Assessment of Halon-1301 as a groundwater age tracer

Abstract. Groundwater dating is an important tool to assess groundwater resources in regards to their dynamics, i.e. direction and time scale of groundwater flow and recharge, to assess contamination risks and manage remediation. To infer groundwater age information, a combination of different environmental tracers, such as tritium and SF6, are commonly used. However, ambiguous age interpretations are often faced, due to a limited set of available tracers and their individual restricted application ranges. For more robust groundwater dating multiple tracers need to be applied complementarily and it is vital that additional, groundwater age tracers are found to ensure robust groundwater dating in future. We recently suggested that Halon-1301, a water soluble and entirely anthropogenic gaseous substance, may be a promising candidate, but its behaviour in water and suitability as a groundwater age tracer had not yet been assessed in detail. In this study, we determine Halon-1301 and infer age information in 17 New Zealand groundwaters and various modern (river) water samples. The samples are simultaneously analysed for Halon-1301 and SF6, which allows identification of issues such as contamination of the water with modern air during sampling. Water at all analysed groundwater sites have also been previously dated with tritium, CFC-12, CFC-11 and SF6, and exhibit mean residence times ranging from modern (close to 0 years) to over 100 years. The investigated groundwater ranged from oxic to highly anoxic, and some showed evidence of CFC contamination or degradation. This allowed us to make a first attempt of assessing the conservativeness of Halon-1301 in water, in terms of presence of local sources and its sensitivity towards degradation etc., which could affect the suitability of Halon-1301 as groundwater age tracer. Overall we found Halon-1301 reliably inferred the mean residence time of groundwater recharged between 1980 and 2014. Where direct age comparison could be made 71% of mean age estimates for the studied groundwater sites were in agreement with ages inferred from tritium and SF6 (within ± 2 years). The remaining (anoxic) sites showed reduced concentrations of Halon-1301 along with even further reduced concentrations of CFCs. The reason(s) for this need to be further assessed, but are likely to be caused by sorption or degradation of the compounds. Despite some groundwater samples showing evidence of contamination from industrial or agricultural sources via elevated CFC concentrations, no sample indicated significantly elevated concentration of Halon-1301, which may indicate a lack of local anthropogenic or geologic sources of Halon-1301 contamination.