The search for life beyond the Solar System is a major activity in exoplanet science. However, even if an Earth-like planet were to be found, it is unlikely to be at a similar stage of evolution as the modern Earth. It is therefore of interest to investigate the sensitivity of biomarker signals for life as we know it for an Earth-like planet but at earlier stages of evolution. Here, we assess biomarkers i.e. species almost exclusively associated with life, in present-day and in 10% present atmospheric level oxygen atmospheres corresponding to the Earths Proterozoic period. We investigate the impact of proposed enhanced microbial emissions of the biomarker nitrous oxide, which photolyses to form nitrogen oxides which can destroy the biomarker ozone. A major result of our work is regardless of the microbial activity producing nitrous oxide in the early anoxic ocean, a certain minimum ozone column can be expected to persist in Proterozoic-type atmospheres due to a stabilising feedback loop between ozone, nitrous oxide and the ultraviolet radiation field. Atmospheric nitrous oxide columns were enhanced by a factor of 51 for the Proterozoic Canfield ocean scenario with 100 times increased nitrous oxide surface emissions. In such a scenario nitrous oxide displays prominent spectral features, so may be more important as a biomarker than previously considered in such cases. The run with Canfield ocean nitrous oxide emissions enhanced by a factor of 100 also featured additional surface warming of 3.5K. Our results suggest that the Proterozoic ozone layer mostly survives the changes in composition which implies that it is indeed a good atmospheric biomarker.
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