Lead isotopes in deep-sea coral skeletons: ground-truthing and a first deglacial Southern Ocean record

Past changes in seawater lead (Pb) isotopes record the temporal evolution of anthropogenic pollution, continental weathering inputs, and ocean current transport. To advance our ability to reconstruct this signature, we present methodological developments that allow us to make precise and accurate Pb isotope measurements on deep-sea coral aragonite, and apply our approach to generate the first Pb isotope record for the glacial to deglacial mid-depth Southern Ocean. Our refined methodology includes a two-step anion exchange chemistry procedure and measurement using a ^(207)Pb-^(204)Pb double spike on a ThermoFinnigan Triton TIMS instrument. By employing a 10^(12) Ω resistor (in place of a 10^(11) Ω resistor) to measure the low-abundance ^(204)Pb ion beam, we improve the internal precision on ^(206,207,208)Pb/^(204)Pb for a 2 ng load of NIST-SRM-981 Pb from typically ∼420 ppm to ∼260 ppm (2 s.e.), and the long term external reproducibility from ∼960 ppm to ∼580 ppm (2 s.d.). Furthermore, for a typical 500 mg coral sample with low Pb concentrations (∼6-10 ppb yielding ∼3-5 ng Pb for analysis), we obtain a comparable internal precision of ∼150-250 ppm for ^(206,207,208)Pb/^(204)Pb, indicating a good sensitivity for tracing natural Pb sources to the oceans. Successful extraction of a seawater signal from deep-sea coral aragonite further relies on careful physical and chemical cleaning steps, which are necessary to remove anthropogenic Pb contaminants and obtain results that are consistent with ferromanganese crusts. Applying our approach to a collection of late glacial and deglacial corals (∼12-40 ka BP) from south of Tasmania at ∼1.4-1.7 km water depth, we generated the first intermediate water Pb isotope record from the Southern Ocean. That record reveals millennial timescale variability, controlled by binary mixing between two Pb sources, but no distinct glacial-interglacial Pb isotope shift. Mixing between natural endmembers is fully consistent with our data and points to a persistence of the same Pb sources through time, although we cannot rule out a minor influence from recent anthropogenic Pb. Whereas neodymium (Nd) isotopes in the Southern Ocean respond to global ocean circulation changes between glacial and interglacial periods, Pb isotopes record more localised mixing within the Antarctic Circumpolar Current, potentially further modulated by climate through changing terrestrial inputs from southern Africa or Australia. Such decoupling between Pb and Nd isotopes in the Southern Ocean highlights their potential to provide complementary insights into past oceanographic variability