Volcanic emissions and the early Earth atmosphere

Despite uncertainties in our understanding of early Earth volcanism and atmospheric composition, thermodynamic modelling is able to offer estimates of the global production of reactive trace species (NO, OH, SO₃, Cl, Br and I) from early Earth volcanism, and thereby to shed light on processes which may have been different in Earth’s early atmosphere. Model results show that thermal decomposition of magmatic H₂O, CO₂ and SO₂ in high-T mixtures of magmatic and atmospheric gases (at T > 1400 °C) generate high levels of reactive trace gas species. Production of these reactive trace species is insensitive to atmospheric CO₂ in mixtures where the atmospheric gas is the minor component and will hence continue during periods of low atmospheric CO₂. Fluxes of NO, OH, Cl, Br and I from early Earth volcanism are predicted to exceed those from modern Earth volcanism as the higher temperature of early Earth emissions compensates for lower levels of O₂ in the atmosphere, compared to the modern Earth. Under certain conditions, the volcanic NO flux from early Earth volcanism is found to be comparable to other sources of reactive N such as lightning NO and photochemical HCN. This is one possible source of fixed nitrogen which may alleviate any postulated Archean nitrogen crisis. Our thermodynamic model reveals that production of SO₃ (a potential precursor for near-source volcanic sulphate and hence ‘primary’ volcanic aerosol) is likely to be significantly lower from early Earth volcanism. Uncertainty in the pathway to near-source sulphate in modern volcanism (i.e., the reaction of SO₃ with water or direct emission) introduces a large uncertainty into the production rate of near-source volcanic sulphate on the early Earth.