Climatic significance of seasonal trace element and stable isotope variations in a modern freshwater tufa

We present a continuous ∼ 14-yr-long (1985 to 1999) high-resolution record of trace element (Mg, Sr, Ba, U) and stable isotope (δ¹³C, δ¹⁸O) variations in a modern freshwater tufa from northwestern Queensland, Australia. By utilizing the temperature dependence of the δ¹⁸O signal, an accurate chronology was developed for the sampled profile, which allowed a comparison of the chemical records with hydrological and meteorological observations. As a consequence, it was possible to constrain the relevant geochemical processes relating climate variables, such as temperature and precipitation, to their chemical proxies in the tufa record. Temperatures calculated from the Mg concentrations of the tufa samples provide close approximations of average annual water temperature variations. Furthermore, we demonstrate that temporal changes in (Mg/Ca)_water can be estimated using an empirically derived equation relating (Mg/Ca)_water to the (Sr/Ba) ratio measured in the tufa samples. By means of this relationship, it is theoretically possible to determine the (Mg/Ca) ratio of paleowaters, and hence to derive reliable estimates of former water temperatures from the Mg concentrations of fossil tufas from the study area. Sympathetic variations in Sr, Ba, and δ¹³C along the sampled profile record changes in water chemistry, which are most probably caused by variable amounts of calcite precipitation within the vadose zone of the karst aquifer. This process is thought to be markedly subdued whenever the amount of wet-season precipitation exceeds a given threshold. Accordingly, distinct minima in Sr, Ba, and δ¹³C are interpreted to reflect years with above-average rainfall. The pronounced seasonal and annual variability of the U concentration along the profile is thought to primarily record changes in the U flux from the soil to the water table. We suggest that during intensive rain events U is transported to the phreatic zone by complexing organic colloids, giving rise to conspicuous U maxima in the tufa after above-average wet seasons. This study demonstrates the potential of freshwater tufas to provide valuable information on seasonal temperature and rainfall variations. If tufa deposits turn out to be reasonably resistant to secondary processes, combined investigation of speleothems and tufas from the same area could become a promising approach in future research. While speleothems offer continuous records of long-term paleoenvironmental changes, tufas could provide high-resolution time windows into selected periods of the past.