Randazzo, Antonio

The chemical composition of volatile organic compounds (VOCs) in interstitial soil gases from hydrothermal areas is commonly shaped by both deep hydrothermal conditions (e.g., temperature, redox, sulfur fugacity) and shallow secondary processes occurring near the soil-atmosphere interface. Caldara di Manziana and Solfatara di Nepi, i.e., two hydrothermal systems characterized by diverse physicochemical conditions located in the Sabatini Volcanic District and Vicano-Cimino Volcanic District, respectively (Central Italy), were investigated to evaluate the capability of VOCs in soil gases to preserve information from the respective feeding deep fluid reservoirs. Hierarchical cluster analyses and robust principal component analyses allowed recognition of distinct groups of chemical parameters of soil gases collected from the two study areas. The compositional dissimilarities from the free-gas discharges were indeed reflected by the chemical features of soil gases collected from each site, despite the occurrence of shallow processes, e.g., air mixing and microbial degradation processes, affecting VOCs. Four distinct groups of VOCs were recognized suggesting similar sources and/or geochemical behaviors, as follows: (i) S-bearing compounds, whose abundance (in particular that of thiophenes) was strictly dependent on the sulfur fugacity in the feeding system; (ii) C4,5,7+ alkanes, n-hexane, cyclics and alkylated aromatics, related to relatively low-temperature conditions at the gas source; (iii) C2,3 alkanes, benzene, benzaldehyde and phenol, i.e., stable compounds and thermal degradation products; and (iv) aliphatic O-bearing compounds, largely influenced by shallow processes within the soil. However, they maintain a chemical speciation that preserves a signature derived from the supplying deep-fluids, with aldehydes and ketones becoming more enriched after intense interaction of the hypogenic fluids with shallow aquifers. Accordingly, the empirical results of this study suggest that the chemical composition of VOCs in soil gases from hydrothermal areas provides insights into both deep source conditions and fluid circulation dynamics, identifying VOCs as promising geochemical tracers for geothermal exploration.

Wetlands are hotspots of CH4 emissions to the atmosphere, mainly sustained by microbial decomposition of organic matter in anoxic sediments. Several knowledge gaps exist on how environmental drivers shape CH4 emissions from these ecosystems, posing challenges in upscaling efforts to estimate global emissions from waterbodies. In this work, CH4 and CO2 diffusive fluxes, along with chemical and isotopic composition of dissolved ionic and gaseous species, were determined from two wetlands of Tuscany (Italy): (i) Porta Lake, a small wetland largely invaded by Phragmites australis reeds experiencing reed die‐back syndrome, and (ii) Massaciuccoli Lake, a wide marsh area including open‐water basins and channels affected by seawater intrusion and eutrophication. Both wetlands were recognized as net sources of CH4 to the atmosphere. Our data show that the magnitude of CH4 diffusive emission was controlled by CH4 production and consumption rates, being mostly governed by (i) water temperature and availability of labile carbon substrates and (ii) water column depth, wind exposure and dissolved O2 contents, respectively. This evidence suggests that the highest CH4 diffusive fluxes were sustained by reed beds, providing a large availability of organic matter supporting acetoclastic methanogenesis, with relevant implications for global carbon budget and future climate models.