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.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Probability Density Function Integrals And Small-Scale Mixing In Turbulent Plumes

We analyse cross-wind-integrated statistics of theconcentration field of a conserved scalar for pointand line sources in grid turbulence. In particular,using wind-tunnel measurements we calculate thecross-wind integrated probability density function(pdf) for the scalar concentration. We then use thatquantity in the exact evolution equation for the pdfto calculate the cross-wind integrated mean of therate of dissipation of scalar variance, conditional onthe scalar concentration. Much of the variation ofthese statistics with distance downstream is accountedfor by scaling with concentration, length and timescales based on the development of the mean plume.This scaling thus suggests some simple practicalparameterisations of these statistics in terms ofmean-field quantities. One of the motivations for thiswork is to find a simple parameterisation for thescalar dissipation that can be used for modellingchemical reactions in plumes.We also consider the cross-wind integral of the firstfew moments of the concentration field and show thatthe integration greatly simplifies the budgets forthese moments. Thus the first moment is just thedownstream flux of the scalar, which is constant. Thesecond moment budget provides a check on the meandissipation estimated directly from the pdf evolutionequation.     

Lithologic and stratigraphic setting of zinc mineralization in Grenville metasediments,Quebec

For many years, high-grade metamorphism and multiphase deformation have discouraged mineral exploration in the Grenville terrain of the Canadian Shield. However, detailed studies of known zinc occurrences in the Grenville Supergroup metasediments of Quebec now reveal that mineralization is stratigraphically controlled and consistently limited to mapable lithologic units. Within the vast regions composed predominantly of calcitic marbles, zinc mineralization is found to be confined to the much more limited areas of dolomitic marble, and more precisely, to the lithologic transition from metaclastic beds to meta-dolomites. Massive sphalerite mineralization of the Balmat-type is very closely restricted to this contact zone, while disseminated sphalerite with sparse amounts of galena are commonly observed in the adjacent dolomite. With these guidelines, and with evidence that mineralization is fundamentally stratiform in nature, it has now been demonstrated that mineralized stratigraphic horizons can be located beyond the areas of previously known sphalerite showings, and consequently the potential for important discoveries of zinc mineralization in the Grenville Supergroup has become very attractive to the present-day mining industry.     

Polarized X-ray absorption spectroscopy of metal ions in minerals

We have made use of the nearly complete linear polarization of synchrotron radiation to study the polarization dependence of X-ray absorption near-edge structure (XANES) and extended fine structure (EXAFS) in oriented single crystals of gillespite (BaFe²⁺ Si₄O₁₀; Fe^{2 +} in square-planar coordination, point symmetry C ₄), anatase (TiO₂; Ti⁴⁺ in octahedral coordination, point symmetry D _2d), and epidote (Ca₂(Al, Fe³⁺)₃SiO₄)₃(OH); Fe³⁺ in distorted octahedral coordination, point symmetry (C _s). For gillespite, the Fe K-XANES spectrum varies strongly with E-vector orientation of the incident X-ray beam. When the E-vector lies in the plane of the FeO₄ group (i.e., perpendicular to the c-axis), multiple-scattering features at 7127 and 7131 eV intensify, whereas when the E-vector is perpendicular to the plane of the FeO₄ group (i.e., parallel to the c-axis), a strongly-polarized 1s to 4p bound state transition occurs at 7116 eV and a localized continuum resonance occurs at 7122 eV. The Fe-K-EXAFS spectrum of gillespite is also highly polarization dependent. When the E-vector is perpendicular to c, all four nearest-neighbor oxygens around Fe²⁺ contribute to the EXAFS signal; when E is parallel to c, the EXAFS signal from nearest-neighbors is reduced by at least 86%. The unpolarized Ti K-XANES spectrum of anatase has three relatively strong pre-edge features at 4967.1, 4969.9, and 4972.7 eV which have resisted definitive interpretation in past studies. The lowest energy feature has a strong xy polarization dependence, suggesting a large amount of 4p _x,y character, and it is also very sharp, indicating a well-defined transition energy. Both of these observations are consistent with an excitonic state with a binding energy of 2.8 eV. The two higher energy features, which are characteristic of octahedrally-coordinated Ti⁴⁺, show little polarization dependence and are probably due to 1s to 3d bound-state transitions, with a small degree of np character in the final state wavefunction. Interpretation of the polarization dependence of Fe K-XANES spectra for epidote is not as straightforward due to the lower space group symmetry (P2₁/m) relative to gillespite (P4/ncc) and anatase (I4₁/amd) and the lower point group symmetry (C _s) of the M(3) site which contains most of the Fe³⁺ in the epidote structure. However, the presence of a shoulder at 7121 eV in the E parallel to b spectrum and its absence in the E normal to bc spectrum are consistent with it being a 1s to 4p _z bound-state transition. Strong, weakly x, y polarized features near 7126 eV in both spectra are most likely due to localized continuum transitions. Also, the 1s to 3d pre-edge intensity varies in intensity with E-vector orientation which is consistent with displacement of Fe³⁺ from the center of the M(3) octahedral site. Analysis of EXAFS spectra of epidote in these two polarizations yields bond distances which are within 0.04 Å of previous single-crystal X-ray diffraction analysis. This study demonstrates the utility of polarized X-ray absorption spectroscopy in quantifying the energies and orbital compositions of final state wavefunctions associated with various X-ray induced transitions in transition-metal containing minerals. It also shows that reasonably accurate M-O distances can be obtained for individual bonds oriented in crystallographically non-equivalent directions.     

Stratiform copper deposits and interactions with co-existing atmospheres, hydrospheres, biospheres and lithospheres

Fundamental evidence from world-class stratiform copper deposits repeatedly indicates that they originated by a two-stage mineralization process: a syn-diagenetic enrichment of the host sediment in iron sulfide, followed by a sub-surface addition of copper during early diagenesis of the sediment. In contrast to the previously favored syngenetic hypothesis, which suggested an open equilibration between atmosphere, hydrosphere, biosphere and upper lithosphere during mineralization, the two-stage model implies that only the initial deposition of iron sulfides should take place with open exchanges between the upper “spheres”. The sub-surface emplacement of copper should occur in relative isolation from surface environments and, therefore, the occurrence and distribution of stratiform copper deposits through time and space should not be used to make direct interpretations of contemporaneous conditions in the upper “spheres”.     

Phase relations of pyroxene and amphibole in greenstone,blueschist and eclogite of the Franciscan Complex,California

The phase relations of pyroxenes, amphiboles and associated minerals in metamorphic rocks of the Franciscan Complex can be graphically depicted on a ternary diagram which has at its apices the metamorphic clinopyroxene end members, viz NaAl-NaFe³⁺-Ca(Fe²⁺, Mg). Phases are plotted by projection from a constant subassemblage of minerals. This analysis allows interpretation of the effects of pressure, temperature, bulk rock composition and fluid composition on stability of minerals within the Franciscan.Pyroxenes in meta-igneous rocks and metagraywackes have a limited compositional range and fall into two groups: the omphacites, with 50±5% diopside +hedenbergite component; and the jadeitic pyroxenes with 10±5% diopside+hedenbergite. Pyroxenes intermediate between these two groups are unstable relative to assemblages containing Na-amphibole+other minerals.Coexisting pyroxenes and amphiboles in eclogites and associated coarse blueschists comprise equilibrium assemblages, and the proportion of pyroxene to amphibole is a function of rock composition. Eclogites are stable at higher temperature than regionally developed fine-grained greenstones and blueschists in the Franciscan, and at higher pressure than amphibolites. X _H2O ^fluid is not an important factor in the stability of Franciscan eclogite relative to amphibolite.     

Peat Accretion Histories During the Past 6,000 Years in Marshes of the Sacramento–San Joaquin Delta,CA, USA

The purpose of this study was to determine how vertical accretion rates in marshes vary through the millennia. Peat cores were collected in remnant and drained marshes in the Sacramento–San Joaquin Delta of California. Cubic smooth spline regression models were used to construct age–depth models and accretion histories for three remnant marshes. Estimated vertical accretion rates at these sites range from 0.03 to 0.49 cm year⁻¹. The mean contribution of organic matter to soil volume at the remnant marsh sites is generally stable (4.73% to 6.94%), whereas the mean contribution of inorganic matter to soil volume has greater temporal variability (1.40% to 7.92%). The hydrogeomorphic position of each marsh largely determines the inorganic content of peat. Currently, the remnant marshes are keeping pace with sea level rise, but this balance may shift for at least one of the sites under future sea level rise scenarios.     

Fractional crystallization and zoning in igneous feldspars: ideal water-buffered liquid fractionation lines and feldspar zoning paths

Diagrams giving plagioclase and sanidine fractionation paths and liquid fractionation lines under conditions of ideal water-buffered fractional crystallization in the ternary feldspar system were constructed graphically using topological reasoning, and experimental data and calculated phase relationships from the literature. The liquidus lines and solidus or solvus paths are unique at constant P and a _{H 2}O. The composition of a liquid evolves with time and moves along a fractionation line by removal of successive crystal fractions, whereas the compositions of each of the crystal fractions lie on and define a solidus or solvus path. Most but not all such water-buffered lines and paths differ only slightly from those in which water is free to build up during crystallization and a _{H 2}O to increase, as in many rocks. Liquid compositions lying along liquidus fractionation lines are not normally preserved, unless erupted as aphyric lavas. The solidus or solvus paths may be preserved either as overgrowth zones in crystals (zoning paths) or as a series of crystal fractions in layered intrusions. The topologies of the lines and paths depend mainly on the nature of the two-feldspar boundary line separating the plagioclase and sanidine fields which is a function of P _{H 2}O or a _{H 2}O at constant P; increases in either progressively lower the liquidi and solidi and cause larger intersections of the solidi with the solvus. One-feldspar solidus paths at high P and a _{H 2}O are simple, whereas they are complex and may bend back on themselves at low P _{H 2}O or low a _{H 2}O at high P. Two-feldspar paths may be simultaneous (cotectic) or sequential (peritectic). The former are simple and do not meet at high P and a _{H 2}O, the critical solution line lying in the gap; they are complex and may bend back or overlap at low P _{H 2}O or low a _{H 2}O at high P, the position of the critical solution line being hard to determine. Liquids which have simultaneously fractionated two feldspars may fractionate only one towards the end, crystallization changing from subsolvus to hypersolvus. Sequential paths may involve overgrowth of an early feldspar by a later one, usually sanidine overgrowths on plagioclase, but plagioclase overgrowths on sanidine occur. These complexities explain in part the difficulties of unravelling the textural and compositional relationships of ternary feldspars in water-poor felsic igneous rocks (even in the absence of alteration or complex magma dynamics) and of trying to deduce phase relationships from natural occurrences of feldspars.C.R.P.G. contribution number 948