The atmospheric composition of trace gases and aerosols is determined by the emission of compounds from the marine and terrestrial biospheres, anthropogenic sources and their chemistry and deposition processes. Biogenic emissions depend upon physiological processes and climate, and the atmospheric chemistry is governed by climate and feedbacks involving greenhouse gases themselves. Understanding and predicting the biogeochemistry of trace gases in past, present and future climates therefore demands an interdisciplinary approach integrating across physiology, atmospheric chemistry, physics and meteorology. Here, we highlight critical issues raised by recent findings in all of these key areas to provide a framework for better understanding the past and possible future evolution of the atmosphere. Incorporating recent experimental and observational findings, especially the influence of CO2 on trace gas emissions from marine algae and terrestrial plants, into earth system models remains a major research priority. As we move towards this goal, archives of the concentration and isotopes of N2O and CH4 from polar ice cores extending back over 650 000 years will provide a valuable benchmark for evaluating such models. In the Pre-Quaternary, synthesis of theoretical modelling with geochemical and palaeontological evidence is also uncovering the roles played by trace gases in episodes of abrupt climatic warming and ozone depletion. Finally, observations and palaeorecords across a range of timescales allow assessment of the Earth's climate sensitivity, a metric influencing our ability to decide what constitutes 'dangerous' climate chan-e. 0