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.

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