Stable isotope evidence for near-surface, low-temperature formation of Mg-(hydro)carbonates in highly altered Greek Mesozoic serpentinites

Authigenic magnesite, hydromagnesite and huntite associated with intensely altered and serpentinized ophiolitic rocks in Attica (mainland Greece) occur predominantly as veinlets and nodules within a totally weathered former-serpentinite groundmass. Carbonate δ¹⁸O values are consistent with post-geothermal fluid temperatures between 25-70 ˚C, but mostly between 25-30 ˚C, from a dominantly meteoric-sourced groundwater, indicating near-surface, low-temperature conditions. Despite the proximity of a volcanic centre with strong CO2 flux, 75% of the carbon isotope data imply little or no incorporation of this CO2 into the authigenic Mg-(hydro)carbonates. Indeed, many δ¹³C values are more negative than soil-zone calcrete values, and in this setting Mg-(hydro)carbonate δ¹³C below -6‰ VPDB probably indicate disequilibrium effects in alkaline groundwaters. Geothermal fluids and groundwaters were mainly routed through structural conduits. Some of the low temperature hydromagnesite subsequently dehydrated to magnesite under near-surface conditions, while huntite is likely a diagenetic transformation of hydromagnesite, forming close to the volcanic centre where fluid Mg/Ca ratios were low. The isotopic signatures are distinct from previously published Balkan-East Mediterranean magnesite data arrays but are consistent with many other ultramafic-associated magnesium carbonates worldwide; their association with likely fluid compositions provide important context for Mg-(hydro)carbonate formation as geothermal conditions cool to near surface temperatures.