The origin of early continental crust: New clues from coupling Ge/Si ratios with silicon isotopes

The recent discovery of heavy Si isotopic compositions in both high-Na Tonalite-Trondhjemite-Granodiorite (TTG) and High-K Granite-Monzonite-Syenite (GMS) suites of early continental crust requires that a notable seawater-derived silica-rich component had been added to their respective protoliths prior to melting. Here we use the Ge/Si ratio as a complementary tracer to δ30Si in order to delineate the exact role of modal quartz and silicified basalts from the Archean seafloor among the primary controls of the early appearance of felsic melts on Earth. We have approached the question by (1) specifying the Ge/Si signatures of various Archean and post-Archean rock types by compiling the Ge-SiO2 data stored within the GEOROC database; (2) coupling Ge/Si investigation to silicon isotopes on a large selection of silicified and unsilicified altered mafic and ultramafic greenstones, felsic volcanics, TTG and GMS granitoids and mineral separates from TTGs of the Barberton Greenstone Belt (BGB) of South Africa. The GEOROC compilation demonstrates that Archean TTGs and granites display much lower Ge/Si (1.15±0.10 and 1.13±0.11 μmol/mol, respectively) than post-Archean adakites, granites, tonalites and granodiorites (with average Ge/Si in the range of 1.64 to 1.85 μmol/mol). This result is corroborated by the Ge/Si ratios we report from BGB rocks that formed prior to Kaapvaal craton stabilisation, including 3.5 Ga Theespruit Formation felsic volcanic rocks, 3.5-3.2 Ga TTGs and 3.2-3.1 Ga GMSs, all of which exhibit low ratios (0.68±0.23; 0.92±0.17; 1.05±0.19 μmol/mol, respectively). Based on their low TTG-like Ge/Si, pre-cratonic GMSs are dismissed as being derived from melting of both TTG and metasedimentary sources. Instead, TTGs and GMSs originated from similar Ge-depleted sources. Low Ge/Si ratios, coupled to heavy Si isotopic signatures (−0.14‰