Clean seawater samples were collected using a GEOTRACES CTD referred to as GT-C/12L GoFlo, and also from the Super-GeoFISH towed surface vehicle. For more information, see the GP17-OCE cruise report.
Water samples were filtered through pre-cleaned, 0.2-micrometer (µm) Pall Acropak Supor filter capsules as described elsewhere (e.g., Cutter et al., 2014; Hatta et al., 2015). Filtered water was collected in 125-milliliter (mL) HDPE bottles (Nalgene) that had been precleaned by soaking in hot 1.2 M HCl (reagent grade) for at least 8 hours with subsequent thorough rinsing with ultrapure distilled deionized water (Barnstead E-pure).
Dissolved gallium (Ga) was determined by isotope dilution ICP-MS using a ThermoFisher Element XR operated in low resolution (Gilbert et al., 2023). Samples (20-30 mL) were concentrated using a SeaFAST system; a dilute HF rinse was used for column cleaning between samples. An enriched isotope spike of known concentration was prepared using purified enriched 71Ga (99.8%), obtained from Oak Ridge National Laboratories. The substantial sample pre-concentration of this method allows for ICP-MS analysis using medium resolution which eliminates isobaric interferences including doubly charged 138Ba with 69Ga.
The reagent blank contribution to the dissolved Ga analysis is typically 0.6 picomoles per kilogram (pmol/kg) and the detection limit (based on 3 times the standard deviation of the blank) is 0.3 pmol/kg. Repeated runs of US GEOTRACES intercalibration samples (GS and GD), in-house reference solutions, and cast overlap samples suggest a precision of ± 4%; the limit of detection for Ga was 1.5 pmol/kg. Recovery of the method, as determined by repeated analysis of a spiked and unspiked seawater sample was 100 ± 7%.
See attached Intercalibration Report for additional information.