Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 AE 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH 4 and CO 2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth. Both interpretations have been questioned based on the susceptibility of chemical sediments to diagenetic alteration over geologic time (2, 4), and for the latter, a lack of geologic evidence for the extreme greenhouse gas concentrations required to sustain such high temperatures under a less luminous young Sun (9).Minerals formed by metasomatic reactions between seawater and oceanic lithosphere provide an alternative proxy for early ocean chemistry (10-14). Here we report hydrogen and oxygen isotope compositions of 114 silicate mineral separates from the ca. 3.8 Ga Isua Supracrustal Belt (ISB) of West Greenland, including metamorphosed basalts, gabbros, and ultramafic rocks that represent fragments of Eoarchaean oceanic crust (see Fig. S1, Table S2). Minerals formed during heterogeneous late-stage CO 2 -or meteoric-dominated metamorphic overprinting are distinguished by characteristic trends in their coupled δD and δ 18 O values (Fig. S2). In contrast, serpentine minerals formed by reaction of seawater with ultramafic rocks (peridotites) preserved in a low-strain enclave of the ISB (15) define a different isotopic trend. Here we use these serpentines to constrain D∕H and 18 O∕ 16 O ratios of the Eoarchaean ocean.
Serpentine Isotope GeochemistrySerpentine-group minerals are hydrous magnesian silicates commonly formed by hydrothermal infiltration of seawater into ultramafic oceanic crust, hydration of the mantle wedge by slabderived fluids, or fluid-rock interaction in continentally emplaced ultramafic lithologies (16)(17)(18). Serpentinized oceanic peridotites are dominantly composed of low-temperature (<300°C) polymorphs lizardite and chrysotile, and to a lesser extent antigorite, which forms at temperatures >250°C (17). In modern oceanic serpentinites, antigorites have δD between −46 and −30‰ (Figs. 1 and 2A, filled squares), values that indicate equilibrium with modern-...