Mariano Valenza

Mobility and fluxes of major, minor and trace metals during basalt weathering and groundwater transport at Mt. Etna volcano (Sicily)

Abstract The concentrations and fluxes of major, minor and trace metals were determined in 53 samples of groundwaters from around Mt Etna, in order to evaluate the conditions and extent of alkali basalt weathering by waters enriched in magma-derived CO 2 and the contribution of aqueous transport to the overall metal discharge of the volcano. We show that gaseous input of magmatic volatile metals into the Etnean aquifer is small or negligible, being limited by cooling of the rising fluids. Basalt leaching by weakly acidic, CO 2 -charged water is the overwhelming source of metals and appears to be more extensive in two sectors of the S-SW (Paterno) and E (Zafferana) volcano flanks, where out flowing groundwaters are the richest in metals and bicarbonate of magmatic origin. Thermodynamic modeling of the results allows to evaluate the relative mobility and chemical speciation of various elements during their partitioning between solid and liquid phases through the weathering process. The facts that rock-forming minerals and groundmass dissolve at different rates and secondary minerals are formed are taken into account. At Mt. Etna, poorly mobile elements (Al, Th, Fe) are preferentially retained in the solid residue of weathering, while alkalis, alkaline earth and oxo-anion-forming elements (As, Se, Sb, Mo) are more mobile and released to the aqueous system. Transition metals display an intermediate behavior and are strongly dependent on either the redox conditions (Mn, Cr, V) or solid surface-related processes (V, Zn, Cu). The fluxes of metals discharged by the volcanic aquifer of Etna range from 7.0 × 10 −3 t/a (Th) to 7.3 × 10 4 t/a (Na). They are comparable in magnitude to the summit crater plume emissions for a series of elements (Na, K, Ca, Mg, U, V, Li) with lithophile affinity, but are minor for volatile elements. Basalt weathering at Mt Etna also consumes about 2.1 × 10 5 t/a of magma-derived carbon dioxide, equivalent to ca. 7% of contemporaneous crater plume emissions. The considerable transport of some metals in Etna’s aquifer reflects a particularly high chemical erosion rate, evaluated at 2.3∗10 5 t/a, enhanced by the initial acidity of magmatic CO 2 -rich groundwater.

Forecasting Etna eruptions by real-time observation of volcanic gas composition

It is generally accepted, but not experimentally proven, that a quantitative prediction of volcanic eruptions is possible from the evaluation of volcanic gas data. By discussing the results of two years of real-time observation of H2O, CO2, and SO2 in volcanic gases from Mount Etna volcano, we unambiguously demonstrate that increasing CO2/SO2 ratios can allow detection of the pre-eruptive degassing of rising magmas. Quantitative modeling by the use of a saturation model allows us to relate the pre-eruptive increases of the CO2/SO2 ratio to the refilling of Etnas shallow conduits with CO2-rich deep-reservoir magmas, leading to pressurization and triggering of eruption. The advent of real-time observations of H2O, CO2, and SO2, combined with well-constrained models of degassing, represents a step forward in eruption forecasting.

Fluid circulation at Stromboli volcano (Aeolian Islands, Italy) from self-potential and CO2 surveys

This work addresses the study of fluid circulation of the Stromboli island using a dense coverage of self-potential (SP) and soil CO2 data. A marked difference exists between the northern flank and the other flanks of the island. The northern flank exhibits (1) a typical negative SP/altitude gradient not observed on the other flanks, and (2) higher levels of CO2. The general SP pattern suggests that the northern flank is composed of porous layers through which vadose water flows down to a basal water table, in contrast to the other flanks where impermeable layers impede the vertical flow of vadose water. In the Sciara del Fuoco and Rina Grande–Le Schicciole landslide complexes, breccias of shallow gliding planes may constitute such impermeable layers whereas elsewhere, poorly permeable, fine-grained pyroclastites or altered lava flows may be present. This general model of the flanks also explains the main CO2 patterns: concentration of CO2 at the surface is high on the porous north flank and lower on the other flanks where impermeable layers can block the upward CO2 flux. The active upper part of the island is underlain by a well-defined hydrothermal system bounded by short-wavelength negative SP anomalies and high peaks of CO2. These boundaries coincide with faults limiting ancient collapses of calderas, craters and flank landslides. The hydrothermal system is not homogeneous but composed of three main subsystems and of a fourth minor one and is not centered on the active craters. The latter are located near its border. This divergence between the location of the active craters and the extent of the hydrothermal system suggests that the internal heat sources may not be limited to sources below the active craters. If the heat source strictly corresponds to intrusions at depth around the active conduits, the geometry of the hydrothermal subsystems must be strongly controlled by heterogeneities within the edifice such as craters, caldera walls or gliding planes of flank collapse, as suggested by the correspondence between SP–CO2 anomalies and structural limits. The inner zone of the hydrothermal subsystems is characterized by positive SP anomalies, indicating upward movements of fluids, and by very low values of CO2 emanation. This pattern suggests that the hydrothermal zone becomes self-sealed at depth, thus creating a barrier to the CO2 flux. In this hypothesis, the observed hydrothermal system is a shallow one and it involves mostly convection of infiltrated meteoric water above the sealed zone. Finally, on the base of CO2 degassing measurements, we present evidence for the presence of two regional faults, oriented N41° and N64°, and decoupled from the volcanic structures.

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

-European Union, -Ministero dell’Universita’ e della Ricerca Scientifica e Tecnologica; -CNR–Gruppo Nazionale per la Vulcanologia.

Soil CO2 degassing on Mt Etna (Sicily) during the period 1989–1993: discrimination between climatic and volcanic influences

Wide variations were measured in the diffuse CO2 flux through the soils in three selected areas of Mt Etna between August 1989 and March 1993. Degassing of CO2 from the area of Zafferana Etnea-S. Venerina, on the eastern slope of the volcano, has been determined to be more strongly influenced by meteorological parameters than the other areas. The seasonal component found in the data from this area has been excluded using a filtering algorithm based on the best fitting equation calculated from the correlation between CO2 flux values and those of air temperature. The filtered data appear to have variations temporally coincident with those from the other areas, thus suggesting a common and probably deep source of gas. The highest fluxes measured in the two most peripheral areas may correlate well with other geophysical and volcanological anomalous signals that preceded the strong eruption of 1991–1993 and that were interpreted as deep pressure increases. Anomalous decreases in CO2 fluxes accompanied the onset and the evolution of that eruption and have been interpreted as a sign of upward migration of the gas source. The variations of CO2 flux at the 1989 SE fracture have also given interesting information on the timing of the magmatic intrusion that has then fed the 1991–1993 eruption.

The aquatic geochemistry of arsenic in volcanic groundwaters from southern Italy

Abstract This paper discusses the abundance, speciation and mobility of As in groundwater systems from active volcanic areas in Italy. Using literature data and new additional determinations, the main geochemical processes controlling the fate of As during gas–water–rock interaction in these systems are examined. Arsenic concentrations in the fluids range from 0.1 to 6940 μg/l, with wide differences observed among the different volcanoes and within each area. The dependence of As content on water temperature, pH, redox potential and major ions is investigated. Results demonstrate that As concentrations are highest where active hydrothermal circulation takes place at shallow levels, i.e. at Vulcano Island and the Phlegrean Fields. In both areas the dissolution of As-bearing sulphides is likely to be the main source of As. Mature Cl-rich groundwaters, representative of the discharge from the deep thermal reservoirs, are typically enriched in As with respect to SO4-rich “steam heated groundwaters”. In the HCO3− groundwaters recovered at Vesuvius and Etna, aqueous As cycling is limited by the absence of high-temperature interactions and by high-Fe content of the host rocks, resulting in oxidative As adsorption. Thermodynamic modelling suggests that reducing H2S-rich groundwaters are in equilibrium with realgar, whereas in oxidising environments over-saturation with respect to Fe oxy-hydroxides is indicated. Under these oxidising conditions, As solubility decreases controlled by As co-precipitation with, or adsorption on, Fe oxy-hydroxides. Consistent with thermodynamic considerations, As mobility in the studied areas is enhanced in intermediate redox environments, where both sulphides and Fe hydroxides are unstable.

Genesis and evolution of the fumaroles of vulcano (Aeolian Islands, Italy): a geochemical model

A geochemical model explaining the presence of fumaroles having different gas composition and temperature at the top of the crater and along the northeastern coast of Vulcano island is proposed. A pressurized biphase (liquid-vapor) reservoir at the depth of about 2 km is hypothesized. Energy and mass balance sheets controlP-T conditions in the system.P-T must vary along a boiling curve of brine as liquid is present. The CO2 content in the steam is governed by the thermodynamic properties of the fluids in the H2-NaCl-CO2 system. On the assumption that oxygen fugacity in the system is between the HM-FMQ oxygen buffers, observed SO2/H2S, CO2/CO, CO/CH4 ratios in the fumarolic gases at the Fossa crater appear in equilibrium with a temperature higher than that observed, such as may exist at depth. The more reduced gas phases present on the sea-side may result from re-equilibrium processes in shallower aquifers. The suggested model would help in monitoring changes in volcanic activity by analyzing fumarolic gases.

MAJOR AND TRACE ELEMENTS GEOCHEMISTRY IN THE GROUND WATERS OF A VOLCANIC AREA: MOUNT ETNA (SICILY, ITALY)

Thirty-five ground-water samples have been collected from wells, springs and drainage galleries on Mt Etna volcano for the determination of major, minor and trace elements in solution. Attention has been focused in particular on dissolved minor and trace elements, for most of which no data were available in the studied area. In general, dissolution of solids into Etnas ground waters follows from strong interaction between water of meteoric origin, CO2 gas of magmatic origin and the volcanic rocks of the aquifers. However, the R-mode analysis allowed to distinguish several sources of solutes: Al, Co, Ni, Fe, Si, As would derive mainly from alteration of the volcanic rocks of Etna; SO4=, K, Na, V, Sr, Mo, Cr and calculated p(CO2) would instead indicate a major contribution of volcanic gases (mostly CO2 and SO2); and TDS, HCO3=, Li Mg, B and Cl− would indicate a derivation from both these sources. Se, Hg, Cu and Mn would derive from hydrothermal fluids, and Ca would derive both from this latter contribution and from rock alteration. The comparison between trace elements abundance in Etnas ground waters and that in the ground waters of other areas of Italy showed that, in general, Etnas waters, like other volcanic ground waters, are enriched in Li, Mn, Si, V, As and Mo. Furthermore, in the areas of Mt Etna where the contribution of volcanic gas to the aquifers is greatest, ground waters are also enriched in B, Se, Co, Hg, Al, Fe and Ni. The obtained results show clearly that, in active volcanic areas, many dissolved elements can attain levels that can be appreciably different from those indicated by WHO for drinking water. Therefore, the local geological factors which can influence the geochemical behavior of these elements in solution should be taken into account when establishing national standards for drinking-water quality. In consideration of the local natural background values, concentrations of dissolved elements that differ from the guideline values should be accepted in areas with peculiar geological characteristics, provided that the elements under consideration do not have a direct influence on health.

Degassing of Trace Volatile Metals During the 2001 Eruption of Etna

This paper provides new data on sulfur, halogens, and minor and trace metal contents in airborne particulate matter from the Mt. Etna volcanic plume. Aerosol samples were collected by conventional filtration techniques before and during the summer 2001 eruption, in order to investigate relations between plume chemistry and volcano dynamics. Data analysis reveals that abundances of trace metals in the plume result from mixing of erosive and volatile components. The former is responsible for the contents of rare earth elements (REE), Ca, Ba, Sr, Ti, Sc, Y, Hf and Th; the latter contributes significantly to the abundance of Cs, Rb, Na and K, probably transported in the plume as metal halides, and Cd, Pb, Zn, Ge, Te, Mo, Re, Se, Sb, Sn, In, Bi, Tl, Cu and Au, associated with sulfur in plume particles. Enrichment factors show that plume particulate matter from the Monti Carcarazzi vent, which opened on the southern flank of the volcano in July 2001, is typically depleted in volatile trace elements with respect to the output from the summit crater, suggesting the secondary nature of the outpouring lavas. The decreasing trend observed throughout the eruption in the enrichment factors of most trace metals probably indicates a small-volume batch of magma with limited feed from depth.

Soil CO2 degassing along tectonic structures of Mount Etna (Sicily): the Pernicana fault

Abstract Carbon dioxide emissions from the soil have been investigated along lines of equally spaced sampling points perpendicular to the Pernicana fault on Mt Etna. Anomalous values of soil CO2 have been found not only along the fault plane, but also along directions parallel to it, both to the N and to the S of the main fault. The acquired data seem to reveal a shallow step-like geometry of the Pernicana fault system with parallel faults being generally not deeper than the interface between Etnas volcanic cover and its sedimentary basement (a few hundred meters). The distribution of the anomalous CO2 emissions has also revealed that the Pernicana fault continues at least as far as the Ionian sea, in an area where only sedimentary rocks crop out. This finding would suggest that the main structure is deeper than the base of the volcanic cover, thus cutting at least the uppermost portion of Etnas sedimentary basement. Isotopic analyses of C carried out in samples from locations of high CO2, seem to indicate that the emitted CO2 is a mixture of an organic shallow component and a minor deeper magmatic one. Both chemical and isotopic data on soil gases emitted in the easternmost part of the studied area distinguished another tectonic structure which seems to be much deeper than the Pernicana fault and is roughly directed NNE-SSW, this direction being coincident with an important structural trend of eastern Sicily.