In order to register agrochemicals in Europe it is necessary to have a detailed understanding of the processes in the environment that break down agrochemicals. The existing framework for environmental assessment includes a consideration of soil water movement and microbial breakdown of products in soil and these processes are relatively understood and represented in models. However the breakdown of agrochemicals by the action of light incident on the soil surface by a process termed photolysis is not so well represented in models of environmental fate.\ud \ud The problem brought by Syngenta (one of the worlds leading agrochemical companies) to the workshop was how to include the effects of light degradation of chemicals into predictive models of environmental fate.\ud \ud Photolysis is known to occur in a very thin layer at the surface of soil. The workshop was asked to consider how the very rough nature of the upper surface of a ploughed field might affect the degradation of chemicals by sunlight. The discussions were directed down two avenues:\ud - firstly to determine how the very small distances over which photolysis occurs might be adequately incorporated into models of transport in soils and,\ud - secondly to consider how the rough surface might modify the illumination of the surface and hence alter degradation.\ud \ud The rate of degradation by photolysis is measured in the laboratory by illuminating a thin, typically about 1 or 2 mm, layer of soil with very strong xenon lamps. The amount of chemical is measured at various intervals and is fitted to a first-order process. Field experiments where the chemical is sprayed on a bare field show evidence of photolysis indicated by biphasic degradation patterns and the presence of breakdown products only formed by photolysis.\ud \ud This report addresses methods for mathematically modelling the action of photolysis on particular relevant chemical species. We start with a general discussion of mechanisms that transport chemicals within soil §2. There is an existing computational model exploited by Syngenta for such modelling and we discuss how this performs and the predictions that can be derived using it §3.\ud The particular mechanism of photolysis is then considered. One aspect of this mechanism that is investigated is how the roughness of the surface of the soil could be adequately incorporated into the modelling. Some results relating to this are presented §4.2. Some of the original experimental data used to derive aspects of the model of photolysis are revisited and a simple model of the process presented and shown to fit the data very well §5.\ud By considering photolysis with a constant diffusion coefficient various analytical results are derived and general behaviour of the system outlined. This simple model is then applied to real field-based data and shown to give very good fit when simply extended to account for the moisture variations by utilising moisture dependent diffusion coefficients derived from the existing computational model §5.3. Some consequences of the simple model are then discussed §6
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