Free and dissolved gases in Castrocaro spa waters (Italy)

Free and dissolved gases in cold water samples from the Castrocaro spa, Northern Italy, were analyzed for their chemical composition. These gases were interpreted as the result of the binary mixing between a N2- and a CH4-rich component. CO2 is generally a minor constituent. N2/Ar ratios below the air typical value suggest that air saturated water (ASW) is the most likely source of atmospheric-derived components. This atmospheric end-member is predominant in low-salinity waters. Conversely, CH4-enriched gases are mainly associated with brackish to saline waters. The occurrence of minor amounts of light hydrocarbons (C2-C3) indicates a predominant biogenic origin of CH4. The He isotopic composition of the CH4-richest sample (3He/4He = 0.22 Ra) is in the range of values measured for cold seeps and mud volcanoes along the Northern Apennines foothills, and indicates a predominant crustal origin of this gas.