Towards a holistic sulfate-water-O2 triple oxygen isotope systematics
Triple oxygen isotope (∆ 17 O with δ 18 O) signals of H 2 O and O 2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas concentrations, and bioproductivity. However, interpretations of the sulfate-water-O 2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O 2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O 2 with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O 2 - versus H 2 O‑oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the ∆ 17 O and δ 18 O of sulfate's O 2 ‑oxygen source. Within this framework, new ∆ 17 O measurements of sulfate constrain ~2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO 2 concentrations prevalent on the early Earth.