Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg(fum) T , plume gaseous elemental Hg(g) 0 and plume particulate Hg(p) II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on HgT/SO2 in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y−1, in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1–3), 115–121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO2 at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg(p) II increases with distance from the fumarole vent, at the expense of Hg(g) 0 and indicates significant in-plume oxidation and condensation of fumarole Hg(fum) T . Relative to the NIST SRM3133 Hg standard, the stable isotopic compositions of Hg are δ202Hg(fum) T =−0.74‰±0.18 (2SD, n=4) for condensed gaseous fumarole Hg(fum) T , δ202Hg(g) 0 =−1.74‰±0.36 (2SD, n=1) for plume gaseous elemental Hg(g) 0 at the F0 fumarole, and δ202Hg(p) II =−0.11‰±0.18 (2SD, n=4) for plume particulate Hg(p) II . The enrichment of Hg(p) II in the heavy isotopes and Hg(g) 0 in the light isotopes relative to the total condensed fumarolic Hg(fum) T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion inambient T° atmosphere. A first order Rayleigh equilibriumcondensation isotope fractionation model yields a fractionation factor αcond-gas of 1.00135±0.00058

Surface Chemistry of Almandine Garnet

Almandine garnet is used commonly in abrasive blasting processes to prepare metallic surfaces for painting. However, there is evidence that the process leads to significant amounts of abrasive embedded in the “cleaned” surface, and hence the surface chemistry of garnet will affect the binding of any coatings subsequently applied. In addition, in marine environments seawater aerosol droplets are expected to impact the exposed surface prior to coating application, depositing both water and dissolved inorganic ions. In this work, we provide indepth analysis of the chemistry of the almandine garnet surface using angle-resolved X-ray photoelectron spectroscopy (XPS) and note a correlation for several elemental oxides between literature values of the binding energy of the surface oxygen 1s XPS peak and the basicity of the hydroxyl group that forms on the surface. We also consider the adsorption to almandine garnet powder of seawater-relevant inorganic ions (sodium, magnesium, and calcium): Binding constants have been determined using titration measurements, solution-depletion isotherms, and numerical modeling, with calcium observed to bind more strongly than magnesium. The relevance of Langmuir-type fits to constant-pH adsorption isotherms is discussed. By contrast, sodium either binds very weakly or is effectively inert toward the garnet surface under the experimental conditions. The complex adsorption behavior observed emphasizes the necessity of using multiple techniques to characterize mineral surfaces