Association of dissolved aluminum with silica: Connecting molecular structure to surface reactivity using NMR

We studied uptake mechanisms for dissolved Al on amorphous silica by combining bulk-solution chemistry experiments with solid-state Nuclear Magnetic Resonance techniques (²⁷Al magic-angle spinning (MAS) NMR, ²⁷Al{¹H} cross-polarization (CP) MAS NMR and ²⁹Si{¹H} CP-MAS NMR). We find that reaction of Al (1 mM) with amorphous silica consists of at least three reaction pathways; (1) adsorption of Al to surface silanol sites, (2) surface-enhanced precipitation of an aluminum hydroxide, and (3) bulk precipitation of an aluminosilicate phase. From the NMR speciation and water chemistry data, we calculate that 0.20 (±0.04) tetrahedral Al atoms nm⁻² sorb to the silica surface. Once the surface has sorbed roughly half of the total dissolved Al (∼8% site coverage), aluminum hydroxides and aluminosilicates precipitate from solution. These precipitation reactions are dependent upon solution pH and total dissolved silica concentration. We find that the Si:Al stoichiometry of the aluminosilicate precipitate is roughly 1:1 and suggest a chemical formula of NaAlSiO₄ in which Na⁺ acts as the charge compensating cation. For the adsorption of Al, we propose a surface-controlled reaction mechanism where Al sorbs as an inner-sphere coordination complex at the silica surface. Analogous to the hydrolysis of , we suggest that rapid deprotonation by surface hydroxyls followed by dehydration of ligated waters results in four-coordinate (>SiOH)₂Al(OH)₂ sites at the surface of amorphous silica.     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol⁻¹, which is within the range reported in the literature for anaerobic processes.     

Seasonal δS variations in two high elevation snow pits measured by S-S double spike thermal ionization mass spectrometry

δ³⁴S and sulfate concentrations were determined in snow pit samples using a thermal ionization mass spectrometric technique capable of 0.2‰ accuracy and requires ≈5 μg (0.16 μmol) natural S. The technique utilizes a ³³S-³⁶S double spike for instrumental mass fractionation correction, and has been applied to snow pit samples collected from the Inilchek Glacier, Kyrgyzstan and from Summit, Greenland. These δ³⁴S determinations provide the first high-resolution seasonal data for these sites, and are used to estimate seasonal sulfate sources. Deuterium (δD) and oxygen (δ¹⁸O) isotope data show that the Inilchek and Summit snow pit samples represent precipitation over ≈20 months.The δ³⁴S values for the Inilchek ranged from +2.6 ± 0.4‰ to +7.6 ± 0.4‰ on sample sizes ranging from 0.3 to 1.8 μmol S. δ³⁴S values for Greenland ranged from +3.6 ± 0.7‰ to +13.3 ± 5‰ for sample sizes ranging from 0.05 to 0.29 μmol S. The concentration ranged from 92.6 ± 0.4 to 1049 ± 4 ng/g for the Inilchek and 18 ± 9 to 93 ± 6 ng/g for the Greenland snow pit. Anthropogenic sulfate dominates throughout the sampled time interval for both sites based on mass balance considerations. Additionally, both sites exhibit a seasonal signature in both δ³⁴S and concentration. The thermal ionization mass spectrometric technique has three advantages compared to gas source isotopic methods: (1) sample size requirements of this technique are 10-fold less permitting access to the higher resolution S isotope record of low concentration snow and ice, (2) the double spike technique permits δ³⁴S and S concentration to be determined simultaneously, and (3) the double spike is an internal standard.     

Upwelling, species, and depth effects on coral skeletal cadmium-to-calcium ratios (Cd/Ca)

Skeletal cadmium-to-calcium (Cd/Ca) ratios in hermatypic stony corals have been used to reconstruct changes in upwelling over time, yet there has not been a systematic evaluation of this tracer’s natural variability within and among coral species, between depths and across environmental conditions. Here, coral skeletal Cd/Ca ratios were measured in multiple colonies of Pavona clavus, Pavona gigantea and Porites lobata reared at two depths (1 and 7 m) during both upwelling and nonupwelling intervals in the Gulf of Panama (Pacific). Overall, skeletal Cd/Ca ratios were significantly higher during upwelling than during nonupwelling, in shallow than in deep corals, and in both species of Pavona than in P. lobata. P. lobata skeletal Cd/Ca ratios were uniformly low compared to those in the other species, with no significant differences between upwelling and nonupwelling values. Among colonies of the same species, skeletal Cd/Ca ratios were always higher in all shallow P. gigantea colonies during upwelling compared to nonupwelling, though the magnitude of the increase varied among colonies. For P. lobata, P. clavus and deep P. gigantea, changes in skeletal Cd/Ca ratios were not consistent among all colonies, with some colonies having lower ratios during upwelling than during nonupwelling. No statistically significant relationships were found between skeletal Cd/Ca ratios and maximum linear skeletal extension, δ¹³C or δ¹⁸O, suggesting that at seasonal resolution the Cd/Ca signal was decoupled from growth rate, coral metabolism, and ocean temperature and salinity, respectively. These results led to the following conclusions, (1) coral skeletal Cd/Ca ratios are independent of skeletal extension, coral metabolism and ambient temperature/salinity, (2) shallow P. gigantea is the most reliable species for paleoupwelling reconstruction and (3) the average Cd/Ca record of several colonies, rather than of a single coral, is needed to reliably reconstruct paleoupwelling events.     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

The iron-isotope fractionation dictated by the carboxylic functional: An ab-initio investigation

The ground-state geometries, electronic energies and vibrational properties of carboxylic complexes of iron were investigated both in vacuo and under the effect of a reaction field, to determine thermodynamic properties of iron-acetates and the role of the carboxylic functional on the isotopic imprinting of this metal in metalorganic complexation. The electronic energy, zero point corrections and thermal corrections of these substances at variational state were investigated at the DFT/B3LYP level of theory with different basis set expansions and the effect of the reaction field on the variational structures was investigated through the Polarized Continuun Model. Thermochemical cycle calculations, combined with solvation energy calculations and appropriate scaling from absolute to conventional properties allowed to compute the Gibbs free energy of formation from the elements of the investigated aqueous species and to select the best procedure to be applied in the successive vibrational analysis. The best compliance with the few existing thermodynamic data for these substances was obtained by coupling the gas phase calculations at DFT/B3LYP level with the [6-31G(d,p)]-[6-31G+(d,p)] (for cations and neutral molecules - anions; respectively) with solvation calculations adopting atomic radii optimized for the HF/6-31G(d) level of theory (UAHF). A vibrational analysis conducted on ⁵⁴Fe, ⁵⁶Fe, ⁵⁷Fe and ⁵⁸Fe gaseous isotopomers yielded reduced partition function ratios which increased not only with the nominal valence of the central cation, as expected, but, more importantly, with the extent of the complexation operated by the organic functional. Coupling thermodynamic data with separative effects it was shown that this last is controlled, as expected, by the relative bond strength of the complex in both aggregation states. Through the Integral Equation Formalism of the Polarized Continuum Model (IEFPCM) the effect of the ionic strength of the solution and of a T-dependent permittivity on the energy and separative effects of the solvated metalorganic complexes were analyzed in detail. The solvent effect in the standard state (hypothetical one-molal solution referred to infinite dilution; T = 298.15 K, P = 1 bar) is a limited reduction of the separative effects of all the isotopomeric couples. With an increase in T (and the concomitant decrease in the dielectric constant of the solvent) this effect diminishes progressively.     

The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km²) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment.     

A spectrophotometric study of Nd(III), Sm(III) and Er(III) complexation in sulfate-bearing solutions at elevated temperatures

The speciation of Nd(III), Sm(III), and Er(III) in sulfate-bearing solutions has been determined spectrophotometrically at temperatures from 25 to 250 °C and a pressure of 100 bars. The data obtained earlier on the speciation of Nd in sulfate-bearing solutions (Migdisov et al., 2006) have been re-evaluated and corrected using a more appropriate activity model and are compared with the corresponding data for Sm(III) and Er(III) and new data for Nd(III). Based on this comparison, the dominant species in the solution are interpreted to be and , with the latter complex increasing in importance at higher temperature. Equilibrium constants were calculated for the following reactions:

     

Nanoscale study of As biomineralization in an acid mine drainage system

Spatial and seasonal variations of the oxidation of Fe(II) and As(III) have been previously documented in the Carnoulès (Gard, France) Acid Mine Drainage (AMD) by bulk analyses. These variations may be correlated with the variations in the activity of indigenous As(III)- and Fe(II)-oxidizing bacteria living in the As-rich Carnoulès water. The activity of these bacteria indeed plays an important role in the nature and composition of the solid phases that sequester arsenic at this site. In order to better understand the interactions of microbes with Fe and As in the Carnoulès AMD, we combined Transmission Electron Microscopy (TEM) and Scanning Transmission X-ray Microscopy (STXM) to collect near-edge X-ray absorption fine structure (NEXAFS) spectra at high spatial and energy resolution and to perform high spatial resolution imaging at the 30-50 nm scale. Spectromicroscopy was performed at the C K-edge, Fe L_2,3-edge, and As L_2,3-edge, which allowed us to locate living and/or mineralized bacterial cells and to characterize Fe and As oxidation states in the vicinity of those cells. TEM was used to image the same areas, providing higher resolution images and complementary crystallographic and compositional information through electron diffraction and EDXS analysis. This approach provides unique information on heterogeneous geochemical processes that occur in a complex microbial community in an AMD environment at the micrometer and submicrometer-scale. Bacterial cells in the Carnoulès AMD were frequently associated with mineral precipitates, and a variety of biomineralization patterns were observed. While many mineral precipitates were not associated with bacterial cells, they were associated with pervasive organic carbon. Finally, abundant biomineralized organic vesicles were observed in the Carnoulès AMD. Such vesicles may have been overlooked in highly mineralized extreme environments in the past and may represent an important component in a common biomineralization process in such environments.     

Geochemistry, petrology and ages of the lunar meteorites Kalahari 008 and 009: New constraints on early lunar evolution

Kalahari 008 and 009 are two lunar meteorites that were found close to each other in Botswana. Kalahari 008 is a typical lunar anorthositic breccia; Kalahari 009 a monomict breccia with basaltic composition and mineralogy. Based on minor and trace elements Kalahari 009 is classified as VLT (very-low-Ti) mare basalt with extremely low contents of incompatible elements, including the REE. The Lu-Hf data define an age of 4286 ± 95 Ma indicating that Kalahari 009 is one of the oldest known basalt samples from the Moon. It provides evidence for lunar basalt volcanism prior to 4.1 Ga (pre-Nectarian) and may represent the first sample from a cryptomare. The very radiogenic initial ¹⁷⁶Hf/¹⁷⁷Hf (εHf = +12.9 ± 4.6), the low REE, Th and Ti concentrations indicate that Kalahari 009 formed from re-melting of mantle material that had undergone strong incompatible trace element depletion early in lunar history. This unusually depleted composition points toward a hitherto unsampled basalt source region for the lunar interior that may represent a new depleted endmember source for low-Ti mare basalt volcanism. Apparently, the Moon became chemically very heterogeneous at an early stage in its history and different cumulate sources are responsible for the diverse mare basalt types.Evidence that Kalahari 008 and 009 may be paired includes the similar fayalite content of their olivine, the identical initial Hf isotope composition, the exceptionally low exposure ages of both rocks and the fact that they were found close to each other. Since cryptomaria are covered by highland ejecta, it is possible that these rocks are from the boundary area, where basalt deposits are covered by highland ejecta. The concentrations of cosmogenic radionuclides and trapped noble gases are unusually low in both rocks, although Kalahari 008 contains slightly higher concentrations. A likely reason for this difference is that Kalahari 008 is a polymict breccia containing a briefly exposed regolith, while Kalahari 009 is a monomict brecciated rock that may never have been at the surface of the Moon.Altogether, the compositions of Kalahari 008 and 009 permit new insight into early lunar evolution, as both meteorites sample lunar reservoirs hitherto unsampled by spacecraft missions. The very low Th and REE content of Kalahari 009 as well as the depletion in Sm and the lack of a KREEP-like signature in Kalahari 008 point to a possible source far from the influence of the Procellarum-KREEP Terrane, possibly the lunar farside.