Development, intercomparison, and evaluation of an improved mechanism for the oxidation of dimethyl sulfide in the UKCA model

Abstract

Abstract. Dimethyl sulfide (DMS) is an important trace gas emitted from the ocean. The oxidation of DMS has long been recognised as being important for global climate through the role DMS plays in setting the sulfate aerosol background in the troposphere. However, the mechanisms in which DMS is oxidised are very complex and have proved elusive to accurately determine in spite of decades of research. As a result the representation of DMS oxidation in global chemistry–climate models is often greatly simplified. Recent field observations and laboratory and ab initio studies have prompted renewed efforts in understanding the DMS oxidation mechanism, with implications for constraining the uncertainty in the oxidation mechanism of DMS as incorporated in global chemistry–climate models. Here we build on recent evidence and develop a new DMS mechanism for inclusion in the UK Chemistry Aerosol (UKCA) chemistry–climate model. We compare our new mechanism (CS2-HPMTF) to a number of existing mechanisms used in UKCA (including the highly simplified three-reactions–two-species mechanism used in CMIP6 studies with the model) and to a range of recently developed mechanisms reported in the literature through a series of global and box model experiments. Global model runs with the new mechanism enable us to simulate the global distribution of hydroperoxylmethyl thioformate (HPMTF), which we calculate to have a burden of 2.6–26 Gg S (in good agreement with the literature range of 0.7–18 Gg S). We show that the sinks of HPMTF dominate uncertainty in the budget, not the rate of the isomerisation reaction forming it and that, based on the observed DMS / HPMTF ratio from the global surveys during the NASA Atmospheric Tomography mission (ATom), rapid cloud uptake of HPMTF worsens the model–observation comparison. Our box model experiments highlight that there is significant variance in simulated secondary oxidation products from DMS across mechanisms used in the literature, with significant divergence in the sensitivity of the rates of formation of these products to temperature exhibited; especially for methane sulfonic acid (MSA). Our global model studies show that our updated DMS scheme performs better than the current scheme used in UKCA when compared against a suite of surface and aircraft observations. However, sensitivity studies underscore the need for further laboratory and observational constraints. In particular our results suggest that as a priority long-term DMS observations be made to better constrain the highly uncertain inputs into the system and that laboratory studies be performed that address (1) the uptake of HPMTF onto aerosol surfaces and the products of this reaction and (2) the kinetics and products of the following reactions: CH3SO3 decomposition, CH3S + O2, CH3SOO decomposition, and CH3SO + O3.