Multiple source components in gas manifestations from north-central Italy

Abstract

Gas manifestations in north-central Italy consist of CO2-rich gases with minor N2-rich emissions and discharge either along with thermal springs or into cold and stagnant waters. 'Cold' gases are prevalently CO2-dominated (> 90%) while gases related to the thermal waters have variable composition: from CO2 > 99.5% to N2 > 90%. The variable composition of 'thermal' gases is caused by differences in the thermal regime and lithology of the ascent paths, where there is mixing of gases from multiple sources, such as N2-rich atmospheric and deep CO2-rich metamorphic end-members. Elevated concentrations of CH4 and H2 in these gases are generally related to the presence of active geothermal systems at shallow depth, such as the Larderello-Travale field in Tuscany. The ??13C values between coexisting CH4 and CO2 in all samples analyzed suggest that CH4 originates abiogenically in 200-400??C hydrothermal systems. Far from geothermal areas, where the thermal gradient is lower or the water/gas ratio is high because of large inflow of meteoric waters, H2 and CH4 are usually lower. In some cases, they can be scrubbed or oxidized (especially H2), while the residual rising gas becomes indirectly enriched in N2 and CO2. Carbon dioxide is also enriched in some discharged gases because it is produced at shallow depth in lower temperature conditions (< 150??C). Heavy ??15N values for N2 to near +7.0??? suggest that, for some gas samples that contain excess nitrogen (e.g. where N2/Ar ??? 83), this component probably derives from ammonia-rich feldspars and micas within the Palaeozoic schist basement rocks. However, other samples show evidence of a shallow component of CH4 and N2 from Neogene basin sediments. The areal distribution of the 3He/4He ratio points to a general prevalence of atmospheric and crustal 4He in the gas discharges in central Italy. A significant component of mantle 3He is only found in the geothermal areas of Larderello where the large regional thermal anomaly suggests the presence of a deep magmatic body. ?? 1997 Elsevier Science B.V.