Mg isotopic systematics during early diagenetic aragonite-calcite transition: Insights from the Key Largo Limestone

Abstract The seawater magnesium (Mg) isotopic composition (δ26MgSW) can be applied to quantify marine Mg cycle in Earth's history. However, reconstruction of δ26MgSW by using marine carbonate has been challenged by the large range of variation in Mg isotopic composition of carbonate (δ26Mgcarb). Such variation, on the one hand, reflects, e.g. the mineralogy, temperature, and precipitation rate dependent isotopic fractionation during Ca‑carbonate precipitation. On the other hand, the pristine seawater record could be modified in carbonate diagenesis, during which less stable carbonate minerals would spontaneously convert to more stable mineral phases. In the modern ocean with high Mg/Ca (molar) ratio (~5), aragonite precipitation is favored. However, aragonite is thermodynamically less stable than low-Mg calcite at ambient surface environment, resulting in the spontaneous transition from aragonite to low-Mg calcite in the earliest stage of diagenesis (i.e. the aragonite-calcite transition). As a common process in the modern ocean, Mg isotopic fractionation in aragonite-calcite transition may provide valuable constraints on the variation of δ26Mgcarb. In this study, we measured Mg isotopic compositions of Pleistocene Key Largo Limestone (Florida), which has been experiencing the aragonite-calcite transition during early diagenesis. The Key Largo Limestone samples consist of a mixture of calcite and aragonite. δ26Mg of aragonite (δ26Mgarag) shows higher and more stable values, while calcite has lower yet more variable Mg isotopes (δ26Mgcal). We suggest a model conceptualizing a water-film attached to the mineral surface, in which the aragonite-calcite transition initiates with aragonite dissolution and the Mg exchange with external fluid can be variable, followed by Mg isotopes fractionate during low-Mg calcite precipitation. In this model, δ26Mgcal is controlled by (1) the chemical composition of water-film, which is dependent on the mineralogical composition of aragonite (i.e. Mg content and δ26Mgarag), the composition of external fluid (i.e. fresh water, seawater, or mixed fresh water and seawater), and the mixing ratio between dissolved aragonite and external fluid, and (2) the isotopic fractionation during calcite precipitation. Because the isotopic fractionation in calcite is sensitive to the rate of calcite precipitation that is dependent on the calcite saturation state of solution. Therefore, δ26Mgcal could be highly heterogeneous depending on the aragonite dissolution and calcite precipitation processes, further complicating the interpretation of carbonate data. Thus, the process-controlled Mg isotopic fractionation should be taken into consideration when reconstructing δ26MgSW by using carbonate sediments/rocks.