The Isotope and REY geochemistry of fault-related calcites document syn-kinematic fluid distribution along the Val d'Agri faults (southern Italy)

Calcite is a common syn-kinematic precipitate in upper crustal fault zones coating slickensides, forming slickenfibers, and infilling veins. Structural and geochemical analyses of fault-related calcites can be used to unravel the source, distribution, and mixing of parental fluids in association with past fault activity. Identifying deeply sourced fluids through syn-kinematic calcites is of paramount importance, as the correlation of the ascent of deep sourced fluids with strong earthquakes, may allow using hydrogeochemical modifications in groundwater as potential seismic precursors. In this study, we investigate the origin of syn-kinematic paleo-fluids that circulated along the Val d’Agri faults, in southern Italy. These faults bound an intermontane basin topping the largest onshore oil field in Western Europe. Since the Val d’Agri Basin is affected by natural seismicity and low magnitude oil production induced earthquakes, it is necessary to assess the potential threats of hydrocarbon fault leakage at shallow crustal levels. With this aim, we collected about 350 syn-tectonic calcites along high-angle extensional-transtensional fault zones. By combining macro- and micro- scale structural observations with carbonate isotopes (C, O, clumped, and Sr) and rare earth elements and yttrium (REY) geochemistry, we identified 5 fluid sources: (1) meteoric waters in geochemical and thermal disequilibrium with the host rocks, which interacted with superficial soil; (2) meteoric waters in geochemical disequilibrium and thermal equilibrium with the host rocks, which had limited interaction with the host rocks; (3) buffered fluids in geochemical and thermal equilibrium with the host rocks; (4) high temperature fluids in geochemical equilibrium and thermal disequilibrium with the host rocks, which ascended from the carbonate hydrocarbon reservoir; (5) hot meteoric waters in thermal and geochemical disequilibrium with the host rocks, which mixed with the deeply sourced fluids. The presence of multiple fluids is consistent with an open fault-related circulation system, which allowed mixing of shallow and deep fluids through the high-angle extensional-transtensional Val d’Agri faults. Given the societal and economic issues of this area, the recognized involvement of deep fluids during past fault activity is crucial for the context of oil exploration and production as well as for environmental monitoring. Furthermore, this suggests that the Val d’Agri Basin is an ideal region to explore fluid-fault relationships throughout the entire seismic cycle through local seismicity records and continuous groundwater monitoring.