Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

It is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere.     

Seasonal patterns of carbon chemistry and isotopes in tufa depositing groundwaters of southwestern Japan

Annually laminated carbonates, known as tufas, commonly develop in limestone areas and typically record seasonal patterns of oxygen- and carbon-isotope compositions. δ¹⁸O values are principally controlled by seasonal changes of water temperature, whereas δ¹³C values are the result of complex reactions among the gaseous, liquid, and solid sources of carbon in the system. We examined the processes that cause the seasonal patterns of δ¹³C in groundwater systems at three tufa-depositing sites in southwestern Japan by applying model calculations to geochemical data. Underground inorganic carbon species are exchanged with gaseous CO₂, which is mainly introduced to the underground hydrological system by natural atmospheric ventilation and by diffusion of soil air. These processes control the seasonal pattern of δ¹³C, which is low in summer and high in winter. Among the three sites we investigated, we identified two extreme cases of the degree of carbon exchange between liquid and gaseous phases. For the case with high radiocarbon composition (Δ¹⁴C) and low pCO₂, there was substantial carbon exchange because of a large contribution of atmospheric CO₂ and a small water mass. For the other extreme case, which was characterized by low Δ¹⁴C and high pCO₂, the contribution of atmospheric CO₂ was small and the water mass was relatively large. Our results suggest that at two of the three sites water residence time within the soil profile was longer than 1 year. Our results also suggested a short residence time (less than 1 year) of water in the soil profile at the site with the smallest water mass, which is consistent with large seasonal amplitude of the springwater temperature variations. The Δ¹⁴C value of tufas is closely related to the hydrological conditions in which they are deposited. If the initial Δ¹⁴C value of a tufa-depositing system is stable, ¹⁴C-chronology can be used to date paleo-tufas.     

Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts

Configurational changes with temperature are important for the thermodynamic and transport properties of most aluminosilicate melts, but in general are not well understood. Here, we present high-resolution ²⁷Al and ¹⁷O NMR data on several calcium aluminosilicate glasses prepared with varying quench rates and thus with fictive temperatures that span ranges up to about 200 K. In all compositions the content of five-coordinated aluminum increases with fictive temperature, in agreement with recent high temperature NMR data on melts. In a glass of CaAl₂Si₂O₈ (“anorthite”) composition, the content of non-bridging oxygens also increases with temperature; however this effect was not observed in a sample with a much higher CaO/Al₂O₃ ratio. We present a consistent notation for reactions among structural species in these systems that clarify why in some cases, high-coordinated network cations may appear on the same side of the reaction, while in others they occur on the opposite sides: the key difference is in accounting for all coordination changes for oxygens. Mixing of non-bridging oxygens and of high-coordinated aluminum make significant contributions to the overall configurational entropy and heat capacity of the melts, as does the mixing of various bridging oxygens and of tetrahedral network cations. Other, less well known, types of increase in disorder with temperature may be important as well.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

The age of the martian meteorite Northwest Africa 1195 and the differentiation history of the shergottites

Samarium-neodymium isotopic analyses of unleached and acid-leached mineral fractions from the recently identified olivine-bearing shergottite Northwest Africa 1195 yield a crystallization age of 347 ± 13 Ma and an value of +40.1 ± 0.9. Maskelynite fractions do not lie on the Sm-Nd isochron and appear to contain a martian surface component with low ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios that was added during shock. The Rb-Sr system is disturbed and does not yield an isochron. Terrestrial Sr appears to have affected all of the mineral fractions, although a maximum initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7016 is estimated by passing a 347 Ma reference line through the maskelynite fraction that is least affected by contamination. The high initial value and the low initial ⁸⁷Sr/⁸⁶Sr ratio, combined with the geologically young crystallization age, indicate that Northwest Africa 1195 is derived from a source region characterized by a long-term incompatible-element depletion.The age and initial Sr and Nd isotopic compositions of Northwest Africa 1195 are very similar to those of Queen Alexandra Range 94201, indicating these samples were derived from source regions with similar Sr-Nd isotopic systematics. These similarities suggest that these two meteorites share a close petrogenetic relationship and might have been erupted from a common volcano. The meteorites Yamato 980459, Dar al Gani 476, Sayh al Uhaymir 005/008, and Dhofar 019 also have relatively old ages between 474 and 575 Ma and trace element and/or isotopic systematics that are indicative of derivation from incompatible-element-depleted sources. This suggests that the oldest group of meteorites is more closely related to one another than they are to the younger meteorites that are derived from less incompatible-element-depleted sources. Closed-system fractional crystallization of this suite of meteorites is modeled with the MELTS algorithm using the bulk composition of Yamato 980459 as a parent. These models reproduce many of the major element and mineralogical variations observed in the suite. In addition, the rare earth element systematics of these meteorites are reproduced by fractional crystallization using the proportions of phases and extents of crystallization that are calculated by MELTS. Other shergottites that demonstrate enrichments in incompatible-elements and have evolved Sr and Nd isotopic systematics have some geochemical systematics that are similar to those observed in the depleted group. Most notably, although they exhibit a very limited range of incompatible trace element and isotopic compositions, they have highly variable major element compositions. This is also consistent with evolution from a common mantle source region by variable amounts of fractional crystallization. If this scenario is correct, it suggests that the combined effects of source composition and fractional crystallization are likely to account for the major element, trace element, and isotopic diversity of all shergottites.     

Cr-spinel/olivine and Cr-spinel/liquid nickel partition coefficients from natural samples

The Nernst partition coefficient of nickel (D^Ni) between Cr-spinel and silicate melt in natural systems has been investigated using mid-ocean ridge basalts (MORB) and other volcanic rocks. The Cr-spinel/olivine D^Ni values in volcanic rocks are between 1.2 and 0.3, indicating that the Cr-spinel/liquid D^Ni values vary from slightly higher to significantly lower than the olivine/liquid D^Ni values in natural systems. The Cr-spinel/liquid D^Ni values from the MORB samples vary between 6 and 11, slightly higher than those from the S-bearing experiments of Satari et al. [Satari P., Brenan J. M., Horn I. and McDonough W. F. (2002) Experimental constraints on the sulfide- and chromite-silicate melt partitioning behavior of rhenium and platinum-group elements. Economic Geology97, 385-398]. The results of the MORB samples and the experiments of Satari et al. (2002) indicate a negative correlation between the Cr-spinel/liquid D^Ni and the X_Cr values in Cr-spinels (Cr cation number on the basis of 3 total cations in the spinel structure). Variations of Cr-spinel/liquid D^Ni values with Cr-spinel compositions can be estimated from an empirical equation based on the results of the MORB samples and the experiments by Satari et al. (2002). The choice of Cr-spinel/liquid D^Ni = 10 for numerical modeling by Righter et al. [Righter K., Leeman W. P. and Hervig R. L. (2006) Partitioning of Ni, Co, and V between spinel-structured oxides and silicate melts: importance of spinel composition. Chemical Geology227, 1-25] is reasonable for basaltic systems. For picritic and komatiitic systems a lower value of ∼5 is more appropriate.     

Size scales over which ordinary chondrites and their parent asteroids are homogeneous in oxidation state and oxygen-isotopic composition

Literature data demonstrate that on a global, asteroid-wide scale (plausibly on the order of 100 km), ordinary chondrites (OC) have heterogeneous oxidation states and O-isotopic compositions (represented, respectively, by the mean olivine Fa and bulk Δ¹⁷O compositions of equilibrated samples). Samples analyzed here include: (a) two H5 chondrite Antarctic finds (ALHA79046 and TIL 82415) that have the same cosmic-ray exposure age (7.6 Ma) and were probably within ∼1 km of each other when they were excavated from the H-chondrite parent body, (b) different individual stones from the Holbrook L/LL6 fall that were probably within ∼1 m of each other when their parent meteoroid penetrated the Earth’s atmosphere, and (c) drill cores from a large slab of the Estacado H6 find located within a few tens of centimeters of each other. Our results indicate that OC are heterogeneous in their bulk oxidation state and O-isotopic composition on 100-km-size scales, but homogeneous on meter-, decimeter- and centimeter-size scales. (On kilometer size scales, oxidation state is heterogeneous, but O isotopes appear to be homogeneous.) The asteroid-wide heterogeneity in oxidation state and O-isotopic composition was inherited from the solar nebula. The homogeneity on small size scales was probably caused in part by fluid-assisted metamorphism and mainly by impact-gardening processes (which are most effective at mixing target materials on scales of ?1 m).     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.     

Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

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.