Volatile organic compounds (VOCs) from diffuse degassing areas: Interstitial soil gases as message bearers from deep hydrothermal reservoirs.

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) C alkanes, n-hexane, cyclics and alkylated aromatics, related to relatively low-temperature conditions at the gas source; (iii) C 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.