Alessandro Aiuppa

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.

Acid gas and metal emission rates during long‐lived basalt degassing at Stromboli Volcano

The discharge of acid gases and metals from Stromboli is determined from airborne and ground-based filter sampling of particulate matter in the volcanic plume, combined with COSPEC measurements of SO2 fluxes. Smaller particle sizes and high enrichment factors distinguish the most volatile elements (by order: S, Se, Br, Cl, Cd, Bi, In, As, Sb, Sn, F, Au, Pb, Cr, Cu) from those strictly (Fe, Mn, REE, Sc, Sr, Th, Ti, V) or mainly (Al, Ba, Ca, Co, K, Na, U) derived from volcanic ash. Time-averaged volatile fluxes show that Stromboli is a representative arc emittor, producing 1–2% of the global volcanic budget of sulfur, halogens and several trace metals, while 15–25% of volcanic emissions of Bi, Cd, Cs, Pb and Sn in southern Italy. Subaerial degassing of its S-Cl-rich shoshonitic magma over the last 2 ky of similar activity may have released as much copper and gold as is encountered in magma-derived high-sulfidation ore deposits.

Natural and anthropogenic factors affecting groundwater quality of an active volcano (Mt. Etna, Italy)

Abstract New geochemical data on dissolved major and minor constituents in 276 groundwater samples from Etna aquifers reveal the main processes responsible for their geochemical evolution and mineralisation. This topic is of particular interest in the light of the progressive depletion of water resources and groundwater quality in the area. Multivariate statistical analysis reveal 3 sources of solutes: (a) the leaching of the host basalt, driven by the dissolution of magma-derived CO2; (b) mixing processes with saline brines rising from the sedimentary basement below Etna; (c) contamination from agricultural and urban wastewaters. The last process, highlighted by increased concentrations of SO4, NO3, Ca, F and PO4, is more pronounced on the lower slopes of the volcanic edifice, associated with areas of high population and intensive agriculture. However, this study demonstrates that natural processes (a) and (b) are also very effective in producing highly mineralised waters, which in turn results in many constituents (B, V, Mg) exceeding maximum admissible concentrations for drinking water.

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.

Unmanned aerial vehicle measurements of volcanic carbon dioxide fluxes

[i] 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 SO 2 flux (8.5 Mg d- 1 ), and an infrared spectrometer, and electrochemical sensor assembly for measuring the plume CO 2 /SO 2 ratio; by multiplying these data we compute a CO 2 flux of 170 Mg d -1 . Given the deeper exsolution of carbon dioxide from magma, and its lower solubility in hydro-thermal systems, relative to SO 2 , the ability to remotely measure CO 2 fluxes is significant, with promise to provide more profound geochemical insights, and earlier eruption forecasts, than possible with SO 2 fluxes alone: the most ubiquitous current source of remotely sensed volcanic gas data.

Gradual caldera collapse at Bárdarbunga volcano, Iceland, regulated by lateral magma outflow

Driven to collapse Volcanic eruptions occur frequently, but only rarely are they large enough to cause the top of the mountain to collapse and form a caldera. Gudmundsson et al. used a variety of geophysical tools to monitor the caldera formation that accompanied the 2014 Bárdarbunga volcanic eruption in Iceland. The volcanic edifice became unstable as magma from beneath Bárdarbunga spilled out into the nearby Holuhraun lava field. The timing of the gradual collapse revealed that it is the eruption that drives caldera formation and not the other way around. Science, this issue p. 262 Magma flow from under the Bárdarbunga volcano drove caldera collapse during the 2014 eruption. INTRODUCTION The Bárdarbunga caldera volcano in central Iceland collapsed from August 2014 to February 2015 during the largest eruption in Europe since 1784. An ice-filled subsidence bowl, 110 square kilometers (km2) in area and up to 65 meters (m) deep developed, while magma drained laterally for 48 km along a subterranean path and erupted as a major lava flow northeast of the volcano. Our data provide unprecedented insight into the workings of a collapsing caldera. RATIONALE Collapses of caldera volcanoes are, fortunately, not very frequent, because they are often associated with very large volcanic eruptions. On the other hand, the rarity of caldera collapses limits insight into this major geological hazard. Since the formation of Katmai caldera in 1912, during the 20th century’s largest eruption, only five caldera collapses are known to have occurred before that at Bárdarbunga. We used aircraft-based altimetry, satellite photogrammetry, radar interferometry, ground-based GPS, evolution of seismicity, radio-echo soundings of ice thickness, ice flow modeling, and geobarometry to describe and analyze the evolving subsidence geometry, its underlying cause, the amount of magma erupted, the geometry of the subsurface caldera ring faults, and the moment tensor solutions of the collapse-related earthquakes. RESULTS After initial lateral withdrawal of magma for some days though a magma-filled fracture propagating through Earth’s upper crust, preexisting ring faults under the volcano were reactivated over the period 20 to 24 August, marking the onset of collapse. On 31 August, the eruption started, and it terminated when the collapse stopped, having produced 1.5 km of basaltic lava. The subsidence of the caldera declined with time in a near-exponential manner, in phase with the lava flow rate. The volume of the subsidence bowl was about 1.8 km3. Using radio-echo soundings, we find that the subglacial bedrock surface after the collapse is down-sagged, with no indications of steep fault escarpments. Using geobarometry, we determined the depth of magma reservoir to be ~12 km, and modeling of geodetic observations gives a similar result. High-precision earthquake locations and moment tensor analysis of the remarkable magnitude M5 earthquake series are consistent with steeply dipping ring faults. Statistical analysis of seismicity reveals communication over tens of kilometers between the caldera and the dike. CONCLUSION We conclude that interaction between the pressure exerted by the subsiding reservoir roof and the physical properties of the subsurface flow path explain the gradual near-exponential decline of both the collapse rate and the intensity of the 180-day-long eruption. By combining our various data sets, we show that the onset of collapse was caused by outflow of magma from underneath the caldera when 12 to 20% of the total magma intruded and erupted had flowed from the magma reservoir. However, the continued subsidence was driven by a feedback between the pressure of the piston-like block overlying the reservoir and the 48-km-long magma outflow path. Our data provide better constraints on caldera mechanisms than previously available, demonstrating what caused the onset and how both the roof overburden and the flow path properties regulate the collapse. The Bárdarbunga caldera and the lateral magma flow path to the Holuhraun eruption site. (A) Aerial view of the ice-filled Bárdarbunga caldera on 24 October 2014, view from the north. (B) The effusive eruption in Holuhraun, about 40 km to the northeast of the caldera

Excess volatiles supplied by mingling of mafic magma at an andesite arc volcano

We present the results of a study of volcanic gases at Soufriere Hills Volcano, Montserrat, which includes the first spectroscopic measurements of the major gas species CO2 and H2S at this volcano using a Multisensor Gas Analyzer System (MultiGAS) sensor. The fluxes of CO2 and H2S were 640.2750 t/d and 84.266 t/d, respectively, during July 2008, during a prolonged eruptive pause. The flux of CO2 is similar to estimates for the entire arc from previous geochemical studies, while the measured H2S flux significantly alters our interpretation of the sulphur budget for this volcano. The fluxes of both sulphur and carbon show considerable excesses over that which can be supplied by degassing of erupted magma. We demonstrate, using thermodynamic models and published constraints on preeruptive volatile concentrations, that the gas composition and fluxes are best modeled by mixing between (1) gases derived from isobaric quenching of mafic magma against cooler andesite magma at depth and (2) gases derived from shallower rhyolitic interstitial melt within the porpyritic andesite. The escape of deep-derived gases requires pervasive permeability or vapor advection extending to several kilometers depth in the conduit and magma storage system. These results provide more compelling evidence for both the contribution of unerupted mafic magma to the volatile budget of this andesitic arc volcano and the importance of the intruding mafic magma in sustaining the eruption. From a broader perspective, this study illustrates the importance and role of underplating mafic magmas in arc settings. These magmas play an important role in triggering and sustaining eruptions and contribute in a highly significant way to the volatile budget of arc volcanoes. Copyright

Volcanic and anthropogenic contribution to heavy metal content in lichens from Mt. Etna and Vulcano island (Sicily).

Major and trace element concentrations were determined in two lichen species (Parmelia conspersa and Xanthoria calcicola) from the island of Vulcano and all around Mt. Etna. In both areas, the average concentrations of Al, Ca, Mg, Fe, Na, K, P and Ti are substantially greater than those of other elements. Several elements (Br, Pb, Sb, Au, Zn, Cu) resulted enriched with respect to the local substrates. The Br and Pb enrichment factors turned out to be the highest among those calculated in both areas. Data indicate that mixing between volcanic and automotive-produced particles clearly explains the range of Pb/Br shown by lichen samples. Sb is also enriched, revealing a geogenic origin at Vulcano and a prevailing anthropic origin at Mt. Etna. Distribution maps of the enrichment factors show a generalized enrichment of Au and Zn near Mt. Etna, whereas Cu appears to be enriched prevalently in the NE-SE area. The highest levels of Au and Cu at Vulcano occur E-SE from the craters, following the prevailing wind direction.

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.