Depth profiles of iodide and iodate during POLARSTERN cruise ANT-XXIV/3 to the Atlantic sector of the Southern Ocean

The biogeochemistry of iodine in the waters of the Atlantic sector of the Southern Ocean was investigated during the Polarstern cruise ANTXXIV-3 ZERO&DRAKE. The speciation and distribution of iodine (iodate and iodide) in seawater was examined across gradients of iron concentrations and phytoplankton abundance, ranging from an open ocean region along the Zero Meridian to the Weddell Sea and Drake Passage. Iodine cycling in high latitudes differs from that in low latitudes due to differences in the plankton community composition and the physicochemical characteristics. Iodate concentrations ranged between 400 and 450 nmol/L from the surface to the bottom. Surface concentrations of iodide (17 to over 60 nmol/L) were about an order of magnitude higher than below the pycnocline. The peak values of iodide lay nearly always within the euphotic zone and showed a weak, positive correlation with nitrite concentrations in the upper 200 m. In all vertical profiles a pronounced sub-surface maximum in iodide appears between 50 and 200 m depth indicating an iodide drawdown at the near surface. Iodide distribution in the Weddell Sea showed elevated levels in Weddell Sea Bottom Water (WSBW) indicating slow oxidation kinetics and the potential for iodide as a tracer of WSBW formation.

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.