Sampling and Analytical Methodology:
1. Sampling:
Size-fractionated particles were collected using McLane Research in-situ pumps (WTS-LV) that had been modified to accommodate two flowpaths (Lam and Morris Patent pending). The wire-out was used to target depths during deployment, and a self-recording Seabird 19plus CTD deployed at the end of the line and RBR data loggers attached to three of the eight pumps were used to correct for actual depths during pumping.

Filter holders used were 142 mm-diameter "mini-MULVFS" style filter holders with two stages for two size fractions and multiple baffle systems designed to ensure even particle distribution and prevent particle loss (Bishop et al. 2012). One of two filter holder/flowpaths was loaded with a 51µm Sefar polyester mesh prefilter followed by paired 0.8 µm Pall Supor800 polyethersulfone filters. Each cast also had "dipped blank" filters deployed. These were the full filters sets (prefilter followed by paired Supor filters) sandwiched within a 1 µm polyester mesh filter, loaded into perforated polypropylene containers, attached with plastic cable ties to a pump frame, and deployed. Dipped blank filters were exposed to seawater for the length of the deployment and processed and analyzed as regular samples, and thus functioned as full seawater process blanks. We analyzed half portions of the top and bottom filters from the "dipped" blank from 1 or more depths for 7 stations.

All filters and filter holders were acid leached prior to use according to methods recommended in the GEOTRACES sample and sample-handing Protocols (Geotraces 2010).

2. Analysis:
The Supor filters were subsampled in an on-shore laboratory at the Woods Hole Oceanographic Institution and shipped to the participating labs for Pa/Th analysis. Twenty-five to 50% of the paired Supor filters, representing 55-350 L of seawater, were used for Pa/Th analysis. Analyses were similar but differed slightly for the Lamont-Doherty Earth Observatory, WHOI and the University of Minnesota. Details of each groups methodologies can be found in reports by Anderson et al. (2012), Auro et al. (2012) and Shen et al. (2002, 2003, 2012), respectively. Below we give a typical procedure used at L-DEO for illustrative purposes.

2.1 L-DEO procedures

Filters were folded into 60 mL Teflon jars and weighed aliquots of the artificial isotope yield monitors 229Th (1 pg) and 233Pa (0.3-0.4 pg) and 7-8 mg dissolved Fe were added to each sample. Filters were first heated in ~5 mL 8 N HNO3 for 1-2 hours at 150°C, then 4-5 mL HClO4 was added and heat was increased to 200°C until dense white fumes appeared for ~10-20 min. The heat was then reduced to 180°C and the samples were covered with a Teflon watch cover. After 1-4 hrs, oxidation of the Supor material accelerated, sometimes producing a foam. A foamed sample would be allowed to cool, and re-heated after the beaker walls and watch cover were washed with small amounts of HNO3 or Milli-Q water. When the Supor material was largely broken down, the watch covers were removed and HF was added in 2 aliquots of ~10-15 drops in between reheating until attaining dense HClO4 fumes for at least 10 min.

After total dissolution of the sample, the sample-HClO4 residue was taken up in dilute HCl, and transferred to 50 mL centrifuge tubes with water rinses. Ten to 20 drops of NH4OH were added to raise pH to 8-8.5 when iron (oxy)hydroxide precipitated. This precipitate was then centrifuged, decanted, washed with Milli-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 (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. All acids and bases used were Fisher Chemical OPTIMA grade.

Concentrations of 232Th, 230Th and 231Pa were calculated by isotope dilution using nuclide ratios determined on a Thermo Scientific Element XR Inductively-couple plasma mass spectrometer (ICP-MS) in low resolution. 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.

2.2 Blank determinations

In addition to laboratory procedural blanks (reagents/labware blanks) and periodic measurements of an intercalibrated working standard solution of 232Th, 230Th and 231Pa, SW STD 2010-1 referred to by Anderson et al. (2012), the participating labs also analyzed a number (n = 23) of "dipped blank" filters, mentioned above, to determine the total blank, associated with the sample collection and handling in addition to the laboratory procedure.

For better statistics, we pooled all procedural blank corrected "dipped" blanks (n = 23) to determine filter blank corrections. "Dipped" filter blanks for 232Th, 230Th, and 231Pa were from 156 ± 57 pg, 5.8 ± 2.0 fg, and 0.12 ± 0.04 fg, respectively. Total blanks were < 10% of the measured isotope amounts, except shallower than 200 m water depth, where blanks could be on the order of 50% of the measured 230Th and 231Pa.

We define the limit of detection as 3 times the standard deviation in the measured "dipped" blanks (170 pg 232Th, 6.0 fg 230Th, and 0.13 fg 231Pa). There were 5 samples for which 231Pa was considered below detection, and all other samples were above the cited limits.

Further details on analysis of seawater particulate radionuclides are given by Anderson et al. (2012).

ThPa_all_GT10-11_v4.csv