L. Brusca

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.

Geochemical mapping of magmatic gas–water–rock interactions in the aquifer of Mount Etna volcano

Abstract Systematic analysis of major and minor elements in groundwaters from springs and wells on the slopes of Mt. Etna in 1995–1998 provides a detailed geochemical mapping of the aquifer of the volcano and of the interactions between magmatic gas, water bodies and their host rocks. Strong spatial correlations between the largest anomalies in pCO2 (pH and alkalinity) K, Rb, Mg, Ca and Sr suggest a dominating control by magmatic gas (CO2) and consequent basalt leaching by acidified waters of the shallow (meteoric) Etnean aquifer. Most groundwaters displaying this magmatic-type interaction discharge within active faulted zones on the S–SW and E lower flanks of the volcanic pile, but also in a newly recognised area on the northern flank, possibly tracking a main N–S volcano-tectonic structure. In the same time, the spatial distribution of T°C, TDS, Na, Li, Cl and B allows us to identify the existence of a deeper thermal brine with high salinity, high content of B, Cl and gases (CO2, H2S, CH4) and low K/Na ratio, which is likely hosted in the sedimentary basement. This hot brine reaches the surface only at the periphery of the volcano near the Village of Paterno, where it gives rise to mud volcanoes called “Salinelle di Paterno”. However, the contribution of similar brines to shallower groundwaters is also detected in other sectors to the W (Bronte, Maletto), SW (Adrano) and SE (Acireale), suggesting its possible widespread occurrence beneath Etna. This thermal brine is also closely associated with hydrocarbon fields all around the volcano and its rise, generally masked by the high outflow of the shallow aquifer, may be driven by the ascent of mixed sedimentary–magmatic gases through the main faults cutting the sedimentary basement.

Geochemistry of rainfall at Stromboli volcano (Aeolian Islands): Isotopic composition and plume‐rain interaction

The chemical and isotopic compositions of the precipitation at Stromboli Island, Italy, were investigated between October 2003 and October 2005. We employed a rain gauge network designed to cover the range in exposures and elevations of the volcanic edifice. The hydrogen and oxygen isotopic ratios vary greatly on a seasonal basis and correlate with air temperature. Deuterium excess values show a positive correlation with altitude. No direct contribution of volcanogenic H or O is evident in the isotopic composition of the rainwater. The chemical composition of the rainwater is principally controlled by the sea aerosol contribution at the coastal sites, whereas it is significantly influenced by volcanic activity near the summit vents. Interaction with volcanic acid gases is indicated by the pH, which is usually 1–2 units lower near the craters than at the coastal sites. The S/Cl, Cl/F, and S/F molar ratios in rainwater 1.5 km from the craters are consistent with those measured in the volcanic plume using other methods (diffusive tubes and Fourier transform infrared spectroscopy). Rising of undegassed magmas changes these molar ratios because of the differential degassing of sulphur, chlorine, and fluorine from the magma. We therefore propose that the chemical composition of precipitation, within 1.5 km of the craters, provides additional information that is useful for monitoring volcanic activity at Stromboli Island. Moreover, this paper presents estimates of the fluxes of F, Cl, S, Na, K, Ca, and Mg to the soil that could be useful for geochemical studies on groundwater.

Evaluation of the environmental impact of volcanic emissions from the chemistry of rainwater: Mount Etna area (Sicily)

Abstract The S, halogen and NO 3 contents of rainwater samples from the Etnean area were studied in order to define the environmental impact of plume emissions on the local environment. Samples, collected on a network of 11 bulk rain gauges, show significant variability in anion content, which can be ascribed to different meteorological and environmental conditions at each sampling site and to a variable distance from the different source areas. Data analysis suggests that S, F, Cl and Br are mainly magma-derived, whereas NO 3 mainly originates from anthropogenic sources. Samples collected from sites close to craters display considerable temporal variability, with increased anion concentrations being recorded during periods of intense plume degassing. Variations in precipitation also induce significant modifications in the chemistry of the meteoric-derived Etnean groundwaters.

Intense magmatic degassing through the lake of Copahue volcano, 2013-2014

Here we report on the first assessment of volatile fluxes from the hyperacid crater lake hosted within the summit crater of Copahue, a very active volcano on the Argentina-Chile border. Our observations were performed using a variety of in situ and remote sensing techniques during field campaigns in March 2013, when the crater hosted an active fumarole field, and in March 2014, when an acidic volcanic lake covered the fumarole field. In the latter campaign, we found that 566 to 1373 t d−1 of SO2 were being emitted from the lake in a plume that appeared largely invisible. This, combined with our derived bulk plume composition, was converted into flux of other volcanic species (H2O ~ 10989 t d−1, CO2 ~ 638 t d−1, HCl ~ 66 t d−1, H2 ~ 3.3 t d−1, and HBr ~ 0.05 t d−1). These levels of degassing, comparable to those seen at many open-vent degassing arc volcanoes, were surprisingly high for a volcano hosting a crater lake. Copahues unusual degassing regime was also confirmed by the chemical composition of the plume that, although issuing from a hot (65°C) lake, preserves a close-to-magmatic signature. EQ3/6 models of gas-water-rock interaction in the lake were able to match observed compositions and demonstrated that magmatic gases emitted to the atmosphere were virtually unaffected by scrubbing of soluble (S and Cl) species. Finally, the derived large H2O flux (10,988 t d−1) suggested a mechanism in which magmatic gas stripping drove enhanced lake water evaporation, a process likely common to many degassing volcanic lakes worldwide.

Salinity variations in the water resources fed by the Etnean volcanic aquifers (Sicily, Italy): natural vs. anthropogenic causes

In this paper, in an attempt to reveal possible changes connected to natural or anthropogenic causes, the main results of hydrogeochemical monitoring carried out at Mount Etna are evaluated. We report on the salinity contents of the groundwaters that flow in fractured volcanics, which make up the flanks of the volcano. These waters, analyzed for major ion chemistry, were sampled regularly from 1994 to 2004. Basing on nonparametric Sen’s slope estimator, time series of groundwater composition reveal that the salinity of most of the Etnean aquifers increased by 0.5% to 3.5% each year during this period. This change in the water chemistry is clearly referable to the overexploitation of the aquifers. This increasing trend needs to be inverted urgently; otherwise, it will cause a shortage of water in the near future, because the maximum admissible concentration of salinity for drinking water will be exceeded.

Variations of Soil Temperature, CO2 Flux, and Meteorological Parameters

The detailed analysis carried out on the data, acquired in two continuous monitoring stations during the 2002―2003 Stromboli eruption, integrated by daily field observations of the scientific personnel working at the volcanological observatory, showed that CO 2 flux and soil temperature are strictly related to volcanic events. Furthermore, the recorded signals showed a strong correlation with wind speed and direction, revealing that during the eruption, in the summit area of Stromboli, air movements were related not only to atmospheric circulation, but were also significantly affected and, in certain cases, caused by volcanic activity. The possible volcanic origin of a peculiar type of air circulation identified in the summit area of Stromboli suggests that the separation between volcanic and atmospheric signals might not be obvious, requiring monitoring of atmospheric parameters over a wide area, rather than a single location.

Plume composition and volatile flux of Nyamulagira volcano, Democratic Republic of Congo, during birth and evolution of the lava lake, 2014–2015

Very little is known about the volatile element makeup of the gaseous emissions of Nyamulagira volcano. This paper tries to fill this gap by reporting the first gas composition measurements of Nyamulagira’s volcanic plume since the onset of its lava lake activity at the end of 2014. Two field surveys were carried out on 1 November 2014, and 13–15 October 2015. We applied a broad toolbox of volcanic gas composition measurement techniques in order to geochemically characterize Nyamulagira’s plume. Nyamulagira is a significant emitter of SO2, and our measurements confirm this, as we recorded SO2 emissions of up to ~ 14 kt/d during the studied period. In contrast to neighbouring Nyiragongo volcano, however, Nyamulagira exhibits relatively low CO2/SO2 molar ratios (< 4) and a high H2O content (> 92% of total gas emissions). Strong variations in the volatile composition, in particular for the CO2/SO2 ratio, were measured between 2014 and 2015, which appear to reflect the simultaneous variations in volcanic activity. We also determined the molar ratios for Cl/S, F/S and Br/S in the plume gas, finding values of 0.13 and 0.17, 0.06 and 0.11, and 2.3·10−4 and 1·10−4, in 2014 and 2015, respectively. A total gas emission flux of 48 kt/d was estimated for 2014. The I/S ratio in 2015 was found to be 3.6·10−6. In addition, we were able to distinguish between hydrogen halides and non-hydrogen halides in the volcanic plume. Considerable amounts of bromine (18–35% of total bromine) and iodine (8–18% of total iodine) were found in compounds other than hydrogen halides. However, only a negligible fraction of chlorine was found as compounds other than hydrogen chloride.

Geochemistry of Zr, Hf, and REE in a wide spectrum of Eh and water composition: The case of Dead Sea Fault system (Israel)

Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the contrary, in waters where Eh< 0 values occur (Group 2), chondritic Zr/Hf values are found. Superchondritic Zr/Hf values are produced by the preferential Hf scavenging onto Fe-oxyhydroxides that is inhibited under reducing conditions consistent with the water oversaturation relative to pyrite. Redox conditions also influence the amplitude of Ce and Eu anomalies. Oxidized Group-1 waters show negative Ce anomalies related to the oxidative Ce scavenging as CeO2 onto Fe-oxyhydroxide. Reduced Group-2 waters show positive Eu anomaly values consistent with the larger Eu concentration relative to Eu in these waters suggested by model calculations. The higher stability of Eu with respect to its trivalent neighbors along the REE series can explain the above mentioned positive Eu anomaly values. The middle-REE enrichment observed in shale-normalized REE patterns of studied waters can be ascribed to carbonate and/or gypsum dissolution.

Annex 2 to: Trace elements mobility in soils from the hydrothermal area of Nisyros (Greece)

A.1 Analytical Tecniques All soil samples were air dried, thoroughly mixed and split into subsamples for analysis. Particular care was taken using a Riffle-type sample splitter to ensure that representative subsamples were obtained. All analyses were made after sieving the soil samples through a 2-mm sieve and, except for pH determination, ground with an agate mortar. [...]