Sulfur and oxygen isotope compositions of Upper Triassic sulfates from northern Apennines (Italy) : paleogeographic and hydrogeochemical implications

Upper Triassic bedded evaporite sulfate of the Burano Formation outcropping at Cerreto Pass between Tuscany and Emilia-Romagna in the Northern Apennines were analyzed for sulfur and oxygen isotope compositions, yielding d34S and d18O values of 15.5±0.4‰ and 10.8±1.2‰, respectively (mean ±99% confidence intervals). Combining these values with those of other Burano Formation sulfate deposits along the Apennine chain, mean for d34S and d18O values are obtained (15.2±0.2‰ and 10.9±0.5‰, respectively). These isotopic signatures are interpreted as preserved primary features, despite the fact that the Burano Formation underwent anchizone to epizone metamorphism during the Apennine orogenesis. An overall d18O value of 10.9±1.5‰ (mean ± pooled standard deviation), obtained by combining consistent sets of data from Italy and Spain, closely approaches that of gypsum deposited from the Tethys ocean during the Late Triassic. In addition, reviewing the isotope data published on Late Triassic evaporite sulfates from the Mediterranean area and abroad, several d34S values appear to be lower than the inferred primary isotopic signature, and seemly decrease from East to West in the Mediterranean region, suggesting a similar trend for the Tethys ocean sulfate. Possibly, 34S-depleted sulfate entered the ocean through oxidation of volcanic SO2 emitted in the atmosphere and degassed from the seafloor during the development of Late Triassic rifting. On the other hand, positive shifts of d34S and d18O values also occur, defining a common trend that may be related to synsedimentary biological effects or post-depositional metasomatic-metamorphic effects, the latter affecting particularly the d18O signature. Therefore, the d34S and d18O signatures of evaporite sulfate may provide a like "slide-rule" diagram to distinguish between isotopic effects related to biological or abiological processes, thus contributing to the reconstruction of paleoenvironments and paleogeographic settings. Based on the d34S-d18O "slide-rule", the isotopic composition of sulfate dissolved in spring and stream waters of northern Tuscany was interpreted in terms of origin of the sulfate and modifying processes in solution. It was concluded that sulfate in springs derives from Upper Triassic evaporite existing locally at depth (Burano Formation), whereas sulfate in streams is manifestly a mixture of Burano Formation sulfate with supergene sulfate from oxidation of sulfide in the rocks. In sulfurous springs, both sulfur and oxygen isotope fractionations with respect to the source sulfate signatures may be ascribed to bacterial effects. However, the oxygen isotope exchange of sulfate with water should have been a very minor process as supported by the nearsurface temperature values estimated by sulfate-water oxygen isotope thermometry