Iron release in aqueous environment by fresh volcanic ash from Mount Etna (Italy) and Popocatépetl (Mexico) volcanoes

In this study, we performed leaching experiments for timescales of hours-to-months in deionized water on fresh volcanic ash from Mt. Etna (Italy) and Popocatépetl (Mexico) volcanos to monitor Fe release as a function of ash mineral chemistry and size, with the aim of clarifying Fe release mechanisms and eventually evaluating the impact of volcanic ash on marine and lacustrine environments. To define sample mineralogy and Fe speciation, inclusive characterization was obtained by means of XRF, SEM, XRPD, EELS and Mössbauer spectroscopies. For Etna and Popocatépetl samples, glass proportions were quantified at 73 and 40%, Fe₂O₃ total contents at 11.6–13.2 and 5.8 wt%, and Fe³⁺/Fe_Tot ratios at 0.33 and 0.23, respectively. Leaching experiments showed that significant amounts of iron, ~?30 to 150 and ~?750 nmol g^?1 l^?1 for pristine Etna and Popocatépetl samples, respectively, are released within the first 30 min as a function of decreasing particle size (from 1 to 0.125 mm). The Popocatépetl sample showed a very sustained Fe release (up to 10 times Etna samples) all along the first week, with lowest values never below 400 nmol g^?1 l^?1 and a maximum of 1672 nmol g^?1 l^?1 recorded after 5 days. This sample, being composed of very small particles (average particle size 0.125 mm) with large surface area, likely accumulated large quantities of Fe-bearing sublimates that quickly dissolved during leaching tests, determining high Fe release and local pH decrease (that contributed to release more Fe from the glass) at short timescale (hours-to-days). The fractional Fe solubility (Fe_S) was 0.004–0.011 and 0.23% for Etna and Popocatépetl samples, respectively, but no correlation was found between Fe released in solution and either ash Fe content, glass/mineral ratio or mineral assemblage. Results obtained suggest that volcanic ash chemistry, mineralogy and particle size assume a relevant role on Fe release mostly in the medium-to-long timescale, while Fe release in the short timescale is dominated by dissolution of surface sublimates (formed by physicochemical processes occurring within the eruption plume and volcanic cloud) and the effects of such a dissolution on the local pH conditions. For all samples, a moderate to sustained Fe release occurred for leaching times comparable with their residence time within the euphotic zone of marine and lacustrine environments (variable from few minutes to few hours), revealing their possible contribution to increase Fe bioavailability.     

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.     

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.