Fe isotopic fractionation during mineral dissolution with and without bacteria

Fe released into solution is isotopically lighter (enriched in the lighter isotope) than hornblende starting material when dissolution occurs in the presence of the siderophore desferrioxamine mesylate (DFAM). In contrast, Fe released from goethite dissolving in the presence of DFAM is isotopically unchanged. Furthermore, Δ⁵⁶Fe_{solution-hornblende} for Fe released to solution in the presence of ligands varies with the affinity of the ligand for Fe. The extent of isotopic fractionation of Fe released from hornblende also increases when experiments are agitated continuously. The Fe isotope fractionation observed during hornblende dissolution with organic ligands is attributed predominantly to retention of ⁵⁶Fe in an altered surface layer, while the lack of isotopic fractionation during goethite dissolution in DFAM is consistent with the lack of an altered layer. When a siderophore-producing soil bacterium is added to the system (without added organic ligands), Fe released to solution from both hornblende and goethite differs isotopically from Fe in the bulk mineral: Δ⁵⁶Fe_{solution-starting material} = −0.56 ± 0.19 (hornblende) and −1.44 ± 0.16 (goethite). Increased isotopic fractionation is attributed in this case to the fact that as bacterial respiration depletes the system in oxygen and aqueous Fe is reduced, equilibration between aqueous ferrous and ferric iron creates a pool of isotopically heavy ferric iron that is assimilated by bacterial cells. Adsorption of isotopically heavy ferrous iron (Fe(II) enriched in the heavier isotope) or precipitation of isotopically heavy Fe minerals may also contribute to observed fractionations.To test whether these Fe isotope signatures are recorded in natural systems, we also investigated extractions of samples of soils from which the bacteria were isolated. These extractions show variability in the isotopic signatures of exchangeable Fe and Fe oxyhydroxide fractions from one soil sample to another, but exchangeable Fe is observed to be lighter than Fe in soil Fe oxyhydroxides and hornblende. This observation is consistent with isotopically light Fe-organic complexes in soil pore water derived from the Fe-silicate starting materials in the presence of growing microorganisms, as documented in experiments reported here. The contributions from phenomena including organic ligand-promoted nonstoichiometric dissolution of Fe silicates, uptake of ferric iron by organisms, adsorption of isotopically heavy ferrous iron, and precipitation of iron minerals should create complex isotopic signatures in soils. Better understanding of these processes and the timescales over which they contribute to fractionation is needed.     

Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn²⁺ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn²⁺ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn²⁺, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.     

Petrogenesis of Quebrada de la Mina and Altar North porphyries (Cordillera of San Juan,Argentina): Crustal assimilation and metallogenic implications

We investigate the geology of Altar North (Cu–Au) and Quebrada de la Mina (Au) porphyry deposits located in San Juan Province (Argentina), close to the large Altar porphyry copper deposit (995 Mt, 0.35% Cu, 0.083 g/t Au), to present constraints on the magmatic processes that occurred in the parental magma chambers of these magmatic-hydrothermal systems. Altar North deposit comprises a plagioclase-amphibole-phyric dacite intrusion (Altar North barren porphyry) and a plagioclase-amphibole-biotite-phyric dacite stock (Altar North mineralized porphyry, 11.98 ± 0.19 Ma). In Quebrada de la Mina, a plagioclase-amphibole-biotite-quartz-phyric dacite stock (QDM porphyry, 11.91 ± 0.33 Ma) crops out. High Sr/Y ratios (92–142) and amphibole compositions of Altar North barren and QDM porphyries reflect high magmatic oxidation states (fO₂ = NNO +1.1 to +1.6) and high fH₂O conditions in their magmas. Zones and rims enriched in anorthite (An_37–48), SrO (0.22–0.33 wt.%) and FeO (0.21–0.37 wt.%) in plagioclase phenocrysts are evidences of magmatic recharge processes in the magma chambers. Altar North and Quebrada de la Mina intrusions have relatively homogeneous isotopic compositions (⁸⁷Sr/⁸⁶Sr_(t) = 0.70450–0.70466, ε_Nd(t) = +0.2 to +1.2) consistent with mixed mantle and crust contributions in their magmas. Higher Pb isotopes ratios (²⁰⁷Pb/²⁰⁴Pb = 15.6276–15.6294) of these intrusions compared to other porphyries of the district, reflect an increase in the assimilation of high radiogenic Pb components in the magmas. Ages of zircon xenocrysts (297, 210, 204, 69 Ma) revealed that the magmas have experienced assimilation of Miocene, Cretaceous, Triassic and Carboniferous crustal rocks.Fluids that precipitated sulfides in the Altar deposit may have remobilized Pb from the host rocks, as indicated by the ore minerals being more radiogenic (²⁰⁷Pb/²⁰⁴Pb = 15.6243–15.6269) than their host intrusions. Au/Cu ratio in Altar porphyries (average Au/Cu ratio of 0.14 × 10^?4 by weight in Altar Central) is higher than in the giant Miocene porphyry deposits located to the south: Los Pelambres, Río Blanco and Los Bronces (Chile) and Pachón (Argentina). We suggest that the increase in Au content in the porphyries of this region could be linked to the assimilation of high radiogenic Pb components in the magmas within these long-lived maturation systems.     

New Constraints on Ages of Glasses Proposed as Reference Materials for Fission-Track Dating

New analyses have been performed in order to enhance the data-set on the independent ages of four glasses that have been proposed as reference materials for fission-track dating. The results are as follows. Moldavite - repeated ⁴⁰Ar/³⁹Ar age determinations on samples from deposits from Bohemia and Moravia yielded an average of 14.34 ± 0.08 Ma. This datum agrees with other recent determinations and is significantly younger than the ⁴⁰Ar/³⁹Ar age of 15.21 ± 0.15 Ma determined in the early 1980s. Macusanite (Peru) -four K-Ar ages ranging from 5.44 ± 0.06 to 5.72 ± 0.12 Ma have been published previously. New ⁴⁰Ar/³⁹Ar ages gave an average of 5.12 ± 0.04 Ma. Plateau fission-track ages determined using the IRMM-540 certified glass and U and Th thin films for neutron fluence measurements agree better with these new ⁴⁰Ar/³⁹Ar ages than the previously published ages. Roccastrada glass (Italy) - a new ⁴⁰Ar/³⁹Ar age, 2.45 ± 0.04 Ma, is consistent with previous determinations. The Quiron obsidian (Argentina) is a recently discovered glass that has been proposed as an additional reference material for its high spontaneous track density (around 100 000 cm^-2). Defects that might produce "spurious" tracks are virtually absent. An independent ⁴⁰Ar/³⁹Ar age of 8.77 ± 0.09 Ma was determined and is recommended for this glass. We believe that these materials, which will be distributed upon request to fission-track groups, will be very useful for testing system calibrations and experimental procedures.