Origin and mechanisms of K–Si-metasomatism of ca. 3.4–3.3 Ga volcaniclastic deposits and implications for Archean seawater evolution: Examples from cherts of Kittys Gap (Pilbara craton, Australia) and Msauli (Barberton Greenstone Belt, South Africa)

The effects of K–Si-metasomatism during the formation of Early Archean replacement cherts have been quantified in this study by the investigation of two well-known stratigraphic sections: the Msauli chert (MC, Barberton greenstone belt, South Africa) and the Kittys Gap chert (KGC, Pilbara craton, Western Australia). The KGCs have a dacitic precursor similar to Duffer Formation dacites (Pilbara craton), while the MCs are derived from Al-depleted komatiites similar to those from the Weltevreden Formation (Barberton greenstone belt). Mass balance calculations reveal that the volcaniclastic deposits had initial porosities of up to 85 vol.% for the KGC and of 65 vol.% for the MC. Secondary porosities (27 vol.%: MC, 8 vol.%: KGC) produced during K-metasomatism are proportional to the dissolution of Fe, Ca, Mg-rich glass and precursor minerals. Komatiites have a higher chemical exchange potential than dacites, each gram releasing 1.2 mmol Fe²⁺, 2.8 mmol Mg²⁺, 1.4 mmol Ca²⁺ and 1.1 mmol Na⁺ to seawater, together with 4.4 mmol O²⁻. K-metasomatism of 1 g of komatiite further implies an uptake of 0.67 mmol of K⁺ and 2.7 mmol of H⁺. The highest silica uptake is achieved for the KGC (82 mmol/g of precursor). This silica enrichment most likely operated in the water column and at the sediment–water interface by sorption mechanisms on the surface of detrital particles and particulate organic matter, as a result of seawater silica-saturation. Acidic conditions (pH 5.5–6.5) and hot temperatures (>70 °C) favored the formation of K-rich phyllosilicates by interaction with seawater during the early diagenetic alteration of the volcaniclastic particles. The widespread occurrence of K–Si-metasomatism in volcanic and sedimentary rocks can be regarded as a general alteration process of the Early Archean seafloor, with a major influence on seawater composition. The highly K-selective metasomatism confirms previous studies suggesting that the Archean ocean was acidic and probably in equilibrium with a CO₂-rich atmosphere.