Partitioning of Mg, Sr, Ba and U into a subaqueous calcite speleothem

The trace-element geochemistry of speleothems is becoming increasingly used for reconstructing palaeoclimate, with a particular emphasis on elements whose concentrations vary according to hydrological conditions at the cave site (e.g. Mg, Sr, Ba and U). An important step in interpreting trace-element abundances is understanding the underlying processes of their incorporation. This includes quantifying the fractionation between the solution and speleothem carbonate via partition coefficients (where the partitioning (D) of element X (DX) is the molar ratio [X/Ca] in the calcite divided by the molar ratio [X/Ca] in the parent water) and evaluating the degree of spatial variability across time-constant speleothem layers. Previous studies of how these elements are incorporated into speleothems have focused primarily on stalagmites and their source waters in natural cave settings, or have used synthetic solutions under cave-analogue laboratory conditions to produce similar dripstones. However, dripstones are not the only speleothem types capable of yielding useful palaeoclimate information. In this study, we investigate the incorporation of Mg, Sr, Ba and U into a subaqueous calcite speleothem (CD3) growing in a natural cave pool in Italy. Pool-water measurements extending back 15 years reveal a remarkably stable geochemical environment owing to the deep cave setting, enabling the calculation of precise solution [X/Ca]. We determine the trace element variability of ‘modern’ subaqueous calcite from a drill core taken through CD3 to derive DMg, DSr, DBa and DU then compare these with published cave, cave-analogue and seawater-analogue studies. The DMg for CD3 is anomalously high (0.042 ± 0.002) compared to previous estimates at similar temperatures (∼8 °C). The DSr (0.100 ± 0.007) is similar to previously reported values, but data from this study as well as those from Tremaine and Froelich (2013) and Day and Henderson (2013) suggest that [Na/Sr] might play an important role in Sr incorporation through the potential for Na to outcompete Sr for calcite non-lattice sites. DBa in CD3 (0.086 ± 0.008) is similar to values derived by Day and Henderson (2013) under cave-analogue conditions, whilst DU (0.013 ± 0.002) is almost an order of magnitude lower, possibly due to the unusually slow speleothem growth rates (<1 μm a−1), which could expose the crystal surfaces to leaching of uranyl carbonate. Finally, laser-ablation ICP-MS analysis of the upper 7 μm of CD3, regarded as ‘modern’ for the purposes of this study, reveals considerable heterogeneity, particularly for Sr, Ba and U, which is potentially indicative of compositional zoning. This reinforces the need to conduct 2D mapping and/or multiple laser passes to capture the range of time-equivalent elemental variations prior to palaeoclimate interpretation

Isotope hydrology of dripwaters in a Scottish cave and implications for stalagmite palaeoclimate research

Dripwater hydrology and hydrogeochemistry is particularly useful to constrain the meaning of speleothem palaeoclimate archives, for example using d18O signatures. Here, we calibrate the relationship between d18O in precipitation, percolation waters and contemporary calcite deposits, at Tartair cave, Sutherland, NW Scotland, an Atlantic site sensitive to regional changes both of temperature and precipitation. Monthly precipitation displayed a 7.1 %0 range in d18O, a negative linear relationship with rainfall amount, and no correlation with temperature. Autogenically-derived cave percolation waters show little variation in d18O during the same period and their annual weighted mean is the same as that of the local precipitation. This evidence together with hydrological data and electroconductivity values indicates that percolation waters are well mixed and dominated by stored water. Calculated values of d18O of calcite deposited in this cave environment indicate that the cave deposits are forming close to isotopic equilibrium and kinetic effects are negligible. Comparison of a high-resolution d18O stalagmite record with the instrumental record of climate indicates that isotopically heavy values are reflective of relatively cold, dry conditions (and vice-versa for warm, wet condition) and hence that stalagmite oxygen isotopes provide an appropriate means of investigating the palaeoclimate in this location

North Atlantic ice-rafting, ocean and atmospheric circulation during the Holocene : insights from Western Mediterranean speleothems

In this study, we present a Holocene rainfall index based on three high-resolution speleothem records from the Western Mediterranean, a region under the influence of the westerly winds belt modulated by the North Atlantic Oscillation (NAO). On centennial to millennial timescales, we show that the North Atlantic ice-rafting events were likely associated with negative NAO-like conditions during the Early Holocene and the Late Holocene. However, our data reveal that this is not clearly the case for the mid-Holocene ice-rafting events, during which we also show evidence of positive NAO-like patterns from other paleo-oceanographic and paleo-atmospheric data. Hence, contradictory mechanisms involving prolonged periods of both north and south shifts of the westerly winds belt (resembling positive and negative NAO-like patterns) might at least partially trigger or amplify the ice-rafting events and the slowdown of the Atlantic Meridional Overturning Circulation. Plain Language Summary During the Holocene, periods of enhanced ice-rafting, associated with cooling and sea ice expansion in the North Atlantic high latitudes, have been recognized over distant regions. While the causes of these events are still a matter of debate, changes in the atmospheric circulation have been proposed as a potential trigger or amplifier. Here, we use speleothems to establish a precisely dated record of rainfall variability in the Western Mediterranean, a highly sensitive region to the westerly winds belt modulated by the North Atlantic Oscillation. Our results reveal new insights about the dynamics of NAO-like patterns during the Holocene. On centennial to millennial timescales, prolonged periods of both north and south shifts of the westerly winds belt might trigger or amplify the slowdown of the Atlantic Meridional Overturning Circulation and the North Atlantic ice-rafting. However, not all ice-rafting events are associated with either positive or negative NAO-like conditions

In situ U-series dating by laser-ablation multi-collector ICPMS: new prospects for Quaternary geochronology

The capabilities and potential applications of in situ dating of Quaternary materials using laser ablation-MC-ICPMS are explored. 234U/238U and 230Th/234U can be measured with precision sufficient for dating at a spatial resolution of 100 ?m or better in samples that contain as a little as 1 ppm uranium. Moreover, U and Th concentrations and U-series isotope ratios can be continuously profiled to determine changes in age that occur with sample growth (e.g. in speleothems). These capabilities additionally permit the dating of bones, teeth and possibly molluscs, which are subject to post-mortem open-system behaviour of U-series isotopes, and can be employed to elucidate processes of U-series migration during weathering and diagenesis. A drawback of laser ablation-MC-ICPMS is that it cannot in general provide U-series age estimates with the high precision and accuracy of conventional TIMS or solution MC-ICPMS methods. However, sample preparation is straightforward, the amount of sample consumed negligible, and it can be used to rapidly characterise or screen and select samples from which more precise and accurate dates can be obtained using conventional methods. Given further instrumental developments and the establishment of suitable matrix-matched standards for carbonates and other materials, we foresee that laser ablation-MC-ICPMS will play an increasingly important role in Quaternary dating research

Hydrothermal silicification and hypogene dissolution of an exhumed Neoproterozoic carbonate sequence in Brazil: Insights from fluid inclusion microthermometry and silicon-oxygen isotopes

Hypogene dissolution-precipitation processes strongly affect the petrophysical properties of carbonate rocks and fluid migration pathways in sedimentary basins. In many deep carbonate reservoirs, hypogene cavernous voids are often associated with silicified horizons. The diagenesis of silica in carbonate sequences is still a poorly-investigated research topic. Studies exploring the complexity of silica dissolution-precipitation patterns in hypogene cave analogues are therefore fundamental to unravel the diagenetic and speleogenetic processes that may affect this kind of reservoir. In this work, we investigated an exhumed and silicified Neoproterozoic carbonate sequence in Brazil hosting a 1.4 km-long cave. Quartz mineralization and silicified textures were analyzed with a multidisciplinary approach combining petrography, fluid inclusion microthermometry, silicon-oxygen stable isotope analyses and U-Th-Pb dating of monazite crystals. We found that an early silicification event caused the replacement of the dolostone layers with micro-crystalline quartz forming chert nodules. This event was likely associated with mixing fluids (ancient Neoproterozoic seawater and hydrothermal solutions sourced from the underlying Mesoproterozoic basement) at relatively low temperatures (ca. 50-100 degrees C) and shallow depth. After the tectonic deformation produced by the Brasiliano orogeny, silica dissolution was promoted by high temperature and alkaline hydrothermal solutions rising from the quartzite basement along deep-rooted structures. Hypogene hydrothermal alteration promoted the dissolution of the cherty layers and the precipitation of chalcedony and megaquartz. Homogenization temperatures from primary fluid inclusions in megaquartz cement indicate minimum formation temperatures of 165-210 degrees C. Similar temperature estimates (110-200 degrees C) were obtained from the delta Si-30 and delta O-18 isotope systematics of quartz precipitated from hydrothermal solutions. The dissolved salts in the fluid inclusions were evaluated as NaCl + CaCl2 from microthermometric data combined with cryogenic Raman spectroscopy, corresponding to salinity ranging between 17 and 25 wt.%. No reliable age constraints for hydrothermal silica dissolution-precipitation phases were obtained from monazite U-Th-Pb dating. However, our results, interpreted in the regional context of the Sao Francisco Craton, suggest that the Cambrian tectono-thermal events could have been amongst the possible drivers for this hypogene process in the basin