Assessing the applicability of global CFC and SF(6) input functions to groundwater dating in the UK

Chlorofluorocarbons (CFCs) and sulphur hexafluoride (SF(6)) are increasingly being used to date recent groundwater components. While these trace gases are generally well-mixed in the atmosphere, there is evidence that local atmospheric excesses (LAEs) exist in some areas of the world, primarily associated with urbanisation and thereby affecting the interpretation of data derived from groundwater studies. Since the soil acts as a low-pass filter for atmospheric trace gas fluctuations, the possible existence of LAEs in the UK has been investigated by measuring the mixing ratios of CFC-11, CFC-12 and SF(6) in soil gases from sites within the UK's two largest cities (London and Birmingham) and a smaller urban area, Bristol. While there was some evidence of excesses, most of the measured mixing ratios for CFC-12 and SF(6) were less than 10% above the current northern hemisphere atmospheric mixing ratio (NH-AMR) values. CFC-11 was more variable, but usually less than 20% above the NH-AMR value. Surface waters were also investigated as possible short-term archives of trace-gas information but were much less consistent in performance. While the lack of significant current LAEs for SF(6) can justifiably be extrapolated to past decades, different global emission patterns mean that this is much harder to justify for the CFCs. Nevertheless, in the absence of further evidence it is concluded that the use of CFC and SF(6) input functions based on the NH-AMR curves is generally justified for the UK, with the proviso that urban groundwater investigations should not rely on the CFCs as age tracers.