Sample storage bottle lids and threads were soaked overnight in 2N reagent grade HCl, then filled with 1N reagent grade HCl to be heated in an oven at 60 degrees C overnight, inverted, heated for a second day, and rinsed 5X with pure distilled water. The bottles were then filled with trace metal clean dilute HCl (~0.01N HCl) and again heated in the oven for one day on either end. Clean sample bottles were emptied, and double-bagged prior to rinsing and filling with sample.

Trace metal-clean seawater samples were collected using the U.S. GEOTRACES sampling system consisting of 24 Teflon-coated GO-FLO bottles that had been pre-rinsed with a 24+ hour treatment of filtered surface seawater at the beginning of the cruise (see Cutter & Bruland, 2012 for more information on the sampling system). At each station, the bottles were deployed open and tripped on ascent at 3 m/min. On deck, the bottles were kept in a trace metal clean sampling van over-pressurized with HEPA-filtered air, except immediately prior to and following deployments, in which cases they were covered on both ends with shower caps to avoid deck contamination.

During sampling in the clean van, the GO-FLO bottles were pressurized to ~0.4 atm with HEPA-filtered air, and their spigots were fitted with an acid-cleaned piece of Bev-a-Line tubing that fed into an Acropak-200 Supor capsule filter (0.2 um pore size made of polyethersulfone). Before use, this filter had been filled with filtered surface seawater that had been acidified to pH 2 with trace metal clean HCl and left overnight to rinse. Before collecting any subsamples, at least 500 mL of seawater was passed through the filter (while eliminating air bubbles in the capsule reservoir). Subsamples were taken into acid-cleaned (see above) Nalgene HDPE bottles after a triple rinse with the sample. Acropak filters were used for at most 3 casts before a new filter was used, and they were stored empty in a refrigerator while not in use. GEOFish surface samples were taken using an all-plastic "towed fish" pumping system as described in Bruland et al. 2005 at approximately 3 m depth and were subsampled identically.

All samples were acidified back in the Boyle laboratory at 2 mL per liter seawater (pH ~2) with trace metal clean 6N HCl.

Samples were analyzed at least 1 month after acidification over 9 mass spectrometry sessions by the method of Reuer et al. (2003) as modified by Boyle et al. (2012) and further slightly modified as noted in the following.

Double magnesium hydroxide co-precipitation followed by anion exchange purification:
This method is a slight adaptation of the isotope ratio method of Reuer et al., 2003, which was further modified as described by Boyle et al. (2012) and as slightly revised as described below. The method includes low-blank pre-concentration by Mg(OH)2 co-precipitation and isotope ratio analysis on a GV/Micromass IsoProbe multicollector ICPMS using a 50 uL/min nebulizer aspirated into an APEX/SPIRO desolvator, using post-desolvator trace N2 addition to boost sensitivity.

Nalgene polypropylene separatory funnels (1000mL) and Corning 50 ml conical centrifuge vials were cleaned by heated submersion for 2 days at 60˚C in 1N reagent grade HCl, followed by a bulk rinse and 4X individual rinse of each vial with pure distilled water. Each vial was then filled with trace metal clean dilute HCl (~0.01N HCl) and heated in the oven at 60 degrees C for one day on either end. Centrifuge vials were kept filled until just before usage.

The separatory funnels were rinsed with distilled water after each use and then filled with high-purity distilled water spiked with high-purity HCl (final concentration ~0.01N) between uses.

1000 mL polypropylene separatory funnels (Nalgene) were weighed, rinsed once with seawater sample and filled with 200-500 ml of sample. Mg(OH)2 coprecipitation was induced by minimal addition of high-purity ammonia solution and mixing (typically <12 uL ammonia per 1 mL seawater sample). The separatory funnels were left to settle overnight, then agitated to move the precipitate down the funnel walls. After complete settling, the precipitate was drawn from the bottom of the funnels into a 50 mL conical centrifuge tubes. The solution/precipitate mix was centrifuged and the solution siphoned off, and then the precipitate was dissolved in a minimal amount of high-purity 6N HCl before undergoing another ammonia addition and Mg(OH)2 coprecipitation. The mixture was centrifuged and the overlying solution was siphoned.

Eichrom AG-1x8 resin was cleaned by three batch rinses with 6N trace metal clean HCl for a ~12 hours on a shaker table, followed by multiple washes with distilled water until the pH of the solution was above 4.5. Resin was stored at room temperature in the dark until use.

The precipitate was dissolved in ~1 ml of high purity 1.1M HBr. The amount of solution was adjusted depending on the Si concentration of the seawater sample; if too little solution is used, the Si precipitates as a gel, impeding the column separation. The resin in the column was first cleaned with 6M HCl, equilibrated with 1.1M HBr, and then sample was loaded onto the column. The column was then washed with 1.1M HBr followed by 2M HCl and then eluted with 6M HCl. The samples in a 5 ml Savillex PTFE vial were then taken to dryness on a hotplate in a recirculating filtered air fume hood, and stored sealed until analysis.

Just before analysis, samples were dissolved for several minutes in 0.2M HNO3 and spiked with an appropriate amount of Tl for mass fractionation correction. IsoProbe multicollector ICPMS Faraday cups were used to collect on 202Hg, 203Tl, 205Tl, 206Pb, 207Pb, and 208Pb. An Isotopx Daly detector with a WARP filter was used to collect on 204Pb+204Hg. This Daly detector is a revised version that eliminates a reflection problem with the electronic circuitry of the previous version. We do not report 206Pb/204Pb data for samples run on the old Daly detector. Because the deadtime of the Daly detector varied from day to day, we calibrated deadtime on each day by running a standard with known 206Pb/204Pb at a high 204 count rate. The counter efficiency drifts during the course of a day, so we established that drift by running a standard with known 206Pb/204Pb (and a 204 count rate comparable to the samples) every five samples. Tailing from one Faraday cup to the next was corrected by the 209Bi half-mass method as described by Thirlwall (2000).

On each analytical date, we calibrated the instrument by running NBS981 and normalized measured sample isotope ratios to our measured raw NBS981 isotope ratios to those established by Baker et al. (2004). Using this method for 45 determinations of an in-house standard (BAB) shows that for samples near the upper range of the Pb signals shown for samples (~1V), 206Pb/207Pb and 208Pb/207Pb can be reproduced to ~200ppm. Low-level samples will be worse than that, but generally better than 1000 ppm in this data set. Because of the drift uncertainty in the Daly detector, 206Pb/204Pb for samples in the mid-to-upper range of sample concentrations will be at best reproducible to ~500 ppm.

We have intercalibrated Pb isotope analyses with two labs as reported in Boyle et al. (2012). Since that report, two more labs have added intercalibration data. The outcome of that intercalibration suggests that the accuracy of our measurements approaches the analytical reproducibility we note above.

About 25% of the samples were analyzed by Yolanda Echegoyen, and the other 75% by Abigail Noble.

References:
Baker, J., D. Peate, T. Waight, and C. Meyzena. 2004. Pb isotopic analysis of standards and samples using a 207Pb–204Pb double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS. Chem. Geol. 211:275-303. doi:10.1016/j.chemgeo.2004.06.030

Boyle, Edward A., Seth John, Wafa Abouchami, Jess F. Adkins, Yolanda Echegoyen-Sanz, Michael Ellwood, Russ Flegal, Kyrstin Fornace, Celine Gallon, Steve Galer, Melanie Gault-Ringold, Francois Lacan, Amandine Radic, Mark Rehkamper, Olivier Rouxel, Yoshiki Sohrin, Claudine Stirling, Claire Thompson, Derek Vance, Zichen Xue, Ye Zhao. 2012. GEOTRACES IC1 (BATS) Contamination-Prone Trace Element Isotopes Cd, Fe, Pb, Zn, (and Mo) Intercalibration, Limnol. Oceanogr. Methods 10:653-665. doi:10.4319/lom.2012.10.653

Reuer, M.K., Boyle, E.A., Grant, B.A. 2003. Lead isotope analysis of marine carbonates and seawater by multiple collector ICP-MS. Chemical Geology 200: 137-153. doi:10.1016/S0009-2541(03)00186-4

Thirlwall, M.F., 2001. Inappropriate tail corrections can cause large inaccuracy in isotope ratio determination by MC-ICP- MS. J. Anal. At. Spectrom. 16, 1121–1125. doi:10.1039/B103828C

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