Development of a protocol to obtain the composition of terrigenous detritus in marine sediments -a pilot study from International Ocean Discovery Program Expedition 361

The geochemical and isotopic composition of terrigenous clays from marine sediments can provide important information on the sources and pathways of sediments. International Ocean Discovery Program Expedition 361 drilled sites along the eastern margin of southern Africa that potentially provide archives of rainfall on the continent as well as dispersal in the Agulhas Current. We used standard methods to remove carbonate and ferromanganese oxides and Stokes settling to isolate the clay fractions. In comparison to most previous studies that aimed to extract the detrital signal from marine sediments, we additionally applied a cation exchange wash using CsCl as a final step in the sample preparation. The motivation behind the extra step, not frequently applied, is to remove ions that are gained on the clay surface due to adsorption of authigenic trace metals in the ocean or during the leaching procedure. Either would alter the composition of the detrital fraction if no cation exchange was applied. Moreover, using CsCl will provide an additional measure of the cation exchange capacity (CEC) of the samples. However, no study so far has evaluated the potential and the limitations of such a targeted protocol for marine sediments. Here, we explore the effects of removing and replacing adsorbed cations on the clay surfaces with Cs+, conducting measurements of the chemical compositions, and radiogenic isotopes on a set of eight clay sample pairs. Both sets of samples underwent the same full leaching procedure except that one batch was treated with a final CsCl wash step. In this study, organic matter was not leached because sediments at IODP Site U1478 have relatively low organic content. However, in general, we recommend including that step in the leaching procedure. As expected, significant portions of elements with high concentrations in seawater were replaced by Cs+ (2SD 2.8%.) from the wash, including 75% of the sodium and approximately 25% of the calcium, 10% of the magnesium, and 8% of the potassium. Trace metals such as Sr and Nd, whose isotopes are used for provenance studies, are also found to be in lower concentrations in the samples after the exchange wash. The exchange wash affected the radiogenic isotope compositions of the samples. Neodymium isotope ratios are slightly less radiogenic in all the washed samples. Strontium and Pb isotopes showed significant deviations to either more or less radiogenic values in different samples. The radiogenic isotopes from the CsCl-treated fractions gave more consistent correlations with each other, and we suggest this treatment offers a superior measure of provenance. Although we observed changes in the isotope ratios, the general trend in the data and hence the overall provenance interpretations remained the same. However, the chemical compositions are significantly different. We conclude that a leaching protocol including a cation exchange wash (e.g. CsCl) is useful for revealing the terrestrial fingerprint. CEC could, with further calibration efforts, be useful as a terrestrial chemical weathering proxy.