Geochemical and isotopic study of Tramutola thermal water (High Agri Valley, Southern Italy): Interaction between crustal and mantle fluids

The southern Apennines are affected by great crustal deformation and tectonic activity, where fluids from different reservoirs mix and rise to the surface through fault structures. Tramutola well (TRW) is an old borehole built by ENI, with the occurrence of bubbling gases located in the High Agri Valley (HAV), Southern Italy. The HAV is an inter-montane basin of the southern Apennine chain characterized by complex geological setting and high seismicity, this area hosts also the largest onshore Western European oil field. TRW is about 400 m deep it crosses clays, silicic clays and silicic limestone and is characterized by the continuous emission of thermal water (28°C) and bubbling gas. The water belong to Na-HCO3 hydrofacies.  TRW gases are CH₄-dominated (82,6 %), and low amounts of N₂ (12,9%), CO₂ (1,7%), C₂H₆ (0,3%). The noble gases are used to discriminate the fluids origin (atmospheric, crustal and mantle). The ⁴He/²⁰Ne ratio values are in three orders of magnitude higher that air-one (0,318) and ⁴⁰Ar/³⁶Ar ratio it is about 320 (Air=295.5; Hilton and Porcelli, 2003), this confirm the atmospheric contribution is present. Value Helium isotope (³He/⁴He, expressed as R/Ra) is between 1,13 and 1,26 Ra, and indicate a radiogenic component with a contribution of a mantle-derived helium (~20%). Methane isotope composition indicates a likely microbial isotopic signature (δ¹³C-CH₄ =-63‰, δD-CH₄= −217‰), probably due to either (1) biodegradation processes of thermogenic hydrocarbons or (2) ongoing microbial methanogenesis in the shallow organic‐rich clays hosting the gas. The δ¹³C-CO₂ value between of -3.5‰ and -6‰ VPDB, consistent with a mantle origin. The gases have low CO₂/³He ratios compared to mantle carbon end-member, probably due to secondary processes such as calcite precipitation. In conclusion, at Tramutola well have three gas sources and their possible mixing processes: (1) Shallow source, highlighted by atmospheric gas and rainwater entering the system through water infliltration; (2) crustal sources, CH4-dominant gas sources in correspondence of the hydrocarbon reservoir; (3) SCLM mantle source, mantle-derived fluids uprising through lithospheric normal faults.