Determination of Ultratrace Level ¹³⁵Cs and ¹³⁵Cs/¹³⁷Cs Ratio in Small Volume Seawater by Chemical Separation and Thermal Ionization Mass Spectrometry

The atomic ratio of ¹³⁵Cs/¹³⁷Cs is a powerful fingerprint for distinguishing the source terms of radioactive contamination and tracing the circulation of water masses in the ocean. However, the determination of the ¹³⁵Cs/¹³⁷Cs ratio is very difficult due to the ultratrace level of ¹³⁵Cs (<0.02 mBq/m³) and ¹³⁷Cs (<2 Bq/m³) in the ordinary seawater samples. In this work, a sensitive method was developed for determination of ¹³⁵Cs concentration and ¹³⁵Cs/¹³⁷Cs ratio in seawater using chemical separation combined with thermal ionization mass spectrometry (TIMS) measurement. Cesium was first preconcentrated from seawater using ammonium molybdophosphate-polyacrylonitrile column chromatography and then purified using cation exchange chromatography to remove the interferences. With this method, decontamination factors of 6.0 × 10⁶ for barium and 1800 for rubidium and a chemical yield of more than 60% for cesium were achieved. By using glucose as an activator, the ionization efficiency of cesium was significantly improved to 50.6%, and a constant high current of Cs⁺ (20 V) can be maintained for more than 180 min, which ensures sensitive and reliable measurement of low level ¹³⁵Cs and ¹³⁷Cs. Detection limits of 4.0 × 10^–17 g/L for both ¹³⁵Cs and ¹³⁷Cs for 200 mL seawater were achieved, which enables the accurate determination of ¹³⁵Cs concentration and ¹³⁵Cs/¹³⁷Cs ratio in a small volume of seawater samples (<200 mL). The developed method has been validated by analysis of seawater reference material IAEA-443. Seawater samples collected from the Greenland Sea, Baltic Sea, and Danish Straits have been successfully analyzed for ¹³⁵Cs concentrations and ¹³⁵Cs/¹³⁷Cs ratios, and the results showed that ¹³⁵Cs concentrations in the seawater of the Baltic Sea is much higher than that in the Greenland Sea, which is attributed to the high deposition of Chernobyl accident derived radiocesium in the Baltic Sea region.