Mount Etna the major point source of metals in the Mediterranean basin: impact on atmospheric precipitation

Mount Etna is a huge volcano in the Mediterranean basin and is located in the eastern part of Sicily. It is considered to be, on the long-term average, the major atmospheric point source of many environmental harmful compounds. Their emission occurs either through continuous passive degassing from open-conduit activity or through sporadic paroxysmal eruptive activity, in the form of gases, aerosols or particulate. Volcanic volatiles and aerosol emitted into the atmosphere fall on the Earth’s surface as wet or dry deposition, and can influence the environment both at local and regional scale. To estimate the environmental impact of magma-derived trace metals and their depositions processes, bulk deposition samples have been collected approximately fortnightly, using a network of 5 rain gauges located at various altitudes on the upper flanks close to the summit craters, from April 2006 to December 2007. Samples were analyzed for the main chemicalphysical parameters (electric conductivity and pH) and for major and trace elements concentrations. The data obtained clearly show that the volcanic contribution is always prevailing in the sampling site closest to the summit craters (∼1.5 km). In the distal sites (5.5-10 km from the summit) and downwind of the summit craters, the volcanic contribution is also detectable but often overwhelmed by anthropogenic or other natural (seawater spray, geogenic dust) contributions. Volcanogenic contribution may derive from both dry and wet deposition of gases and aerosols from the volcanic plume, but sometimes also from leaching of freshly emitted volcanic ashes. In fact, in our background site (7.5 km in the upwind direction), after an ash deposition event high concentration of lithophiles elements (Si, Al, Fe, Ti) have been measured. Sulphur, Chlorine and Fluorine, represent the main constituents that characterize the volcanic contribution in the bulk deposition on Mt. Etna, although high concentrations of many trace elements (Si, Al, Fe, Ti, Cu, As, Rb, Pb, Tl, Cd, Cr, U and Ag) display, in the site most exposed to the volcanic emissions, average concentrations of about two orders of magnitude higher than those measured in the background site (Mount Intraleo)

Atmospheric impact of volcanic volatiles: trace elements in snow and bulk deposition samples at Mount Etna (Italy)

Volcanoes represent an important natural source of several trace elements to the atmosphere. For some species (e.g., As, Cd, Pb and Se) they may be the main natural source and thereby strongly influencing geochemical cycles from the local to the global scale. Mount Etna is one of the most actively degassing volcanoes in the world, and it is considered to be, on the long-term average, the major atmospheric point source of many environmental harmful compounds. Their emission occurs either through continuous passive degassing from open-conduit activity or through sporadic paroxysmal eruptive activity, in the form of gases, aerosols or particulate. To estimate the environmental impact of magma-derived trace metals and their depositions processes, rainwater and snow samples were collected at Mount Etna area. Five bulk collectors have been deployed at various altitudes on the upper flanks around the summit craters of the volcano; samples were collected every two week for a period of one year and analyzed for the main chemical-physical parameters (electric conductivity and pH) and for major and trace elements concentrations. Chemical analysis of rainwater clearly shows that the volcanic contribution is always prevailing in the sampling site closest to the summit crater (about 1.5 km). In the distal sites (5.5-10 km from the summit) and downwind of the summit craters, the volcanic contribution is also detectable but often overwhelmed by anthropogenic or other natural (seawater spray, geogenic dust) contributions. Volcanic contribution may derive from both dry and wet deposition of gases and aerosols from the volcanic plume, but sometimes also from leaching of freshly emitted volcanic ashes. In fact, in our background site (7.5 km in the upwind direction) volcanic contribution has been detected only following an ash deposition event. About 30 samples of fresh snow were collected in the upper part of the volcano, during the winters 2006 and 2007 to estimate deposition processes at high altitude during cold periods. Some of the samples were collected immediately after a major explosive event from the summit craters to understand the interaction between snow and fresh erupted ash. Sulphur, Chlorine and Fluorine, are the major elements that prevailingly characterize the volcanic contribution in atmospheric precipitation on Mount Etna, but high concentrations of many trace elements are also detected in the studied samples. In particular, bulk deposition samples display high concentration of Al, Fe, Ti, Cu, As, Rb, Pb, Tl, Cd, Cr, U and Ag, in the site most exposed to the volcanic emissions: median concentration values are about two orders of magnitude higher than those measured in our background site. Also in the snow samples the volcanic signature is clearly detectable and decreases with distance from the summit craters. Some of the analysed elements display very high enrichment values with respect to the average crust and, in the closest site to the summit craters, also deposition values higher than those measured in polluted urban or industrial sites

The bridge volcanic LIdar-BILLI: A review of data collection and processing techniques in the Italian most hazardous volcanic areas

Volcanologists have demonstrated that carbon dioxide (CO2) fluxes are precursors of volcanic eruptions. Controlling volcanic gases and, in particular, the CO2 flux, is technically challenging, but we can retrieve useful information from magmatic/geological process studies for the mitigation of volcanic hazards including air traffic security. Existing techniques used to probe volcanic gas fluxes have severe limitations such as the requirement of near-vent in situ measurements, which is unsafe for operators and deleterious for equipment. In order to overcome these limitations, a novel range-resolved DIAL-Lidar (Differential Absorption Light Detection and Ranging) has been developed as part of the ERC (European Research Council) Project "BRIDGE", for sensitive, remote, and safe real-time CO2 observations. Here, we report on data collection, processing techniques, and the most significant findings of the experimental campaigns carried out at the most hazardous volcanic areas in Italy: Pozzuoli Solfatara (Phlegraen Fields), Stromboli, and Mt. Etna. The BrIdge voLcanic LIdar-BILLI has successfully obtained accurate measurements of in-plume CO2 concentration and flux. In addition, wind velocity has also been retrieved. It has been shown that the measurements of CO2 concentration performed by BILLI are comparable to those carried out by volcanologists with other standard techniques, heralding a new era in the observation of long-term volcanic gases

Unmanned aerial vehicle measurements of volcanic carbon dioxide fluxes

We report the first measurements of volcanic gases with an unmanned aerial vehicle (UAV). The data were collected at La Fossa crater, Vulcano, Italy, during April 2007, with a helicopter UAV of 3 kg payload, carrying an ultraviolet spectrometer for remotely sensing the SO2 flux (8.5 Mg d−1), and an infrared spectrometer, and electrochemical sensor assembly for measuring the plume CO2/SO2 ratio; by multiplying these data we compute a CO2 flux of 170 Mg d−1. Given the deeper exsolution of carbon dioxide from magma, and its lower solubility in hydrothermal systems, relative to SO2, the ability to remotely measure CO2 fluxes is significant, with promise to provide more profound geochemical insights, and earlier eruption forecasts, than possible with SO2 fluxes alone: the most ubiquitous current source of remotely sensed volcanic gas data

Rainwater-induced leaching of selenium, arsenic and vanadium from Etnean volcanic soils

Active volcanoes emit considerable amounts of contaminants such as As, Se and V. Mount Etna is the biggest volcano of Europe and an excellent geochemical site to study water-soil processes. Due to its volcanic activity, the rainwater has a strong compositional gradient, both in time and space. At present, the behaviour of trace elements in the soils around Mt Etna is poorly understood. To determine the influence of the rainwater pH on the potential mobilization of geogenic pollutants, batch experiments have been performed with synthetic rainwater for 25 soils collected along the flanks of the volcano. Our results show that: i) The maximum concentrations in the leaching solutions are higher for acid rain than for neutral rain (e.g. 7.7 vs 1.3 mg/L for Se). ii) With neutral rain conditions the soils upwind from the volcano have higher concentrations of Se than those downwind (up to 1.3 mg/L compared to ≤0.3 mg/L for the other samples). This trend is less clear for As and V. iii) For soils collected from 2 to 10 km downwind of the craters, Se concentrations in acid rain leachates decrease one order of magnitude with increasing distance. A similar pattern is also observed upwind from the volcano. For As and V no clear relationship between concentrations and location with respect to the volcanic craters is observed. Both i) and ii) result in a low pH dependence for samples upwind from the volcano. The biggest difference between acid and neutral leaching for As and V is observed for a sample 2 km downwind from the craters. The observed patterns are influenced by potential controlling factors, such as organic matter content, total concentrations, mineralogy, influence of the volcanic plume, etc. Our results have implications for the chemical composition of the Etnean aquifer, the only water resource to the one million inhabitants around Mt Etna, as well as for the bioavailability and potential toxicity through agricultural activities, essential to the local economy

Vulcamera: a program for measuring volcanic SO2 using UV cameras

We report here on Vulcamera, a stand-alone program for the determination of volcanic SO2 fluxes using ultraviolet cameras. The code enables field image acquisition and all the required post-processing operations

Geogenic element behaviour in soil-rainwater interaction at Mt Etna, Sicily: preliminary results

Active volcanoes emit considerable amounts of contaminants such as As, Se and V. Previous studies have shown that the volcanic activity at Mt Etna (Sicily) has a strong influence on local rainwater compositions. However to date, the behaviour of trace elements in the soils around Mt Etna is poorly understood. 4-hr batch experiments have been performed with 1:5 soil solutions of air-dried soil (fraction <2 mm) and synthetic (acid) rainwater (using either deionized water with a pH of ~6 or a ~500 ppm of sulphuric acid solution with a pH of ~2). In general trace element concentrations are more enriched in soil solutions with low pH (e.g. enrichment factor (EF) acid compared to neutral soil solution is up to 4.3x102 for V, 2.5x102 for As and 50 for Se). However, it seems that the EF especially for As and V has a correlation with the distance to the crater. Additional, some soils located downwind of the volcano have EFs smaller than 1 (i.e. the elements are more enriched in neutral rainwater), for several elements like V, As and Se. For As and V the EF seems to be vary with distance to the crater. Some possible explanations for these trends will be discussed. These results might have important implications for the chemical composition of the Etnean aquifer, the only water resource to the one million inhabitants around Mt Etna, as well as the bioavailability and therefore potential toxicity through agricultural activities, essential to the local economy

Recent advances in ground-based ultraviolet remote sensing of volcanic SO2 fluxes

Measurements of volcanic SO2 emission rates have been the mainstay of remote-sensing volcanic gas geochemistry for almost four decades, and they have contributed significantly to our understanding of volcanic systems and their impact upon the atmosphere. The last ten years have brought stepchange improvements in the instrumentation applied to these observations, which began with the application of miniature ultraviolet spectrometers that were deployed in scanning and traverse configurations, with differential optical absorption spectroscopy evaluation routines. This study catalogs the more recent empirical developments, including: ultraviolet cameras; wideangle field-of-view differential optical absorption spectroscopy systems; advances in scanning operations, including tomography; and improved understanding of errors, in particular concerning radiative transfer. Furthermore, the outcomes of field deployments of sensors during the last decade are documented, with respect to improving our understanding of volcanic dynamics and degassing into the atmosphere

UV camera measurements of fumarole field degassing (La Fossa crater, Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO2 flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO2 gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO2 flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO2 flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d−1, with a total emission from the entire system of ~ 20 t d−1 and ~ 13 t d−1, in November 2009 and February 2010 respectively. These data were augmented with molar H2S/SO2, CO2/SO2 and H2O/SO2 ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO2 flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO2 (684 t d−1 and 293 t d−1), H2S (8 t d−1 and 7.5 t d−1) and H2O (580 t d−1 and 225 t d−1).Published47-52JCR Journalrestricte

Mercury concentration, speciation and budget in volcanic aquifers: Italy and Guadeloupe (Lesser Antilles)

Quantifying the contribution of volcanism to global mercury (Hg) emissions is important to understand the pathways and the mechanisms of Hg cycling through the Earth's geochemical reservoirs and to assess its environmental impacts. While previous studies have suggested that degassing volcanoes might contribute importantly to the atmospheric budget of mercury, little is known about the amount and behaviour of Hg in volcanic aquifers. Here we report on detailed investigations of both the content and the speciation of mercury in aquifers of active volcanoes in Italy and Guadeloupe Island (Lesser Antilles). In the studied groundwaters, total Hg (THg) concentrations range from 10 to 500 ng/l and are lower than the 1000 ng/l threshold value for human health protection fixed by the World Health Organization [WHO (1993): WHO Guidelines for Drinking Water Quality- http://www.who.int/water_sanitation_health/GDWQ/index.htlm]. Positive co-variations of (THg) with sulphate indicate that Hg-SO4-rich acid groundwaters receive a direct input of magmatic/hydrothermal gases carrying mercury as Hg0 (gas). Increasing THg in a volcanic aquifer could thus be a sensitive tracer of magmatic gas input prior to an eruption. Since the complex behaviour and toxicity of mercury in waters depend on its chemical speciation, we carefully determined the different aqueous forms of this element in our samples.We find that dissolved elemental Hg0 (aq) and particulate-bound Hg (HgP) widely prevail in volcanic aquifers, in proportions that highlight the efficiency of Hg adsorption onto colloidal particles. Moreover, we observe that dissolved Hg0 aq and Hg(II) forms coexist in comparable amount in most of the waters, in stark contrast to the results of thermodynamic equilibrium modelling. Therefore, chemical equilibrium between dissolved mercury species in volcanic waters is either prevented by natural kinetic effects or not preserved in collected waters due to sampling/storage artefacts. Finally, we provide a first quantitative comparison of the relative intensity of aqueous transport and atmospheric emissions of mercury at Mount Etna, a very active basaltic volcano