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Aqueous S[IV] species (, ) derived from volcanogenic atmospheric SO₂are important to planetary habitability through their roles in proposed origins‐of‐life chemistry and influence on atmospheric sulfur haze formation, but the early cycling of S[IV] is poorly understood. Here, we combine new laboratory constraints on S[IV] disproportionation kinetics with a novel aqueous photochemistry model to estimate the concentrations of S[IV] in natural waters on prebiotic Earth. We show that S[IV] disproportionation is slow in pH ≥ 7 waters, with timescaleT ≥ 1 year at room temperature, meaning that S[IV] was present in prebiotic natural waters. However, we also show that photolysis of S[IV] by UV light on prebiotic Earth limited [S[IV]] < 100 µM in global‐mean steady‐state. Because of photolysis, [S[IV]] was much lower in natural waters compared to the concentrations generally invoked in laboratory simulations of origins‐of‐life chemistry (≥10 mM), meaning further work is needed to confirm whether laboratory S[IV]‐dependent prebiotic chemistries could have functioned in nature. [S[IV]] ≥ 1 µM in terrestrial waters for: (a) SO₂outgassing ≥20× modern, (b) pond depths <10 cm, or (c) UV‐attenuating agents present in early waters or the prebiotic atmosphere. Marine S[IV] was sub‐saturated with respect to atmospheric SO₂, meaning that atmospheric SO₂deposition was efficient and that, within the constraints of present knowledge, UV‐attenuating sulfur hazes could only have persisted on prebiotic Earth if sulfur emission rates were very high (≳100× modern). Our work illustrates the synergy between planetary science, geochemistry and synthetic organic chemistry toward understanding the emergence and maintenance of life on early Earth.

 

Two important ions, K+ and Na+, are unequally distributed across the contemporary phospholipid-based cell membrane because modern cells evolved a series of sophisticated protein channels and pumps to maintain ion gradients. The earliest life-like entities or protocells did not possess either ion-tight membranes or ion pumps, which would result in the equilibration of the intra-protocellular K+/Na+ ratio with that in the external environment. Here, we show that the most primitive protocell membranes composed of fatty acids, that were initially leaky, would eventually become less ion permeable as their membranes evolved towards having increasing phospholipid contents. Furthermore, these mixed fatty acid-phospholipid membranes selectively retain K+ but allow the passage of Na+ out of the cell. The K+/Na+ selectivity of these mixed fatty acid-phospholipid semipermeable membranes suggests that protocells at intermediate stages of evolution could have acquired electrochemical K+/Na+ ion gradients in the absence of any macromolecular transport machinery or pumps, thus potentially facilitating rudimentary protometabolism.