Pristine or altered: low-Mg calcite shells survived from massive dolomitization? A case study from Miocene carbonates

Abstract

Low-Mg calcite shells have been widely used to reconstruct the chemistry of ancient seawater. There is always a question: are the shells chemically pristine? This paper presents the isotope and elemental geochemistry of low-Mg calcite bivalve shells in late Miocene platform carbonates, SE Spain. The platform carbonates were extensively dolomitized, and limestone is restricted to older stratal units, and to units mainly in topographically higher and more landward strata. Low-Mg calcite oyster shells were completely dissolved out in the basinward dolomite, but are well preserved in the limestone. These shells appear to retain the original growth microstructures, based on hand samples. Under the microscope, however, dissolution and recrystallization, as well as pristine growth lines are all present. Sr isotopes in these shells range from that of normal Miocene seawater to radiogenic values. δ18O and δ13C values, and Mg, Sr, and Na concentrations in these shells are rather variable. The high end members are consistent with the typical values of modern/late Miocene normal-seawater low-Mg calcite shells, whereas the low end members are close to those of diagenetic calcite cements, which have low δ18O, δ13C, Sr and Na values, and radiogenic Sr. The Nijar shells were altered physically and chemically to different degrees by diagenesis, although these shells are consistent with some “criteria” of unalteration. The isotopic and trace-element data collected in altered and pristine (or less altered) portions coexisting in the same shells are clearly differentiable. Quantitative simulation of covariations of geochemical pairs indicates that solid mixing of unaltered and altered portions by sampling is consistent with the variations in isotopic and elemental data recorded in the Nijar shells. The geological significance of this study is that ancient fabric-retentive calcite shells may have been altered geochemically although they may appear pristine. Calcite shells that underwent intensive diagenesis should be examined rigorously under the microscope, coupled with investigations of multiple geochemical proxies to assess chemical alteration. Only the data of unaltered shells can be used to reconstruct the chemistry of ancient seawater.