Carbonatization of oceanic crust by the seafloor hydrothermal activity and its significance as a CO2 sink in the Early Archean1

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Scientific paper

Early Archean (3.46 Ga) hydrothermally altered basaltic rocks exposed near Marble Bar, eastern Pilbara Craton, have been studied in order to reveal geological and geochemical natures of seafloor hydrothermal carbonatization and to estimate the CO2 flux sunk into the altered oceanic crust by the carbonatization. The basaltic rocks are divided into basalt and dolerite, and the basalt is further subdivided into type I, having original igneous rock textures, and type II, lacking these textures due to strong hydrothermal alteration. Primary clinopyroxene phenocrysts are preserved in some part of the dolerite samples, and the alteration mineral assemblage of dolerite (chlorite + epidote + albite + quartz ± actinolite) indicates that the alteration condition was typical greenschist facies. In other samples, all primary minerals were completely replaced by secondary minerals, and the alteration mineral assemblage of the type I and type II basalts (chlorite + K-mica + quartz + carbonate minerals ± albite) is characterized by the presence of K-mica and carbonate minerals and the absence of Ca-Al silicate minerals such as epidote and actinolite, suggesting the alteration condition of high CO2 fugacity. The difference of the alteration mineral assemblages between basalt and dolerite is probably attributed to the difference of water/rock ratio that, in turn, depends on their porosity. Carbonate minerals in the carbonatized basalt include calcite, ankerite, and siderite, but calcite is quite dominant. The δ13C values of the carbonate minerals are -0.3 ± 1.2‰ and mostly within the range of marine carbonate, indicating that the carbonate minerals were formed by seafloor hydrothermal alteration and that carbonate carbon in the altered basalt was derived from seawater. Whole-rock chemical composition of the basaltic rocks is essentially similar to that of modern mid-ocean ridge basalt (MORB) except for highly mobile elements such as K2O, Rb, Sr, and Ba. Compared to the least altered dolerite, all altered basalt samples are enriched in K2O, Rb, and Ba, and are depleted in Na2O, reflecting the presence of K-mica replacing primary plagioclase. In addition, noticeable CO2 enrichment is recognized in the basalt due to the ubiquitous presence of carbonate minerals, but there was essentially neither gain nor loss of CaO. This suggests that the CO2 in the hydrothermal fluid (seawater) was trapped by using Ca originally contained in the basalt. The CaO/CO2 ratios of the basalt are generally the same as that of pure calcite, indicating that Ca in the basalt was almost completely converted to calcite during the carbonatization, although Mg and Fe were mainly redistributed into noncarbonate minerals such as chlorite. The carbon flux into the Early Archean oceanic crust by the seafloor hydrothermal carbonatization is estimated to be 3.8 × 1013 mol/yr, based on the average carbon content of altered oceanic crust of 1.4 × 10-3 mol/g, the alteration depth of 500 m, and the spreading rate of 1.8 × 1011 cm2/yr. This flux is equivalent to or greater than the present-day total carbon flux. It is most likely that the seafloor hydrothermal carbonatization played an important role as a sink of atmospheric and oceanic CO2 in the Early Archean.

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