Photochemical Runaway in Exoplanet Atmospheres: Implications for Biosignatures

About 2.5 billion years ago, microbes learned to harness plentiful solar energy to reduce CO2 with H2O, extracting energy and producing O-2 as waste. O-2 production from this metabolic process was so vigorous that it saturated its photochemical sinks, permitting it to reach "runaway" conditions and rapidly accumulate in the atmosphere despite its reactivity. Here we argue that O-2 may not be unique: diverse gases produced by life may experience a "runaway" effect similar to O-2. This runaway occurs because the ability of an atmosphere to photochemically cleanse itself of trace gases is generally finite. If produced at rates exceeding this finite limit, even reactive gases can rapidly accumulate to high concentrations and become potentially detectable. Planets orbiting smaller, cooler stars, such as the M dwarfs that are the prime targets for the James Webb Space Telescope (JWST), are especially favorable for runaway, due to their lower UV emission compared to higher-mass stars. As an illustrative case study, we show that on a habitable exoplanet with an H-2-N-2 atmosphere and net surface production of NH3 orbiting an M dwarf (the "Cold Haber World" scenario), the reactive biogenic gas NH3 can enter runaway, whereupon an increase in the surface production flux of one order of magnitude can increase NH3 concentrations by three orders of magnitude and render it detectable by JWST in just two transits. Our work on this and other gases suggests that diverse signs of life on exoplanets may be readily detectable at biochemically plausible production rates.