Halon-1301 – further evidence of its performance as an age tracer in New Zealand groundwater

Abstract. We recently discovered a new groundwater age tracer, Halon-1301, which can be used to date groundwater recharged after the 1970s. In a previous study, we showed that Halon-1301 reliably inferred groundwater age at the majority of groundwater sites studied. At those sites, ages inferred from Halon-1301 agreed with those inferred from SF₆ and tritium, two reliable widely applied groundwater age tracers. A few samples, however, showed reduced concentrations of Halon-1301, preventing meaningful age interpretation from its concentration. These reduced concentrations were likely a result of degradation or retardation of Halon-1301 in the aquifer. However, we could not provide full evidence for this due to the limited number of groundwater samples analysed (18 in total). In this study, we assess the potential of Halon-1301 as a groundwater age tracer for a larger dataset of groundwater samples under specific groundwater conditions, including highly anoxic young groundwater which can significantly degrade Halon-1301, to gain more information on the magnitude of occurrence and the causes of reduced Halon-1301 concentrations.

In this study, we analysed 302 groundwater samples for Halon-1301, SF₆, tritium and the CFCs CFC-11, CFC-12 and CFC-113. Comparison of age information inferred from the concentrations of these tracers allows assessment of the performance of Halon-1301 compared to other well established and widely used age tracers. The samples are taken from different groundwater environments in New Zealand and include anoxic and oxic waters with mean residence times ranging from < 2 years to over 150 years (tritium-free).

The majority of assessed samples have reduced or elevated concentrations of CFCs, which makes it impossible to infer a reliable age using the CFCs for these samples. Halon-1301, however, reliably infers ages for CFC-contaminated waters. Three other groundwater samples were found to have elevated SF₆ concentrations (contaminated). Again, at these SF₆-contaminated sites, ages inferred from Halon-1301 agree with ages inferred from tritium. A few samples (14 sites) exhibit reduced concentrations of Halon-1301, which result in elevated inferred Halon-1301 ages in comparison to those inferred from SF₆, tritium and/or CFC-113. Assessment of the groundwater environment at these sites gives further insight into the potential causes of Halon-1301 reduction in groundwater.

Overall, Halon-1301 gives age information that matches ages inferred from SF₆ and/or tritium for the majority (97 %) of the assessed groundwater sites. These findings suggest that Halon-1301 is a reasonably reliable groundwater age tracer, and is in particular significantly more reliable than the CFCs, which may have contamination and degradation problems. Halon-1301 thus has potential to become a useful groundwater age tracer where SF₆ and the CFCs are compromised, and where additional independent tracers are needed to constrain complex mixing models.