Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.

Paleoclimate record combinatio of speleothems and of sediment core GeoB3910-2

A substantial strengthening of the South American monsoon system (SAMS) during Heinrich Stadials (HS) points toward decreased cross-equatorial heat transport as the main driver of monsoonal hydroclimate variability at millennial time-scales. In order to better constrain the exact timing and internal structure of HS1 over tropical South America we assessed two precisely dated speleothem records from central-eastern and northeastern Brazil in combination with two marine records of terrestrial organic and inorganic matter input into the western equatorial Atlantic. During HS1 we recognize at least two events of widespread intensification of the SAMS across the entire region influenced by the South Atlantic Convergence Zone (SACZ) at 16.11-14.69 kyr BP and 18.1-16.66 kyr BP (labeled as HS1a and HS1c, respectively), separated by a dry excursion from 16.66-16.11 kyr BP (HS1b). In view of the spatial structure of precipitation anomalies, the widespread increase of monsoon precipitation over the SACZ domain was termed 'Mega-SACZ'.