Precipitation of carbonate minerals in travertine-depositing hot springs: Driving forces, microenvironments, and mechanisms

Travertine-depositing hot springs can generate various carbonate minerals with or without the participation of microorganisms. They thus serve as good natural laboratories to study abiotic and biotic factors controlling the precipitation of different carbonate minerals and CaCO₃ polymorphism. Through tens of years' investigations on travertines, considerable advances about carbonate mineral precipitation have been made. Here, we summarized general hydrological features of travertine systems, and driving forces, microenvironments, and mechanisms of the precipitation of different carbonate minerals in travertine-depositing hot springs by integrating present advances and conducting hydrochemical simulations. Travertine-depositing hot springs can be divided into near-neutral pH hot springs and hyperalkaline hot springs and contain four types of microenvironments: hypogean solid-water interface, epigean solid-water interface, air-water interface, and subaerial exposure surface. Both abiotic (passive CO₂ degassing, atmospheric CO₂ uptake, evaporation, and fluid mixing) and biotic (metabolism, organism-related crystal nucleation, and trapping and binding) processes may drive carbonate formation. The specific driving forces, however, depend on bulk water hydrochemistry and microenvironments. Calcite and aragonite are the most common minerals in travertines and the calcite-aragonite polymorphism might be under decisive influences from bulk water chemistry, especially [Mg²⁺]/[Ca²⁺], in some conditions. However, calcium carbonate precipitation in hot springs is controlled by solute transport in microenvironments, and any local change induced by hydrodynamics, microorganisms, and extracellular polymeric substances may significantly modify CaCO₃ precipitation and polymorphism. Such integrated control from bulk water composition and microenvironments also affects the formation of other carbonate minerals, but their exact roles remain unclear. Overall, despite the fruitful recent findings, further investigations, especially those focusing on microenvironments, are still imperative to better understand carbonate precipitation in hot springs. These microenvironment-scale studies might also provide insights on carbonate precipitation in other environments.