Environmental setting, (micro)morphologies and stable C–O isotope composition of cold climate carbonate precipitates—a review and evaluation of their potential as paleoclimatic proxies

Given the growing interest in carbonate deposits from polar regions as paleoclimatic proxies, this review paper first provides a classification of the various types of cold-climate carbonate precipitates followed by a summary of the 13C and 18O composition of the carbonate deposits and parent water from which the carbonates precipitated. The cold-climate carbonate precipitates were classified into three broad categories: powders, crusts and speleothem. The carbonate powders include those that precipitated in relation to aufeis aggradation (cryogenic aufeis calcite) and in relation to the growth of various annual/perennial ice formations in freezing caves (cryptocrystalline calcite and calcite pearls). The carbonate crusts can be further subdivided based on their lithic environment; those that precipitated on the upper surface of bedrock/clasts (i.e. subglacially precipitated calcite and evaporative calcite crusts); those that are located on the underside of clasts (i.e. pedogenic carbonates); and those that precipitated in rock outcrop fissures (i.e. endostromatolites). The cold-climate carbonate precipitates have a highly variable isotopic composition with δ18O values ranging between −6.5‰ and 28‰ VSMOW and δ13C values in the −10–20‰ VPDB range. However, each type of carbonate precipitates has a specific δ13C and δ18O range, suggesting that their environmental setting and the mechanism by which they formed controls their 13C and 18O signature. It was found that carbonate deposits that precipitated under equilibrium physico-chemical conditions had a δ13C value that is in equilibrium with that of the parent water, while its δ18O composition was more variable, as it is in part controlled by the temperature of reaction and by the δ18O and calcite saturation state of the parent water. By contrast, the δ18O composition of biologically precipitated carbonate deposits (endostromatolites) reflect that of the parent water, while its δ13C composition was enriched over that of the parent water due to bacterial methanogenesis. In the case of kinetically precipitated carbonate deposits, the δ18O and δ13C values are out-of-equilibrium relative to that of the parent water due to the faster rate of reaction.