Faster phototransformation of the formate (terrestrial) versus methanesulphonate (marine) markers of airborne particles: implications for modelling climate change

Atmospheric particulate matter is altering climate. For instance marine biogenic particles are cooling climate. Organic markers are major tools to elucidate the sources of atmospheric particulate matter. Formate is commonly used as a marker of continental aerosols, whereas methanesulphonate is used as tracer of biogenic marine aerosols. However, transformation processes during aerosol transport may modify their relative concentrations and, in turn, introduce a bias in the assessment of particle sources. Actually very little is known about the transformation of formate and methanesulphonate in aerosols. Therefore, we irradiated formate and methanesulphonate in the presence of nitrate and haematite. Nitrate and haematite are aerosol photosensitisers, producing reactive species that degrade organic compounds. The time evolution of formate and methanesulphonate was monitored by ion chromatography. Our results show that formate is transformed from 1.6 to 4.1 times faster than methanesulphonate. This trend is partly due to higher reactivity with the hydroxyl radical and partly due to additional reaction with other transients such as nitrogen dioxide. Such results strongly suggest faster formate transformation during particle transport. Therefore, when formate and methanesulphonate are used as particle tracers, an overestimation of marine biogenic versus continental particle sources is expected. This bias has major implications for climate prediction models, because marine biogenic particles have a cooling effect on climate.