Comparative evaluation of 2 H- versus 3 H-based enrichment factor determination on the uncertainty and accuracy of low-level tritium analyses of environmental waters

Analysis of low-level tritium ( H) in environmental waters requires pre-concentration using electrolytic enrichment prior to decay counting. Accurate and precise electrolytic enrichment factors (EF) are required to determine the sample's environmental H concentration. Two methods are used to determine EFs: i) the Spike Proxy Method (SPM) and ii) the Deuterium Method (DM) with each having several modalities. We conducted a comparative assessment of four EF strategies using 250 mL and 500 mL electrolytic enrichment of three low-level H proficiency water standards (0.5-7 TU) to see which strategy gave the most accurate H results based on z- and Zeta-scores. Our comparative evaluation revealed the DM offers consistently superior H results, with more precise EF determinations compared to the three SPM strategies. The DM gave the best z-scores with an EF relative combined uncertainty of about 0.5‰ and a negligible contribution to the overall uncertainty budget due to the EF determination. Moreover, the DM can improve productivity by eliminating the spike and gravimetric procedures from routine analyses and can give rapid cell enrichment performance feedback prior to decay counting. We recommend low-level tritium laboratories consider adopting the DM into their H sample enrichment and analysis operations.