Review of calcium carbonate polymorph precipitation in spring systems

Many spring deposits throughout the world are characterized by spectacular deposits of calcium carbonate that are formed of various combinations of aragonite and calcite, and in very rare cases vaterite. The factors that control the precipitation of the aragonite and calcite have been the subject of considerable debate that has been based on natural precipitates and information gained from numerous laboratory experiments. Synthesis of this information indicates that there is probably no single universal factor that controls calcite and aragonite precipitation in all springs. Instead, the reason for aragonite as opposed to calcite precipitation should be ascertained by considering the following ordered series of possibilities for each system. First, aragonite, commonly with calcite as a co-precipitate, will form from spring water that has a high CO2 content and rapid CO2 degassing, irrespective of the Mg:Ca ratio and scale of precipitation. Second, aragonite can be precipitated from waters that have low levels of CO2 degassing provided that the Mg:Ca ratio is high enough to inhibit calcite precipitation. Third, the presence of biofilms may lead to the simultaneous precipitation of aragonite and calcite (irrespective of CO2 degassing or Mg:Ca ratio) either within the different microdomains that develop in the biofilm or because of diurnal changes in various geochemical parameters associated with the biofilm. Although the precipitation of calcite and aragonite has commonly been linked directly to water temperature, there is no clear evidence for this proposition. It is possible, however, that temperature may be influencing another parameter that plays a more direct role in the precipitation of these CaCO3 polymorphs. Despite the advances that have been made, the factors that ultimately control calcite and aragonite are still open to debate because this long-standing problem has still not been fully resolved.