Methodological advances for measuring low-level radium isotopes in seawater

A new approach for quantifying radium isotopes in seawater was developed in advance of the international GEOTRACES program, which has the goal of identifying processes and quantifying fluxes that control the distribution of trace elements and isotopes (TEIs) in the ocean. High-resolution water column samples were collected via a commercially available in situ pump modified to accept multiple filter media including a manganese-oxide (MnO2) impregnated acrylic cartridge for extracting dissolved radionuclides from seawater. The modifications mitigated prefilter clogging and allowed for up to 1,800 L filtrations in 4 h of pumping. Different MnO2 cartridge preparation methods were investigated to achieve maximum radium (Ra) extraction efficiency under high sample flow rates. Full-ocean depth profiles were measured for short-lived radium isotopes (Ra-223 and Ra-224) in shipboard laboratories using a delayed coincidence alpha scintillation counter (RaDeCC). Samples were reanalyzed 4 weeks and 2 months after collection for Th-228 and Ac-227 to correct for supported Ra-224 and Ra-223, respectively. Finally, the cartridges were measured on a gamma-ray spectrometer for the long-lived radium isotopes (Ra-226 and Ra-228). Parallel 20 L samples at each pumping depth were collected from Niskin bottles and analyzed via alpha scintillation for Ra-226 to determine radium extraction efficiencies for the cartridges. These modified methods will allow for increased sample throughput, and hence higher spatial resolution for radium isotopes in the ocean. Such resolution will greatly improve the determination of oceanic vertical and horizontal mixing rates over small and large scales, which in turn can be used to calculate fluxes of TEIs into the ocean.