A compact tritium enrichment unit for large sample volumes with automated re-filling and higher enrichment factor.

Tritium (3H) in natural waters is a powerful tracer of hydrological processes, but its low concentrations require electrolytic enrichment before precise measurements can be made with a liquid scintillation counter. Here, we describe a newly developed, compact tritium enrichment unit which can be used to enrich up to 2L of a water sample. This allows a high enrichment factor (>100) for measuring low 3H contents of <0.05TU. The TEU uses a small cell (250mL) with automated re-filling and a CO2 bubbling technique to neutralize the high alkalinity of enriched samples. The enriched residual sample is retrieved from the cell under vacuum by cryogenic distillation at -20°C and the tritium enrichment factor for each sample is accurately determined by measuring pre- and post- enrichment 2H concentrations with laser spectrometry.

Measurement of extremely (2) H-enriched water samples by laser spectrometry: application to batch electrolytic concentration of environmental tritium samples.

RATIONALE: Natural water samples artificially or experimentally enriched in deuterium ((2) H) at concentrations up to 10,000 ppm are required for various medical, environmental and hydrological tracer applications, but are difficult to measure using conventional stable isotope ratio mass spectrometry. METHODS: Here we demonstrate that off-axis integrated cavity output (OA-ICOS) laser spectrometry, along with (2) H-enriched laboratory calibration standards and appropriate analysis templates, allows for low-cost, fast, and accurate determinations of water samples having δ(2) HVSMOW-SLAP values up to at least 57,000 ‰ (~9000 ppm) at a processing rate of 60 samples per day. RESULTS: As one practical application, extremely (2) H-enriched samples were measured by laser spectrometry and compared to the traditional (3) H Spike-Proxy method in order to determine tritium enrichment factors in the batch electrolysis of environmental waters. Highly (2) H-enriched samples were taken from different sets of electrolytically concentrated standards and low-level (<10 TU) IAEA inter-comparison tritium samples, and all cases returned accurate and precise initial low-level (3) H results. CONCLUSIONS: The ability to quickly and accurately measure extremely (2) H-enriched waters by laser spectrometry will facilitate the use of deuterium as a tracer in numerous environmental and other applications. For low-level tritium operations, this new analytical ability facilitated a 10-20 % increase in sample productivity through the elimination of spike standards and gravimetrics, and provides immediate feedback on electrolytic enrichment cell performance. Copyright © 2016 John Wiley & Sons, Ltd.