Pyle, David M.

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.

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.

Volatile elements play an important role in many aspects of the physicochemical architecture of sub-volcanic plumbing systems, from the liquid line of descent to the dynamics of magma storage and eruption. However, it remains difficult to constrain the behaviour of magmatic volatiles on short timescales before eruption using established petrological techniques (e.g. melt inclusions); specifically, in the final days to months of magma storage. This study presents a detailed model of pre-eruptive volatile behaviour in the Campi Flegrei system (Italy), through combined analyses of apatite crystals and glass. The deposits of eight eruptions were examined, covering the full spectrum of melt compositions, eruptive styles and periods of activity at Campi Flegrei in the past 15 kyr. Measured apatite compositions are compared with thermodynamic models that predict the evolution of the crystal compositions during different fractional crystallization scenarios, including (1) volatile-undersaturated conditions, (2) H2O-saturated conditions and (3) varying P–T conditions. The compositions of clinopyroxene-hosted and biotite-hosted apatite inclusions are consistent with crystallization under volatile-undersaturated conditions that persisted until late in magmatic evolution. Apatite microphenocrysts show significantly more compositional diversity, interpreted to reflect a mixed cargo of crystals derived from volatile-undersaturated melts at depth and melts that have undergone cooling and degassing in discrete shallow-crustal magma bodies. Apatite microphenocrysts from lavas show some re-equilibration during cooling at the surface. Clinopyroxene-hosted melt inclusions within the samples typically contain 2–4 wt % H2O, indicating that they have been reset during temporary magma storage at 1–3km depth, similar to the depth of sill emplacement during recent seismic crises at Campi Flegrei. Comparable apatite compositional trends are identified in each explosive eruption analysed, regardless of volume, composition or eruption timing. However, apatites from the different epochs of activity appear to indicate subtle changes in the H2O content of the parental melt feeding the Campi Flegrei system over time. This study demonstrates the potential utility of integrated apatite and glass analysis for investigating pre-eruptive volatile behaviour in apatite-bearing magmas

Restless silicic calderas present major geological hazards, and yet many also host significant untapped geothermal resources. In East Africa, this poses a major challenge, although the calderas are largely unmonitored their geothermal resources could provide substantial economic benefits to the region. Understanding what causes unrest at these volcanoes is vital for weighing up the opportunities against the potential risks. Here we bring together new field and remote sensing observations to evaluate causes of ground deformation at Aluto, a restless silicic volcano located in the Main Ethiopian Rift (MER). Interferometric Synthetic Aperture Radar (InSAR) data reveal the temporal and spatial characteristics of a ground deformation episode that took place between 2008 and 2010. Deformation time series reveal pulses of accelerating uplift that transition to gradual long-term subsidence, and analytical models support inflation source depths of 5 km. Gases escaping along the major fault zone of Aluto show high CO2 flux, and a clear magmatic carbon signature (CO2-d13C of 24.2&to 24.5&). This provides compelling evidence that the magmatic and hydrothermal reservoirs of the complex are physically connected. We suggest that a coupled magmatic-hydrothermal system can explain the uplift-subsidence signals. We hypothesize that magmatic fluid injection and/or intrusion in the cap of the magmatic reservoir drives edifice-wide inflation while subsequent deflation is related to magmatic degassing and depressurization of the hydrothermal system. These new constraints on the plumbing of Aluto yield important insights into the behavior of rift volcanic systems and will be crucial for interpreting future patterns of unrest

Magma reservoirs are thought to grow relatively slowly, assembling incrementally under volatile-saturated conditions. Eruptions may be triggered by injections of volatile-rich melt, or generation of over-pressure due to protracted crystallization. Here, we analyse fluorine, chlorine and water in apatite crystals trapped at di erent stages of magma evolution, and in melt inclusions from clinopyroxene and biotite crystals expelled during an explosive eruption of the Campi Flegrei caldera, Italy, about 4,000 years ago. We combine our geochemical analyses with thermodynamic modelling to reconstruct the evolution of magmatic volatile contents leading up to the explosive eruption. We find that the magma reservoir remained persistently water-undersaturated throughout most of its lifetime. Even crystals in contact with the melt shortly before eruption show that the magma was volatile-undersaturated. Our models suggest that the melt reached volatile saturation at low temperatures, just before eruption.We suggest that late-stage volatile saturation probably triggered the eruption, and conclude that ‘priming’ of the magma system for eruption may occur on timescales much shorter than the decadal to centennial timescales thought typical for magma reservoir assembly. Thus, surface deformation pulses that record magma assembly at depth beneath Campi Flegrei and other similar magmatic systems may not be immediately followed by an eruption; and explosive eruptions may begin with little warning.

Volcanoes are complex systems that evolve in space and time as a result of their internal dynamics. These internal dynamics span both long and short time scales, reflecting the different steps for the magma to form, accumulate and evolve before being eventually erupted. All of these stages may be influenced by processes external to the volcano, although most of the evidence that has been gathered on this has considered influences on the magmatic fluids stored at crustal depths, or emerging at surface. External forcing acts either through the stress or gravitational fields that may accelerate or slow down the transfer of magma towards the surface. Changing tectonic stresses and Earth tides may induce changes in the dynamical state of volcanoes, ultimately providing the triggers that may lead to eruption. Water, which is ubiquitous on Earth, and present in its different fluid and solid envelopes, appears to play a key role, acting on volcanic systems from pore- to global-scale in various ways (hydrological modulation, ice cap loading), due to its physico-chemical properties. This Research Topic brings together contributions, which provide new constraints and lines of evidence on the nature and variety of external processes influencing activity at quiet, restless and erupting volcanoes.

Volcanogenic halogens, in particular bromine, potentially play an important role in the ozone depletion of the atmosphere. Understanding bromine behaviour in magmas is therefore crucial to properly evaluate the contribution of volcanic eruptions to atmospheric chemistry and their environmental impact. To date, bromine partitioning between silicate melts and the gas phase is very poorly constrained, with the only relevant experimental studies limited to investigation of synthetic melt with silicic compositions. In this study, fluid/melt partitioning experiments were performed using natural silicate glasses with mafic, intermediate and silicic compositions. For each composition, experiments were run with various Br contents in the initial fluid (H2O–NaBr), at T–Pconditions representative of shallow magmatic reservoirs in volcanic arc contexts (100–200MPa, 900–1200◦C). The resulting fluid/melt partition coefficients (DBrf/m) are: 5.0 ±0.3 at 1200◦C–100MPa for the basalt, 9.1 ±0.6 at 1060◦C–200MPa for the andesite and 20.2 ±1.2 at 900◦C–200MPa for the rhyodacite. Our experiments show that DBrf/mincreases with increasing SiO2content of the melt (as for chlorine) and suggest that it is also sensitive to melt temperature (increase of DBrf/mwith decreasing temperature). We develop a simple model to predict the S–Cl–Br degassing behaviour in mafic systems, which accounts for the variability of S–Cl–Br compositions of volcanic gases from Etna and other mafic systems, and shows that coexisting magmatic gas and melt evolve from S-rich to Cl–Br enriched (relative to S) upon increasing degree of degassing. We also report first Br contents for melt inclusions from Etna, Stromboli, Merapi and Santorini eruptions and calculate the mass of bromine available in the magma reservoir prior to the eruptions under consideration. The discrepancy that we highlight between the mass of Br in the co-existing melt and fluid prior to the Merapi 2010 eruption (433 and 73 tons, respectively) and the lack of observed BrO (from space) hints at the need to investigate further Br speciation in ‘ash-rich’ volcanic plumes. Overall, our results suggest that the Br yield into the atmosphere of cold and silicic magmas will be much larger than that from hotter and more mafic magmas.