Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

Thermo-mechanical structure beneath the young orogenic belt of Taiwan

We investigate the thermo-mechanical properties beneath the young orogenic belt of Taiwan by constructing a shear strength profile from a vertical stratified rheological structure. The stratified rheological structure is estimated based on the recently developed thermal structure and its likely composition. Subduction–collision in the young orogenic belts and the thick accretionary wedge make a significant contribution to the growth of sialic crust in the hinterland. The sialic bulk crust not only results in a low seismic velocity but also produces weak crust in the hinterland. The earthquake depth–frequency distribution in the foreland and hinterland correlates very well with the regimes of the brittle/ductile transition revealed in the strength profile. Our results show that the observed two-layer seismicity in the foreland is due to a moderate geotherm and an intermediate mafic bulk composition; while single-layer seismicity in the hinterland is due to its felsic bulk composition. In the foreland, the mechanically strong crust (MSC) and the mechanically strong lithosphere (MSL) coincide with frequent seismicity. The shallow MSC in the hinterland is consistent with the 20- to 25-km seismicity occurring there. The total lithospheric integrated strength (LIS) in the hinterland is only about half of that in the foreland, suggesting a weak lower crust and lithosphere mantle in the hinterland. The results confirm that the earthquake cutoff depth is a proxy for temperature. The calculated decrease of effective elastic thickness (EET) from the orogenic margin (foreland) to the center (hinterland) is consistent with the results of flexure modeling in most orogenic belts. Due to the weak LIS in the hinterland, crustal thinning and rifting may occur in the future. Our results, thus, suggest that the mechanical structure is also closely related to the composition and is not directly reflected in the thermal structure.     

Mercury in Eastern Kentucky coals: Geologic aspects and possible reduction strategies

Mercury emissions from US coal-fired power plants will be regulated by the US Environmental Protection Agency (USEPA) before the end of the decade. Because of this, the control of Hg in coal is important. Control is fundamentally based on the knowledge of the amounts of Hg in mined, beneficiated, and as-fired coal. Eastern Kentucky coals, on a reserve district level, have Hg contents similar to the USA average for coal at mines. Individual coals show greater variation at the bench scale, with Hg enrichment common in the top bench, often associated with enhanced levels of pyritic sulfur. Some of the variation between parts of eastern Kentucky is also based on the position relative to major faults. The Pine Mountain thrust fault appears to be responsible for elemental enrichment, including Hg, in coals on the footwall side of the thrust.Eastern Kentucky coals shipped to power plants in 1999, the year the USEPA requested coal quality information on coal deliveries, indicate that coals shipped from the region have 0.09 ppm Hg, compared to 0.10 ppm for all delivered coals in the USA. On an equal energy basis, and given equal concentrations of Hg, the high volatile bituminous coals from eastern Kentucky would emit less Hg than lower rank coals from other USA regions.     

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Isotopic variability in the aragonite shells of freshwater gastropods living in springs with nearly constant temperature and isotopic composition

We conducted a year-long, intensive monitoring program of live aquatic gastropods (Helisoma duryi, Melanoides tuberculata, Physa virgata, Pyrgulopsis sp., and Tyronia sp.) and their host springs in the Ash Meadows National Wildlife Refuge of southern Nevada. Our purpose was to constrain the degree of natural variation in the isotopic values of shell aragonite for gastropods living in near-constant conditions. Inter- and intraspecies variations, as well as within-shell variations, of δ¹⁸O and δ¹³C values for all taxa were larger than predicted based on variations in environmental conditions alone. This result suggests that different organisms growing in identical or nearly identical environmental conditions may not produce shells with equilibrium isotopic compositions and that these offsets from equilibrium may differ by small, but statistically significant amounts. For the gill-breathing, fully aquatic gastropods M. tuberculata, Pyrgulopsis sp., and Tyronia sp., the deviation of measured isotopic values compared to predicted values based on average environmental conditions were consistent with differences between taxa in the seasonal timing of shell growth. Measured values for the lung-breathing gastropods H. duryi and P. virgata were higher for δ¹⁸O and lower for δ¹³C than predicted at isotopic equilibrium, even when accounting for seasonality effects. We suggest that explaining the differences between the shell isotopic composition of lung- and gill-breathing snails requires a combination of both behavioral and physiologic factors. Our results illustrate the potential complexities of interpreting stable isotopic data from fossil gastropod shells even when environmental conditions are nearly constant, and place limitations on the paleoenvironmental deductions that can be made from the isotopic measurements on fossil gastropods.     

Nucleosynthetic zirconium isotope anomalies in acid leachates of carbonaceous chondrites

Stepwise dissolutions of the carbonaceous chondrites Orgueil (CI), Murchison (CM) and Allende (CV) reveal large nucleosynthetic anomalies for Zr isotopes that contrast with the uniform compositions found in bulk meteorites. Two complementary nucleosynthetic components are observed: one enriched and one depleted in s-process nuclides. The latter component, characterized by excess ⁹⁶Zr, is most distinctive in the acetic acid leachate (up to ε⁹⁶Zr ≈ 50). The excess decreases with increasing acid strength and the final leaching steps of the experiment are depleted in ⁹⁶Zr and thus enriched in s-process nuclides. Presolar silicon carbide grains are likely host phases for part of the anomalous Zr released during these later stages. However, by mass balance they cannot account for the ⁹⁶Zr excesses observed in the early leaching steps and this therefore hints at the presence of at least one additional carrier phase with significant amounts of anomalous Zr. The data provide evidence that average solar system material consists of a homogenized mixture of different nucleosynthetic components, which can be partly resolved by leaching experiments of carbonaceous chondrites.