Sampling and Analytical Methodology - BATS station:
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 were equipped with nylon-coated closure springs and Viton O-rings. After collection seawater was filtered by in-line filtration (47 mm 0.45 µm pore diameter Supor polysulfone membranes in acid cleaned Teflon filter holders) from pressurized Niskin bottles. Bottles were pressurized at 8-10 psi (54-70 kPa) with a system that distributed filtered air from a compressor via a manifold to each bottle through a fitting placed in its air vent. Each distribution line from the manifold was fitted with a valve so that each bottle could be pressurized or vented independently, while still allowing for the possibility to simultaneously filter all the bottles. Pressurized bottles were held closed with Irwin Quick-Grip bar clamps spanning the endcaps. No attempt was made to evaluate the blank contributed by the pressurization scheme. Filtered water was collected in low-density polyethylene cubitainers (10 liter volume; Hedwin Corp.). 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 (Fisher Scientific OPTIMA grade) and were double bagged for storage at room temperature 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. 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 (checked with pH paper) by adding 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 Bio-rad resin (AG1-X8, 100-200 mesh size) and a 45 µm porous polyethylene frit (for details see Anderson et al., 2012). 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. Total procedural blanks for 232Th, 230Th, and 231Pa ranged from 63-93 pg, 12.1-12.4 fg, and 1.9-2.4 fg respectively.

Sampling and Analytical Methodology - SAFe station:
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 were equipped with nylon-coated closure springs and Viton O-rings. 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 low-density polyethylene cubitainers (1 gallon volume; Hedwin Corp.). Approximately 4 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 (Fisher Scientific OPTIMA grade) and were double bagged for storage at room temperature 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. 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 (checked with pH paper) by adding 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 bed of Bio-rad resin (AG1-X8, 100-200 mesh size) and a 45 µm porous polyethylene frit (for details see Anderson et al., 2012). 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 3-4 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 4 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 19-24 pg, 1.4-2.8 fg, and 0.4 fg respectively.

To test the overall method, 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 3 L of Milli-Q water (acidified to pH 2) and also processed like a sample.

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

GT_IntCal_ThPa.csv