U enrichment and Th/U fractionation in Archean boninites: Implications for paleo-ocean oxygenation and U cycling at juvenile subduction zones

Abstract

Phanerozoic boninites record enrichments of U over Th, giving Th/U 0.5-1.6, relative to intraoceanic island arc tholeiites (IAT) where Th/U averages 2.6. Uranium enrichment is attributed to incorporation of shallow, oxidized fluids, U-rich but Th-poor, from the slab into the melt column of boninites which form in near-trench to forearc settings of suprasubduction zone ophiolites. Well preserved Archean komatiite-tholeiite, plume-derived, oceanic volcanic sequences have primary magmatic Th/U ratios of 4.4-3.6, and Archean convergent margin IAT volcanic sequences, having REE and HFSE compositions similar to Phanerozoic IAT equivalents, preserve primary Th/U of 4-3.6. The best preserved Archean boninites of the 3.0 Ga Olondo and 2.7 Ga Gadwal greenstone belts, hosted in convergent margin ophiolite sequences, also show relative enrichments of U over Th, with low average Th/U ∼ 3 relative to coeval IAT, and Phanerozoic counterparts which are devoid of crustal contamination and therefore erupted in an intraoceanic setting, with minimal contemporaneous submarine hydrothermal alteration. Later enrichment of U is unlikely as Th-U-Nb-LREE patterns are coherent in these boninites whereas secondary effects induce dispersion of Th/U ratios. The variation in Th/U ratios from Archean to Phanerozoic boninites of greenstone belts to ophiolitic sequences reflect on genesis of boninitic lavas at different tectono-thermal regimes. Consequently, if the explanation for U enrichment in Phanerozoic boninites also applies to Archean examples, the implication is that U was soluble in oxygenated Archean marine water up to 600 Ma before the proposed great oxygenation event (GOE) at approx. 2.4 Ga. This interpretation is consistent with large Ce anomalies in some hydrothermally altered Archean volcanic sequences aged 3.0-2.7 Ga.