Abstract
Determination of highly siderophile element (HSE; Au, Pt, Pd, Ir, Os, Rh and Ru) concentrations in relatively unweathered and unaltered marine shales from the Barberton, Witwatersrand and Transvaal supergroups in the Kaapvaal Craton revealed systematic differences, interpreted to reflect secular changes in the HSE content of Mesoarchaean to Palaeoproterozoic seawater. Most of the studied marine shales have HSE concentrations in the range given for average Archaean crustal rocks (0.5–5 ppb), with the exception of the shales in the Witwatersrand Supergroup. These shales contain up to three times more HSE, independent of source rock lithology in the granitoid-greenstone-dominated hinterland. Although sedimentary pyrite incorporated gold from synsedimentary to early diagenetic waters, its modal proportion (<3 vol.%) is too small to account for the total amount of Au and PGE in the studied marine shales. Instead, our results suggest that in addition to contributions from pyrite, some colloidal gold was attached to clay-sized sediments during source area weathering. Probably, colloidal gold and some of the platinum group elements were mechanically aggregated during sediment suspension and deposited synchronously with the host marine sediments.
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Acknowledgments
This work was supported by the National Research Foundation (NRF) of South Africa to G. Nwaila (Grant UID: 88323). We thank Sibanye Gold Limited for providing the Witwatersrand Supergroup samples, as well as Helene Brätz and Ulrich Schüßler for assistance with the ICP-MS and XRF analyses, respectively. Chris Heubeck and Axel Hofmann are acknowledged for supplying some of the Barberton Supergroup samples. We thank Ross Large and Christopher Lawley for their constructive reviews of the original manuscript and Maarten Broekmans for editorial handling.
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Fig. S1
Negative correlation between Au content and sediment provenance indicator elemental ratios (a - Zr/Ni, b – Th/Sc) for the Booysens Formation shales, indicating preferred derivation of gold from mafic source rocks. (PNG 4.62 MB)
Fig. S2
Index of chemical variability (ICV) versus chemical index of weathering (CIW) for marine shales of the Kaapvaal Craton. Notes: ICV = (CaO + K2O + Na2O + Fe2O3 (T) + MgO + MnO + TiO2)/Al2O3 and CIW = Al2O3/ (Al2O3 + Na2O + CaO*) × 100). Values for Archaean rain water pH are from Krupp et al. 1994, values for Archaean river water pH are from Frimmel 2005, and values from Archean seawater pH are from Halevy and Bachan 2017.(PNG 4.58 MB)
Supplementary data S1
Whole–rock major (wt%) and trace element (ppm) concentrations including gold and platinum group elements for marine shales of the Barberton, Witwatersrand and Transvaal supergroups. (XLSX 107 kb)
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Nwaila, G.T., Frimmel, H.E. Highly siderophile elements in Archaean and Palaeoproterozoic marine shales of the Kaapvaal Craton, South Africa. Miner Petrol 113, 307–327 (2019). https://doi.org/10.1007/s00710-018-0650-3
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DOI: https://doi.org/10.1007/s00710-018-0650-3