What determines the calcium concentration of speleothem-forming drip waters?

Abstract

Cave drip water calcium ion concentration is a primary determinant of speleothem deposition and growth rate. The factors that determine drip water calcium ion concentrations are the soil and vadose zone CO2 concentrations, and the hydrogeochemical evolution of the water from soil to cave. Here, we use a systematic literature review of cave drip water calcium concentrations, combined with PHREEQC equilibrium modelling, to investigate the global relationship between calcium concentration and surface climate. Our results are discussed in the context of understanding the climatic and environmental controls on drip water calcium concentration, speleothem growth rates and proxies of past climate and environmental change. We use an empirical, global soil CO2 concentration–temperature relationship to derive PHREEQC modelled cave drip water calcium concentrations. The global mean modelled drip water calcium concentration is close to that observed, but it over-predicts at high and low temperatures, and significantly under-predicts at temperate conditions. We hypothesise that closed system hydrochemical evolution due to water saturation is an important control on carbonate dissolution at colder temperatures. Under warmer conditions, for example temperate climates with a dry and hot or warm summer, seasonally-limited water availability can lead to: <100% soil cover; water-limitations on microbial and root respiration; wildfire; and prior calcite precipitation, all of which limit drip water calcium concentrations. In temperate climates with no dry season, higher CO2 concentrations than modelled from soil values are necessary to explain the observed drip water calcium values, which we propose is from an additional source of CO2 from microbial activity and root respiration in the vadose zone during open system hydrochemical evolution.