Crystallization pathways, fabrics and the capture of climate proxies in speleothems: examples from the tropics

The quality of climate proxy data from speleothem archives depends to varying degrees on crystallization processes, which result in diverse fabrics. Here, we document shifts in calcite growth mechanisms, from ion-by-ion to nanoparticle/nanocrystal attachment, in stalagmites from the tropical island of Atiu (South Pacific). Changes in solution stoichiometry and organic matter content result in the development of two columnar fabrics that are common elsewhere in settings characterized by seasonal contrast. A porous columnar fabric, characterized by intracrystalline micro and nanoporosity grows via a non-classical pathway through amorphous calcium carbonate (ACC) nanoparticles (∼2–4 nm in diameter) and calcite nanocrystal attachment. Despite subsequent transformation of nanoparticles/crystals into a large calcite crystal, the porous columnar fabric appears to preserve a δ18O signal that faithfully reflects that of the parent fluid via quasi-equilibrium fractionation. Furthermore, the porous fabric shows random and fuzzy lateral distributions of Sr, another hydrological proxy, yet this element's incorporation follows equilibrium partitioning. The chemical properties of compact columnar fabrics, which appear to grow by classical ion-by-ion attachment, may not directly reflect those of the original depositional environment because of degassing, the presence of growth inhibitors (such as Na) and very early diagenetic modifications. Columnar porous calcite fabrics that formed through non-classical pathways in other settings may faithfully record the original properties of the parent drip water, whereas compact fabrics that formed through classical pathways elsewhere may not. It is concluded that the study of fabrics at the nano-scale is a necessary complement to speleothem research to identify the influence of crystallization pathways on the accuracy of proxy data.