Sampling and Analytical Methodology:
Water samples were collected with a Sea-Bird Electronics CTD carousel fitted with 24 10-liter PVC Niskin bottles. The carousel was lowered from the ship with steel wire. Niskin bottles caps were held together with rubber tubing. After collection seawater was drained with Teflon-lined TygonTM tubing and filtered through Pall AcropakTM 500 filters on deck (gravity filtration, 0.8/0.45 µm pore size) into Fisher I-Chem series 300 LDPE cubitainers. Approximately 9-10 L was collected per desired depth. Prior to the cruise, the tubing, filters and cubitainers were cleaned by immersion in 1.2 M HCl (Fisher Scientific Trace Metal Grade) for 4-5 days. Once filtered, samples were adjusted to a pH ~2 with ultra-clean 6 M HCl (Tama Chemicals, TAMAPURE-AA-100 grade), double-bagged and stored at room temperature as packaged until analysis.

In the on-shore laboratory, samples were weighed to determine sample size, taking into account the weight of the cubitainer and of the acid added at sea. Four to five liters of the original sample was used for Th/Pa analysis, the remaining sample kept as archive. Then weighed aliquots of the artificial isotope yield monitors 229Th (20 pg) and 233Pa (0.5 pg) and 15 mg dissolved Fe were added to each sample. After allowing 1 day for spike equilibration, the pH of each sample was raised to 8-8.5 by adding ~10 mL of concentrated NH4OH (Fisher Scientific OPTIMA grade) which caused iron (oxy)hydroxide precipitates to form. This precipitate was allowed to settle for 1-2 days before the overlaying seawater was siphoned off. The Fe precipitate was transferred to centrifuge tubes for centrifugation and rinsing with Milli-Q H2O (>18 MO) to remove the major seawater ions. The precipitate was then dissolved in 16 M HNO3 (Fisher Scientific OPTIMA grade) and transferred to a Teflon beaker for a high-temperature (180-200°C) digestion with HClO4 and HF (Fisher Scientific OPTIMA grade) on a hotplate in a HEPA-filtered laminar flow hood. After total dissolution of the sample, another precipitation of iron (oxy)hydroxide followed and the precipitate was washed with Mill-Q H2O, centrifuged, and dissolved in 12 M HCl for a series of anion-exchange chromatography using 6 mL polypropylene columns each containing a 1 mL bed of Bio-rad resin (AG1-X8, 100-200 mesh size) and a 45 µm porous polyethylene frit. The final column elutions were dried down at 180°C in the presence of 2 drops of HClO4 and taken up in approximately 1 mL of 0.16 M HNO3/0.026 M HF for mass spectrometric analysis.

Concentrations of 232Th, 230Th and 231Pa were calculated by isotope dilution using nuclide ratios determined on a VG Elemental AXIOM Single Collector Magnetic Sector ICP-MS with a Resolving Power of ~400 to ensure the highest sensitivity. All measurements were done using a peak jumping routine in ion counting mode. A solution of SRM129, a natural U standard, was run to determine the mass bias correction (assuming that the mass fractionation for Th and Pa are the same as for U). Each sample measurement was bracketed by measurement of an aliquot of the run solution, used to correct for the instrument background count rates on the masses measured. To correct for potential tailing of 232Th into the minor Th and Pa isotopes, beam intensities were measured at the half masses above and below each mass for 230Th, 231Pa, and 233Pa. Tailing under each minor isotope was estimated as the log mean intensity of the half masses on either side of each minor isotope.

Water samples were analyzed in batches of 10-12. Procedural blanks were determined by processing 4-5 L of Milli-Q water in an acid-cleaned cubitainer acidified to pH ~2 with 6 M HCl as a sample in each batch. An aliquot of an intercalibrated working standard solution of 232Th, 230Th and 231Pa, SW STD 2010-1 referred to by Anderson et al. (2012), was added to a separate cubitainer with 5 L of Milli-Q water (acidified to pH 2) and also processed like a sample in each batch. Total procedural blanks for 232Th, 230Th, and 231Pa ranged from 7.1-24.3 pg, 0.8-1.6 fg, and 0.02-0.2 fg respectively. One batch had an anomalously high 232Th blank of 140 pg (with 230Th and 231Pa in the reported range). Application of this blank correction to the analyzed SW STD caused an anomalously low estimate of its 232Th concentration (approximately 990 ± 15 pg/g). From this we concluded the blank was due to random contamination of the procedural blank and it should not be used to blank-correct samples. Instead, we determined what magnitude of blank correction would be necessary for the analyzed SW STD to achieve the intercalibrated concentration. This was 12 pg 232Th, which is close to the average blank value measured throughout the course of this project.

Further details on sampling and analysis are given by Anderson et al. (2012).