Chlorine Transport in a Small Catchment

It is generally known that chlorine compounds are ubiquitous in the environment. In recent years, researchers have concluded that chlorine is part of a biogeochemical cycle in soil involving an interaction between chloride (Clin) and organic-matter-bound chlorine (Clorg). Even though there is indisputable evidence that Clorg is formed naturally, there are actually few simultaneous field measurements of Clorg and Clin. Previously stipulated conclusions with respect to underlying processes and transport estimates have thus been deduced from rather few concentration measurements. It is well known that the chemical composition in soil and runoff water varies widely over time and in space. The main objective of the thesis is to investigate the on-site variation of Clin, Clorg and VOCls in runoff water in order to (i) construct a chlorine budget on a catchment scale to visualize the relative contribution of Clin, Clorg, and VOCls; (ii) more reliably estimate how and why the concentrations of Clin, Clorg, and VOCls in runoff water vary; and (iii) analyze the influence of various environmental variables on the transport. The present thesis highlights the on-site variation and fluxes of Clin, Clorg, and VOCls in a small forested catchment in southeast Sweden. Field flux data collected during a twoyear period and a constructed overall chlorine budget were evaluated. The results show that the storage is dominated by Clorg whereas the transport is dominated by Clin and that the storage is far much larger than the transport. Still, input and output is nearly in balance for all investigated chlorine species. It is interesting to note that these observations resemble observations made for carbon, nitrogen and sulphur; i.e. a large storage, small transport, complex biogeochemical cycling processes at hand but still close to steady state conditions with respect to output-input balances. It appears as if topsoil acts as a sink for Clin, while deeper soil acts as a source of Clin. In addition, the results of the thesis suggest that on-site variation depend on seasonal variations. These variations are to some extent caused by water discharge, but also by water residence time, internal chlorination/dechlorination of organic matter, and different soil water origins. Furthermore, both a net retention and a net release of Clin were observed in laboratory studies. The study indicates that simultaneous retention and release of Clin takes place in soil, which probably has an impact on the Clin import and export fluxes. Finally, the results show for the first time that tetrachloromethane can be emitted from laboratory incubated soil, and that soil nitrogen concentrations has quite different effects on the emission rates of chloroform and tetrachloromethane. The results of the thesis, considered together with results of previous research, suggest that the turnover of chlorine in soils is extensive and potentially important for chlorine cycling in general, which must be taken into account if one wishes to increase the understanding of the cycling of anthropogenic chlorine compounds in the environment.