Origin of the Breno and Esino dolomites in the western Southern Alps (Italy): Implications for a volcanic influence

The Esino Limestone of the western Southern Alps represents a differentiated Ladinian-Lower Carnian (?) carbonate platform comprised of margin, slope and peritidal inner platform facies up to 1000 m thick. A major regional subaerial exposure event lead to coverage by another peritidal Lower Carnian carbonate platform (Breno Formation). Multiphase dolomitization affected the carbonate sediments. Petrographic examinations identified at least three main generations of dolomites (D1, D2, and D3) that occur as both replacement and fracture-filling cements. These phases have crystal-size ranges of 3–35 μm (dolomicrite D1), 40–600 μm (eu-to subhedral crystals D2), and 200 μm to 5 mm (cavity- and fracture-filling anhedral to subhedral saddle dolomite D3), respectively. The fabric retentive near-micritic grain size coupled with low mean Sr concentration (76 ± 37 ppm) and estimated δ18O of the parent dolomitizing fluids of D1 suggest formation in shallow burial setting at temperature ∼ 45–50 °C with possible contributions from volcanic-related fluids (basinal fluids circulated in volcaniclastics or related to volcanic activity), which is consistent with its abnormally high Fe (4438 ± 4393 ppm) and Mn (1219 ± 1418 ppm) contents. The larger crystal sizes, homogenization temperatures (D2, 108 ± 9 °C; D3, 111 ± 14 °C) of primary two-phase fluid inclusions, and calculated salinity estimates (D2, 23 ± 2 eq wt% NaCl; D3, 20 ± 4 eq wt% NaCl) of D2 and D3 suggest that they formed at later stages under mid-to deeper burial settings at higher temperatures from dolomitizing fluids of higher salinity, which is supported by higher estimated δ18O values of their parent dolomitizing fluids. This is also consistent with their high Fe (4462 ± 4888 ppm; and 1091 ± 1183 ppm, respectively) and Mn (556 ± 289 ppm and 1091 ± 1183 ppm) contents, and low Sr concentrations (53 ± 31 ppm and 57 ± 24 ppm, respectively). The similarity in shale-normalized (SN) REE patterns and Ce (Ce/Ce*)SN and La (Pr/Pr*)SN anomalies of the investigated carbonates support the genetic relationship between the dolomite generations and their calcite precursor. Positive Eu anomalies, coupled with fluid-inclusion gas ratios (N2/Ar, CO2/CH4, Ar/He), high F− concentration, high F/Cl and high Cl/Br molar ratios suggest an origin from diagenetic fluids circulated through volcanic rocks, which is consistent with the co-occurrence of volcaniclastic lenses in the investigated sequence.