Ivia Closset

GEOTRACES Intercalibration of the Stable Silicon Isotope Composition of Dissolved Silicic Acid in Seawater

The first inter-calibration study of the stable silicon isotope composition of dissolved silicic acid in seawater, δ30Si(OH)4, is presented as a contribution to the international GEOTRACES program. Eleven laboratories from seven countries analyzed two seawater samples from the north Pacific subtropical gyre (Station ALOHA) collected at 300 m and at 1000 m water depth. Sampling depths were chosen to obtain samples with a relatively low (9 μmol L-1, 300 m) and a relatively high (113 μmol L-1, 1000 m) silicic acid concentration as sample preparation differs for low- and high- concentration samples. Data for the 1000m water sample were not normally distributed so the median is used to represent the central tendency for the two samples. Median δ30Si(OH)4 values of +1.66 ‰ for the low-concentration sample and +1.25 ‰ for the high-concentration sample were obtained. Agreement among laboratories is overall considered very good; however, small but statistically significant differences among the mean isotope values obtained by different laboratories were detected likely reflecting interlaboratory differences in chemical preparation including pre-concentration and purification methods together with different volumes of seawater volume analyzed, and the use of different mass spectrometers including the Neptune MC-ICP-MS (Thermo Fisher™, Germany), the Nu Plasma MC-ICP-MS (Nu Instruments™, Wrexham, UK), and the Finnigan™ (now Thermo Fisher™, Germany) MAT 252 IRMS. Future studies analyzing δ30Si(OH)4 in seawater should also analyze and report values for these same two reference waters in order to facilitate comparison of data generated among and within laboratories over time.

Seasonal variations, origin, and fate of settling diatoms in the Southern Ocean tracked by silicon isotope records in deep sediment traps

The Southern Ocean plays a pivotal role in the control of atmospheric CO 2 levels, via both physical and biological sequestration processes. The biological carbon transfer to the ocean interior is tightly coupled to the availability of other elements, especially iron as a trace-limiting nutrient and dissolved silicon as the mineral substrate that allows diatoms to dominate primary production. Importantly, variations in the silicon cycling are large but not well understood. Here we use δ 30 Si measurements to track seasonal flows of silica to the deep sea, as captured by sediment trap time series, for the three major zones (Antarctic, AZ; Polar Frontal, PFZ; and Sub-Antarctic, SAZ) of the open Southern Ocean. Variations in the exported flux of biogenic silica (BSi) and its δ 30 Si composition reveal a range of insights, including that (i) the sinking rate of BSi exceeds 200 m d −1 in summer in the AZ yet decreases to very low values in winter that allow particles to remain in the water column through to the following spring, (ii) occasional vertical mixing events affect the δ 30 Si composition of exported BSi in both the SAZ and AZ, and (iii) the δ 30 Si signature of diatoms is well conserved through the water column despite strong BSi and particulate organic carbon (POC) attenuation at depth and is closely linked to the Si consumption in surface waters. With the strong coupling observed between BSi and POC fluxes in PFZ and AZ, these data provide new constraints for application to biogeochemical models of seasonal controls on production and export.