Consumption of Atmospheric Carbon Dioxide through Weathering of Ultramafic Rocks in the Voltri Massif (Italy): Quantification of the Process and Global Implications

Chemical weathering is the main natural mechanism limiting the atmospheric carbon dioxide levels on geologic time scales (>1 Ma) but its role on shorter time scales is still debated, highlighting the need for an increase of knowledge about the relationships between chemical weathering and atmospheric CO2 consumption. A reliable approach to study the weathering reactions is the quantification of the mass fluxes in and out of mono lithology watershed systems. In this work the chemical weathering and atmospheric carbon dioxide consumption of ultramafic rocks have been studied through a detailed geochemical mass balance of three watershed systems located in the metaophiolitic complex of the Voltri Massif (Italy). Results show that the rates of carbon dioxide consumption of the study area (weighted average = 3.02 1.67 105 mol km2 y1) are higher than the world average CO2 consumption rate and are well correlated with runo, probably the stronger weathering controlling factor. Computed values are very close to the global average of basic and ultrabasic magmatic rocks, suggesting that Voltri Massif is a good proxy for the study of the feedbacks between chemical weathering, CO2 consumption, and climate change at a global scale

The acidic waters in Italy: a brief overview

The present study is aimed at providing a brief overview of the Italian acidic waters based on literature and unpublished data. Acidic waters in Italy, as elsewhere, are relatively common and associated with extremely variable geological settings. Owing to their peculiar features, these waters may seriously affect the environment and the ecosystems. Along the Apennine belt, the western and inner sectors of the Italian peninsula record an anomalous geothermal gradient, mostly overlapping with the Neogene-to-present magmatism, that explains the presence of a huge amount of CO2(H2S)-rich gas and thermal water discharges, geothermal fields (e.g. Larderello and Mt. Amiata) and ore deposits (e.g. Fe- and polymetallic sulfides, e.g. Elba Island and Colline Metallifere). Acidic waters (pH ≤5) from volcanic and geothermal areas show outlet temperatures and Total Dissolved Solids (TDS) from 10 to 96°C and <1 to ≈30 g/L, respectively, with a chemical composition usually belonging to the Ca-SO4, NH4-SO4 or Na-Cl facies. Frequently, they are related to bubbling and boiling pools due to the interaction between deepsourced gases and shallow aquifers or meteoric waters. Concentrations of heavy metals and metalloids are in most cases high. Extremely high contents of metals are also recorded for those acidic waters that characterize the main Italian mining districts, mostly located in Sardinia (not included in the present study), Tuscany and NW Alps, where they are related to Acid Mine Drainage l.s. or Acid Rock Drainage. The pH values are as low as 2.08, with variable TDS concentrations. Compositionally, they are Na-SO4, Ca(Mg)-SO4, and/or Mg(Ca)-SO4 waters, prevalently due to oxidative processes affecting polymetallic sulfides

Biogeochemical and microbial community structure differently modulates CO2 and CH4 dynamics in two adjacent volcanic lakes (Monticchio, Italy)

By hosting significant amounts of extra-atmospheric dissolved gases, including geogenic CO2 and CH4, volcanic lakes provide relevant ecosystem services through the key role the aquatic microbial community in mediating freshwater carbon fluxes. In view of elucidating the mechanisms governing the microbial spatial distribution and the possible implications for ecosystem functioning, we compared the hydrogeochemical features and the microbial community structure of two adjacent stratified volcanic lakes (Lake Grande - LG and Lake Piccolo - LP). Water chemistry, gases and their isotopic composition were coupled with microbial pigment profiling, cell counting, and phylogenetic analyses. LP showed transparent waters with low concentrations of chlorophyll-a and the occurrence of phycoerytrin-rich cyanobacteria. LG was relatively more eutrophic with a higher occurrence of diatoms and phycocyanine-rich cyanobacteria. Considering the higher concentrations of CO2 and CH4 in bottom waters, the oligotrophic LP was likely a more efficient sink of geogenic CO2 in comparison to the adjacent eutrophic LG. The prokaryotic community was dominated by the mixothrophic hgcI clade (family Sporichthyaceae) in the LG surface waters, while in LP this taxon was dominant down to -15 m. Moreover, in LP, the bottom dark waters harbored a unique strictly anaerobic bacterial assemblage associated with methanogenic Archaea (i.e. Methanomicrobiales), resulting in a high biogenic methane concentration. Water layering and light penetration were confirmed as major factors affecting the microbial distribution patterns. The observed differences in the geochemical and trophic conditions reflected the structure of the aquatic microbial community, with direct consequences on the dynamics of dissolved greenhouse gases

Active Moss biomonitoring of mercury in the mine-polluted area of Mt. Amiata (Central Italy)

In the winter 2013, mercury concentrations in air from the mine-polluted area of Mt. Amiata (1738 m a.s.l.), in southern Tuscany (Central Italy), were measured by active moss biomonitoring. This area is part of the geologic anomaly of Hg in the Mediterranean basin, which contains about 65 % of the world’s cinnabar (HgS). Mt. Amiata covers some 400 km2 and is drained by several rivers. Esploitation activity at Abbadia S. Salvatore, in the SE sector of the mountain, sprang up during the 19th century as one of the largest mercury mining and smelting plants in Europe, after those of Almaden Spain. In this area, Sphagnum moss bags were exposed for about two months, from October to December 2013. At each site (10 sites), one covered and one uncovered moss bag were deployed. Concentrations of mercury in air were also investigated in the same sites with a portable spectrophotometer (Lumex RA-915M). After exposure, mosses were oven-dried, grinded and each sample was divided in two aliquots: one was analyzed for mercury by using a Hydra C cold vapor atomic absorption analyzer (INGV-Palermo), following 7473 US EPA method; the second was microwave digested in acid solution (HNO3 + H2O2). Extraction solutions were analyzed by ICP-MS for total concentrations of a large suite of trace elements, including potentially toxic elements e.g. As, Cd, Cr, Cu, Mo, Sb, Se, V. Mercury air concentrations measured with the Lumex showed extremely high values in the mine district of Abbadia, with median values ranging from 2,000 to 4,000 ng/m3 and maximum values up to 20,000 ng/m3, in contrast with the lower values (median values from 20 to 200 ng/m3) measured in the distal sites few kilometres from the mine-district area. In agreement with these results, in the vicinity of the district uncovered bags were in the range of 10,000 – 100,000 ng/g of Hg, whereas in the distal sites they were in the range of 1,000 – 10,000 ng/g. The moss-blank (unexposed moss) was ~100 ng/g. Covered moss bags were not significantly enriched in Hg with respect to the concentrations recovered from the moss-blank, suggesting that the mercury trapped in the mosses was mainly in particulate form. The particles carried from the winds were probably associated with soils re-mobilization, as also confirmed by the associated enrichments of some lithophile elements (Li and lanthanides) and anthropogenic element (As, Cr, Cd, Fe, Se, V). These preliminary results confirm the intense contamination of the study area not only for mercury but also for other potentially toxic elements

Origin and Distribution of Thiophenes and Furans in Gas Discharges from Active Volcanoes and Geothermal Systems

The composition of non-methane organic volatile compounds (VOCs) determined in 139 thermal gas discharges from 18 different geothermal and volcanic systems in Italy and Latin America, consists of C2–C20 species pertaining to the alkanes, alkenes, aromatics and O-, S- and N-bearing classes of compounds. Thiophenes and mono-aromatics, especially the methylated species, are strongly enriched in fluids emissions related to hydrothermal systems. Addition of hydrogen sulphide to dienes and electrophilic methylation involving halogenated radicals may be invoked for the formation of these species. On the contrary, the formation of furans, with the only exception of C4H8O, seems to be favoured at oxidizing conditions and relatively high temperatures, although mechanisms similar to those hypothesized for the production of thiophenes can be suggested. Such thermodynamic features are typical of fluid reservoirs feeding high-temperature thermal discharges of volcanoes characterised by strong degassing activity, which are likely affected by conspicuous contribution from a magmatic source. The composition of heteroaromatics in fluids naturally discharged from active volcanoes and geothermal areas can then be considered largely dependent on the interplay between hydrothermal vs. magmatic contributions. This implies that they can be used as useful geochemical tools to be successfully applied in both volcanic monitoring and geothermal prospection