Seasonal variations in Sr, Mg and P in modern speleothems (Grotta di Ernesto, Italy)

Abstract

Sub-annual variations in trace element chemistry and luminescence have recently been demonstrated from speleothems and offer the potential of high-resolution palaeoclimatic proxies. However, no studies have yet examined microscopic trace element variations in relation to modern cave conditions. In this study, the spatial variations in trace element (Sr, Mg and P) concentrations in speleothems (a stalagmite and a soda straw stalactite) from the alpine Ernesto cave (temperature 6.6±0.1°C) in a forested catchment in NE Italy have been studied using secondary ion mass spectrometry (SIMS) and compared with environmental parameters and waters in the modern cave. An annual lamination exists in the stalagmite and soda straw stalactite in the form of clear calcite with narrow visible layers, which are UV-fluorescent and interpreted to contain soil-derived humic/fulvic acids washed into the cave during autumn rains. Microanalyses were undertaken of seven annual laminae, probably deposited during the 1960s in the stalagmite, and seven laminae in the 1990s for the stalactite. The analysis results show that Sr consistently has a trough and P, a peak centred on the inclusion-rich layer. Mg shows mainly a negative covariation with Sr in laminae formed in the 1990s, but a positive covariation in the stalagmite formed in 1960s. The spatial scale of the main geochemical variations is the same as that of annual laminae of inclusion-poor and inclusion-rich couplets. Mass balance arguments are used to show that the P is inorganic in form and presumably occurs as individual phosphate ions within the calcite. Most drip waters show limited chemical variations, but a summer peak in trace elements in 1995 and a decrease in Mg/Ca in the following winter are notable. More pronounced covariations in Mg/Ca and Sr/Ca are shown by a site with highly variable drip rates where ratios increase at slow drip rates. The strongest seasonal variations are found in pool waters, where ratios increase reflecting significant Ca removal from the water into the calcite during the winter in response to seasonal PCO 2 variations in cave air. Thus, the cave waters' compositions tend to reflect climate conditions, such that Mg/Ca and Sr/Ca are tentatively interpreted to be higher when climate conditions are dry. Combining results from the speleothems and cave water along with the behaviour of each trace species, Mg/Ca variations in the speleothems are considered to reflect their variation in the cave waters, whereas, Sr incorporation is also dependent on precipitation rate, in this case, mainly controlled by temporal variations in PCO 2 in the cave (and conceivably, also by inhibitors such as phosphate). P adsorption (a fraction of which is subsequently incorporated within calcite) depends on aqueous phosphate concentration and water flux, both of which should increase during the autumn. Therefore, multiple trace element profiles in speleothems reflect multiple aspects of environment seasonality and conditions, and hence, a calibration against weather records is desirable to establish their palaeoclimatological meaning. The strong annual variation of trace elements, and particularly P, can provide chronological markers for high-resolution studies of other climate proxies, such as stable isotopes.