Texture-specific Si isotope variations in Barberton Greenstone Belt cherts record low temperature fractionations in early Archean seawater

Sedimentary cherts are unusually abundant in early Archean (pre-3.0 Ga) sequences, suggesting a silica cycle that was profoundly different than the modern system. Previously applied for the purpose of paleothermometry, Si isotopes in ancient cherts can offer broader insight into mass fluxes and mechanisms associated with silica concentration, precipitation, diagenesis, and metamorphism. Early Archean cherts contain a rich suite of sedimentological and petrographic textures that document a history of silica deposition, cementation, silicification, and recrystallization. To add a new layer of insight into the chemistry of early cherts, we have used wavelength-dispersive spectroscopy and then secondary ion mass spectrometry (SIMS) to produce elemental and Si and O isotope ratio data from banded black-and-white cherts from the Onverwacht Group of the Barberton Greenstone Belt, South Africa. This geochemical data is then interpreted in the framework of depositional and diagenetic timing of silica precipitation provided by geological observations. SIMS allows the comparison of Si and O isotope ratios of distinct silica phases, including black carbonaceous chert beds and bands (many including well-defined sedimentary grains), white relatively pure chert bands including primary silica granules, early cavity-filling cements, and later quartz-filled veins. Including all chert types and textures analyzed, the δ^(30)Si dataset spans a range from −4.78‰ to +3.74‰, with overall mean 0.20‰, median 0.51‰, and standard deviation 1.30‰ (n = 1087). Most samples have broadly similar δ^(30)Si distributions, but systematic texture-specific δ^(30)Si differences are observed between white chert bands (mean +0.60‰, n = 750), which contain textures that represent primary and earliest diagenetic silica phases, and later cavity-filling cements (mean −1.41‰, n = 198). We observed variations at a ∼100 μm scale indicating a lack of Si isotope homogenization at this scale during diagenesis and metamorphism, although fractionations during diagenetic phase transformations may have affected certain textures. We interpret these systematic variations to reflect fractionation during silica precipitation as well as isotopically distinct fluids from which later phases originated. SIMS δ^(18)O values fall in a range from 16.39‰ to 23.39‰ (n = 381), similar to previously published data from bulk gas source mass spectrometry of Onverwacht cherts. We observed only limited examples of texture-related variation in δ^(18)O and did not observe correlation of δ^(18)O with δ^(30)Si trends. This is consistent with hypotheses that Si isotope ratios are more resistant to alteration under conditions of rock-buffered diagenesis (Marin-Carbonne et al., 2011). Our results indicate that low temperature processes fractionated silicon isotopes in early Archean marine basins, a behavior that probably precludes the application of chert δ^(30)Si as a robust paleothermometer. The values we observe for facies that sedimentological and petrographic observations indicate formed as primary and earliest diagenetic silica precipitates from seawater are more ^(30)Si-rich than that expected for bulk silicate Earth. This is consistent with the hypothesis that the silicon isotope budget is balanced by the coeval deposition of ^(30)Si-enriched cherts and ^(30)Si-depleted iron formation lithologies. Precipitation of authigenic clay minerals in both terrestrial and marine settings may have also comprised a large ^(30)Si-depleted sink, with the corollary of an important non-carbonate alkalinity sink consuming cations released by silicate weathering.