The Role of Cloud Processing in the Relationship Between Wet Deposited Sulphur and Sulphur Dioxide Emissions

It is well established that wet deposition of sulphate in the UKhas fallen by a much smaller fraction than have emissions of sulphur dioxide. Dry deposition of sulphur has decreased in proportion to the decline in emissions. A number of suggestionshave been made which offer possible explanations for this non-linearity between emissions and wet deposition. In this paper amodel of the processing of sulphur dioxide by aqueous phase cloudchemistry in a cloudy boundary layer is presented. This work doesnot simulate all the details of the mechanisms by which sulphate is incorporated into precipitation. It does, however, explorethe non-linearity of this oxidation process. It is shown that theoxidation of sulphur dioxide, in these conditions, over the UK isdominated by oxidation by ozone. The rate of sulphate productionis then controlled by the availability of the one basic trace gasin the atmosphere ammonia. Using realistic concentrations of thereacting species this is found to simulate well the observed non-linearity. The model predicts that sulphate and sulphur dioxideconcentrations will be uncorrelated in the cloudy boundary layerbut that ammonium and sulphate will be well correlated. Fieldobservations at a cloudy site in Northern England are consistentwith these predictions.