A single vs. double spike approach to improve the accuracy of 234Th measurements in small-volume seawater samples

234Th is a particle-reactive radionuclide widely used to trace biogeochemical oceanic processes occurring over short timescales. During the last few years, small-volume techniques based on the co-precipitation of 234Th with MnO2 coupled with beta-counting have been developed as an alternative to large volume gamma-spectrometric techniques. Here a procedure has been developed to enhance quantitative measurement of 234Th in MnO2 precipitates. The main objectives were to obtain a purified Th fraction for beta-counting and to determine the chemical recovery of 234Th using Th spikes and alpha-spectrometry as an alternative to ICP-MS based methods. Two variations of the procedure are presented. In the first “1 spike” method a 230Th tracer is added to the sample prior to precipitation of MnO2, and UTEVA® extraction chromatography is used to obtain a NdF3(Th) purified source that can be used for both beta-counting of 234Th and alpha-spectrometry of 230Th. In the “2 spike” method a 230Th spike is added and the MnO2(Th) precipitate is directly beta-counted for 234Th and subsequently spiked with 228Th or 229Th prior to UTEVA® purification and alpha-spectrometry. The results confirm the need to process small-volume seawater samples for 234Th measurement in presence of a yield tracer, and show that both the 1 spike and 2 spike methods allow an accurate and precise determination of 234Th (relative percent difference, RPD, between expected and mean measured value < 1%; CV between replicate samples < 3%). Our work also suggests that, although the combined analytical uncertainty on total 234Th measurements accomplished with both versions of the NdF3 procedure is promising ( 6% for 2-L samples), the precision of the 234Th flux estimation will ultimately depend on the degree of disequilibrium between 234Th and 238U.