Witt, M. L. I.

Measuring Hg/SO2 ratios in volcanic emissions is essential for better apportioning the volcanic contribution to the global Hg atmospheric cycle. Here, we report the first real-time simultaneous measurement Hg and SO2 in a volcanic plume, based on Lumex and MultiGAS techniques, respectively. We demonstrate that the use of these novel techniques allows the measurements of Hg/SO2 ratios with a far better time resolution than possible with more conventional methods. The Hg/SO2 ratios in the plume of F0 fumarole on La Fossa Crater, Vulcano Island spanned an order of magnitude over a 30 minute monitoring period, but was on average in qualitative agreement with the Hg/SO2 ratio directly measured in the fumarole (mean plume and fumarole ratios being 1.09 x 10-6 and 2.9 x 10-6, respectively). The factor 2 difference between plume and fumarole compositions provides evidence for fast Hg chemical processing the plume.

Mt. Etna is a major natural source of Hg to the Mediterranean region. Total mercury concentrations, [Hg]tot,in Castanea sativa (sweet chestnut) leaves sampled 7–13 km from Etna's vents (during six campaigns in 2005–2011) were determined using atomic absorption spectroscopy. [Hg]tot in C. sativa was greatest on Etna's SE flank reflecting Hg deposition from the typically overhead volcanic plume. [Hg]tot also showed Hg accumulation over the growing season, increasing with leaf age and recent eruptive activity. [Hg]tot in C. sativa was not controlled by [Hg]tot in soils, which instead was greatest on Etna's NW flank, and was correlated with the proportion of organic matter in the soil (% Org). An elevated [Hg]tot/% Org ratio in soils on Etna's SE flank is indicative of increased Hg deposition. This ratio was also found to decrease with local soil pH, suggesting that Hg deposited to the low pH and organic-poor soils on Etna's SE flank may not be retained but will instead be released to groundwater or re-emitted to the atmosphere. These results show that the deposition of volcanic Hg has clear impacts and confirm that Etna is an important source of Hg to the local environment.

Here we report results from a multidisciplinary field campaign at Villarrica volcano, Chile, in March 2009. A range of direct sampling and remote sensing techniqueswas employed to assess gas and aerosol emissions from the volcano, and extend the time series of measurements that have been made during recent years. Airborne traverses beneath the plume with an ultraviolet spectrometer yielded an average SO2 flux of 3.7 kg s−1. This value is similar to previous measurements made at Villarrica during periods of quiescent activity. The composition of the plume was measured at the crater rim using electrochemical sensors and, for the first time, open-path Fourier transforminfrared spectroscopy, yielding a composition of 90.5 mol% H2O, 5.7% CO2, 2.6%SO2, 0.9% HCl, 0.3% HF and b0.01% H2S. Comparison with previous gas measurements made between 2000 and 2004 shows a correlation between increased SO2/HCl ratios and periods of increased activity. Base-treated filter packs were also employed during our campaign, yielding molar ratios of HBr/SO2=1.1×10−4, HI/SO2=1.4×10−5 and HNO3/SO2=1.1×10−3 in the gas phase. Our data represent the most comprehensive gas inventory at Villarrica to date, and the first evaluation of HBr and HI emissions from a South American volcano. Sun photometry of the plume showed the near-source aerosol size distributions were bimodal with maxima at b0.1 and ~1 μm. These findings are consistent with results from analyses in 2003. Electron microscope analysis of particulatematter collected on filters showed an abundance of sphericalmicron-sized particles that are rich in Si, Mg and Al. Non-spherical, S-rich particles were also observed.

We report measurements of Hg, SO2, and halogens (HCl, HBr, HI) in volcanic gases from Masaya volcano, Nicaragua, and gaseous SO2 and halogens from Telica volcano, Nicaragua. Mercury measurements were made with a Lumex 915+ portable mercury vapor analyzer and gold traps, while halogens, CO2 and S species were monitored with a portable multi gas sensor and filter packs. Lumex Hg concentrations in the plume were consistently above background and ranged up to 350 ng/m3. Hg/SO2 mass ratios measured with the real-time instruments ranged from 1.1*10-7 to 3.5*10-5 (mean 2*10-5). Total gaseous mercury TGM)concentrations measured by gold trap ranged from 100 to 225 ng/m3. Reactive gaseous mercury accounted for 1% of TGM, while particulate mercury was 5% of the TGM. Field measurements of Masaya’s SO2 flux, combined with the Hg/SO2 ratio, indicate a Hg flux from Masaya of 7.2 Mg/a-1. At Masaya’s low temperature fumaroles, Hg/CO2 mass ratios were consistently around 2*10-8, lower than observed in the main vent (Hg/CO2 10-7). Low-temperature fumarole Hg fluxes from Masaya are insignificant (150 g a-1). Ratios of S, C and halogen species were also measured at Masaya and Telica volcanoes. CO2/SO2 ratios at Masaya ranged from 2.8 to 3.9, comparable to previously published values. At Masaya molar Br/SO2 was 3*10-4 and I/SO2 was 2*10-5, suggesting fluxes of 0.2–0.5 Mg HBr d-1 and 0.02–0.05 Mg HI d-1. At Telica the Br/SO2 ratio was also 3*10-4 and the I/SO2 ratio was 5.8*10-5, with corresponding fluxes of 0.2 Mg HBr d-1 and 0.06 Mg HI d-1. Gases at both volcanoes are enriched in I relative to Br and Cl, compared to gases from volcanoes elsewhere.

Volcanic plume samples taken in 2008 and 2009 from the Halemàumàu eruption at Kīlauea provide new insights into Kīlauea's degassing behaviour. The Cl, F and S gas systematics are consistent with syn-eruptive East Rift Zone measurements suggesting that the new Halemàumàu activity is fed by a convecting magma reservoir shallower than the main summit storage area. Comparison with degassing models suggests that plume halogen and S composition is controlled by very shallow (<3m depth) decompression degassing and progressive loss of volatiles at the surface. Compared to most other global volcanoes, Kīlauea's gases are depleted in Cl with respect to S. Similarly, our Br/S and I/S ratio measurements in Halemàumàu's plume are lower than those measured at arc volcanoes, consistent with contributions from the subducting slab accounting for a significant proportion of the heavier halogens in arc emissions. Analyses of Hg in Halemàumàu's plume were inconclusive but suggest a flux of at least 0.6kgday -1 from this new vent, predominantly (>77%) as gaseous elemental mercury at the point of emission. Sulphate is an important aerosol component (modal particle diameter ∼0.44μm). Aerosol halide ion concentrations are low compared to other systems, consistent with the lower proportion of gaseous hydrogen halides. Plume concentrations of many metallic elements (Rb, Cs, Be, B, Cr, Ni, Cu, Mo, Cd, W, Re, Ge, As, In, Sn, Sb, Te, Tl, Pb, Mg, Sr, Sc, Ti, V, Mn, Fe, Co, Y, Zr, Hf, Ta, Al, P, Ga, Th, U, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm) are elevated above background air. There is considerable variability in metal to SO 2 ratios but our ratios (generally at the lower end of the range previously measured at Kīlauea) support assertions that Kīlauea's emissions are metal-poor compared to other volcanic settings. Our aerosol Re and Cd measurements are complementary to degassing trends observed in Hawaiian rock suites although measured aerosol metal/S ratios are about an order of magnitude lower than those calculated from degassing trends determined from glass chemistry. Plume enrichment factors with respect to Hawaiian lavas are in broad agreement with those from previous studies allowing similar element classification schemes to be followed (i.e., lithophile elements having lower volatility and chalcophile elements having higher volatility). The proportion of metal associated with the largest particle size mode collected (>2.5μm) and that bound to silicate is significantly higher for lithophiles than chalcophiles. Many metals show higher solubility in pH 7 buffer solution than deionised water suggesting that acidity is not the sole driver in terms of solubility. Nonetheless, many metals are largely water soluble when compared with the other sequential leachates suggesting that they are delivered to the environment in a bioavailable form. Preliminary analyses of environmental samples show that concentrations of metals are elevated in rainwater affected by the volcanic plume and even more so in fog. However, metal levels in grass samples showed no clear enrichment downwind of the active vents. © 2011 Elsevier Ltd.

A major uncertainty regarding the environmental impacts of volcanic Hg is the extent to which Hg is deposited locally or transported globally. An important control on dispersion and deposition is the oxidation state of Hg compounds: Hg(0) is an inert, insoluble gas, while Hg(II) occurs as reactive gases or in particles, which deposit rapidly and proximally, near the volcanic vent. Using a new high temperature thermodynamic model, we show that although Hg in Etna's magmatic gases is almost entirely Hg(0) (i.e., gaseous elemental mercury), significant quantities of Hg(II) are likely formed at Etna's vents as gaseous HgCl2, when magmatic gases are cooled and oxidised by atmospheric gases. These results contrast with an earlier model study and allow us to explain recent measurements of Hg speciation at the crater rim of Etna without invoking rapid (b1 min) low temperature oxidation processes. We further model Hg speciation for a series of additional magmatic gas compositions. Compared to Etna, Hg(II) production (i.e., Hg(II)/Hgtot) is enhanced in more HCl-rich magmatic gases, but is independent of the Hg, HBr and HI content of the magmatic gases. Hg(II) production is not strongly influenced by the initial oxidation state of magmatic gases above NNO, although production is hindered in more reduced magmatic gases. The modelandresults arewidely applicable to other open-vent volcanoes and may be used to improve the accuracy of chemical kinetic models for low temperature Hg speciation in volcanic plumes.