that of the high-grade metasedimentary rocks, indicating that partial melting did not result in significant fractionation of δ³⁴S. The exception to this is one granite sample from a part of the batholith characterized by abundant metasedimentary inclusions. This sample contains pyrite with heterogeneous and low δ³⁴S values (down to −16‰) which likely resulted from incomplete homogenization of sulfur between the granitic melt and metasedimentary inclusions. Small (several tenths of a permil), mostly positive Δ³³S are observed in both the metasedimentary rocks and granites. Our results suggest that Archean strongly peraluminous granites could be a high-fidelity archive to quantify the bulk sulfur isotope composition of the Archean siliciclastic sediments. Further, our findings indicate that subduction of reduced sulfur-bearing sediments in the Archean with δ³⁴S at or near 0‰ should result in release of sulfur-bearing fluids in the mantle wedge with similar values (within a few permil). S-MIF (if initially present in Archean surface material) may be preserved during this process. However, the absence of S-MIF in igneous rocks does not preclude assimilation of Archean sedimentary material as either S-MIF may not be originally present in the Archean sedimentary sulfur and/or homogenization or dilution could obscure any S-MIF originally present in assimilated Archean sediments

Post-entrapment modification of volatiles and oxygen fugacity in olivine-hosted melt inclusions

The solubilities of volatiles (H_2O, CO_2, S, F, and Cl) in basaltic melts are dependent on variables such as temperature, pressure, melt composition, and redox state. Accordingly, volatile concentrations can change dramatically during the various stages of a magma's existence: from generation, to ascent through the mantle and crust, to final eruption at the Earth's surface. Olivine-hosted melt inclusions have the potential to preserve volatile concentrations at the time of entrapment due to the protection afforded by the host olivine against decompression and changes to the oxidation state of the external magma. Recent studies, however, have demonstrated that rapid diffusive re-equilibration of H_2O and oxygen fugacity (f_(O_2)) can occur within olivine-hosted melt inclusions. Here we present volatile, hydrogen isotope, and major element data from dehydration experiments and a quantitative model that assesses proposed mechanisms for diffusive re-equilibration of H_2O and f_(O_2) in olivine-hosted melt inclusions. Our comprehensive set of data for the behavior of common magmatic volatiles (H_2O, CO_2, F, Cl, and S) demonstrates that post-entrapment modification of CO_2, and to a lesser extent S, can also occur. We show that the CO_2 and S concentrations within an included melt decrease with progressive diffusive H_2O loss, and propose that this occurs due to dehydration-induced changes to the internal pressure of the inclusion. Therefore, deriving accurate estimates for pre-eruptive CO_2 and S concentrations from olivine-hosted melt inclusions requires accounting for the amount of CO_2 and S hosted in vapor bubbles. We find, however, that Cl and F concentrations in olivine-hosted melt inclusions are not affected by diffusive re-equilibration through the host olivine nor by dehydration-induced pressure changes within the melt inclusion. Our results indicate that measured H_2O, CO_2 and S concentrations and Fe^(3+)/ΣFe ratios of included melts are not necessarily representative of the melt at the time of entrapment and thus are not reliable proxies for upper mantle conditions

Predictors of subgroups based on maximum drinks per occasion over six years for 833 adolescents and young adults in COGA.

ObjectiveA person's pattern of heavier drinking often changes over time, especially during the early drinking years, and reflects complex relationships among a wide range of characteristics. Optimal understanding of the predictors of drinking during times of change might come from studies of trajectories of alcohol intake rather than cross-sectional evaluations.MethodThe patterns of maximum drinks per occasion were evaluated every 2 years between the average ages of 18 and 24 years for 833 subjects from the Collaborative Study on the Genetics of Alcoholism. Latent class growth analysis identified latent classes for the trajectories of maximum drinks, and then logistic regression analyses highlighted variables that best predicted class membership.ResultsFour latent classes were found, including Class 1 (69%), with about 5 maximum drinks per occasion across time; Class 2 (15%), with about 9 drinks at baseline that increased to 18 across time; Class 3 (10%), who began with a maximum of 18 drinks per occasion but decreased to 9 over time; and Class 4 (6%), with a maximum of about 22 drinks across time. The most consistent predictors of higher drinking classes were female sex, a low baseline level of response to alcohol, externalizing characteristics, prior alcohol and tobacco use, and heavier drinking peers.ConclusionsFour trajectory classes were observed and were best predicted by a combination of items that reflected demography, substance use, level of response and externalizing phenotypes, and baseline environment and attitudes