Dataset: GN01 Particulate Thorium and Protactinium
Deployment: HLY1502

GN01 Particulate Thorium and Protactinium

Principal Investigator:

Robert F. Anderson (Lamont-Doherty Earth Observatory, LDEO)

R. Lawrence Edwards (University of Minnesota Twin Cities, UMTC)

Co-Principal Investigator:

Hai Cheng (University of Minnesota Twin Cities, UMTC)

Martin Q. Fleisher (Lamont-Doherty Earth Observatory, LDEO)

Contact:

Sebastian M. Vivancos (Lamont-Doherty Earth Observatory, LDEO)

Analyst:

Xianglei Li (University of Minnesota Twin Cities, UMTC)

Sebastian M. Vivancos (Lamont-Doherty Earth Observatory, LDEO)

Pu Zhang (University of Minnesota Twin Cities, UMTC)

BCO-DMO Data Manager:

Shannon Rauch (Woods Hole Oceanographic Institution, WHOI BCO-DMO)

Project:

Collaborative Research: U.S. GEOTRACES Arctic Section: Thorium-230, Thorium-232, and Protactinium-231 tracers of trace element supply and removal. (GEOTRACES Arctic Th Pa)

U.S. Arctic GEOTRACES Study (GN01) (U.S. GEOTRACES Arctic)

Deployment Synonyms:

GN01, U.S. GEOTRACES Arctic, 32H120150809

Data URL:

https://www.bco-dmo.org/dataset-deployment/834755/data

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Description

This dataset contains concentrations of size-fractionated particulate thorium and protactinium isotopes (Th-232, Th-230, Pa-231) in seawater collected during the U.S. GEOTRACES Arctic cruise (HLY1502, GN01) on USCGC Healy from August to October 2015. This is compiled data produced by two laboratories with the following associations: Lamont-Doherty Earth Observatory of Columbia University (LDEO) and the University of Minnesota (UMN). All data have been deemed intercalibrated by the International GEOTRACES Standards and Intercalibration (S&I) Committee.

Naming Conventions:
Parameter names in the form such as "Th_232_SPT_CONC_PUMP" are adopted based on a recommendation from the GEOTRACES community (https://www.geotraces.org/parameter-naming-conventions/).

The "small particulate" (SPT) data refers to the particle size class 0.8-51 µm and is sometimes also called the "suspended" size fraction. The "large particulate" (LPT) data refers to particles greater than 51 µm and is sometimes referred to as the "sinking" size fraction. The particulate samples were collected by in-situ pumping over two loaded filter holders/flowpaths. One filter holder/flowpath was loaded with paired 0.8 µm Pall Supor800 polyethersulfone filters behind a 51 µm Sefar polyester mesh prefilter ("Supor-side") and the other filter holder/flowpath was loaded with paired 1 µm Whatman QMA quartz fiber filters behind a 51 µm Sefar polyester mesh prefilter ("QMA-side") (see Xiang and Lam, 2020 for particulate sampling methodology). Analysis of the paired Supor filters represents a particle size class approximating 0.45-51 µm (Bishop et al., 2012), while the top filter alone represents 0.8-51 µm and it is this size class referred to here as the "small particulate" fraction. We measured a select number of top and bottom Supor filters separately for radionuclides and found that the bottom filters had radionuclide levels that were indistinguishable from procedural blanks ("dipped" filter blanks). Therefore, whether or not samples were analyzed as paired Supor filters, or the top Supor filter alone, we infer the "small particulate" data to represent the 0.8-51 µm particle size class or "suspended" size fraction. The "large particulate" data is based on the analysis of the QMA-side 51 µm Sefar polyester mesh prefilters. Only a selection of "large particulate" samples were analyzed and those analyses were all performed at the University of Minnesota (UMN).

Units of Measurement:
Radionuclide concentrations are given as micro-Becquerel (10e-6 Bq, µBq or micro-Bq) per kilogram seawater for Th-230 and Pa-231, and picomole (10e-12 mol, pmol) per kilogram seawater for Th-232. A Becquerel is the SI unit for radioactivity and is defined as 1 disintegration per second. These units are recommended by the GEOTRACES community.

Methods & Sampling

Dataset acquisition description

Sampling Methods at Sea:
Sampling methods at sea followed the GEOTRACES cookbook (Cutter et al., 2017). Large-volume size-fractionated particulate samples were collected using McLane Research in-situ pumps (WTS-LV) that had been modified to accommodate two flowpaths (Lam and Morris, 2013). The wire-out was used to target depths during deployment and both a self-recording Seabird 19plus CTD deployed at the end of the line and an RBR pressure logger attached to the pump at the middle of the line were used to correct for actual depths during pumping. The RBR was used for all casts in the entire cruise, whereas the CTD was only deployed in the northbound leg due to electronic problems.

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 filter holder/flowpath was loaded with paired 0.8 µm Pall Supor800 polyethersulfone filters behind a 51 µm Sefar polyester mesh prefilter ("Supor-side") and the other filter holder/flowpath was loaded with paired 1 µm Whatman QMA quartz fiber filters behind a 51 µm Sefar polyester mesh prefilter ("QMA-side") (see Xiang and Lam, 2020 for particulate sampling methodology). Each cast also had “dipped” filter blanks deployed. These were the full filter sets (prefilter followed by paired Supor or paired QMA 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" filter blanks were exposed to seawater for the length of the deployment, processed and analyzed as regular samples, and thus functioned as full seawater particulate procedural blanks. For the "small particulate" dataset, we analyzed either quarter top (or bottom) Supor filter cuts (LDEO) or eighth paired Supor filter cuts (UMN) from the "dipped" Supor filter blanks from 1 or more depths for nearly every station (18 of 20). For the "large particulate" dataset, UMN analyzed eighth filter cuts from the "dipped" Sefar prefilter blanks from 1 or more depths for every station where samples were selected for analysis (10 of 10).

All filters and filter holders were acid leached prior to use according to methods recommended in the GEOTRACES cookbook (Cutter et al., 2017).

Analytical Methods at LDEO:
Quarter filter cuts of the Supor filters ("small particulate", 0.8-51 µm particle size class, "suspended" size fraction) were folded into 60 mL Teflon jars and weighed aliquots of artificial isotope yield monitors Th-229 (1 pg) and Pa-233 (0.05-0.12 pg) and 5 mg dissolved Fe were added to each sample, which then sat overnight in 5 mL concentrated (16 M) HNO3 (Fisher Scientific OPTIMA grade). The next day, the filters were heated for ~1 hour at 180°C, at which point 4-5 mL of concentrated HClO4 (Fisher Scientific OPTIMA grade) were added and the hot plate temperature was increased to 220°C. Samples were heated until dense white perchloric fumes appeared. After 10-20 minutes, the samples were covered with a Teflon watch glass. After 30-60 minutes, rapid oxidation of the Supor material would occur, at which point the Supor material was almost completely broken down. The watch glasses were removed and jar walls were rinsed down with 2 mL concentrated (16 M) HNO3 (Fisher Scientific OPTIMA grade) and placed back on the hot plate at 220°C. Once the samples were back to fuming perchloric, 0.5 mL of concentrated HF (Fisher Scientific OPTIMA grade) were added to the samples and heated at 220°C back to perchloric fumes before another 0.25-0.50 mL of concentrated HF (Fisher Scientific OPTIMA grade) were added. Following the second addition of concentrated HF, the samples were dried down at 220°C to a viscous residue.

The sample residue was taken up in dilute (0.6 M) HCl and transferred to 50 mL centrifuge tubes with Milli-Q H2O rinses. Then, ~1.5 mL of concentrated NH4OH (Fisher Scientific OPTIMA grade) were added to raise the pH to 8.0-8.5 when iron (oxy)hydroxide precipitated. This precipitate was then centrifuged and the supernatant was decanted. The precipitate was then dissolved in concentrated (16 M) HNO3 (Fisher Scientific OPTIMA grade), ready for a series of anion-exchange chromatography steps to purify Th and Pa, as outlined in Anderson et. al., 2012. The purified Th and Pa solutions were dried down at 180-200°C in the presence of 2 drops of concentrated HClO4 (Fisher Scientific OPTIMA grade) and taken up in 0.5 mL of 0.16 M HNO3/0.026 M HF for mass spectrometric analysis.

Concentrations of Th-232, Th-230 and Pa-231 were calculated by isotope dilution, relative to the calibrated tracers Th-229 and Pa-233 added at the beginning of sample processing. Analyses were carried out on a Thermo-Finnigan ELEMENT XR Single Collector Magnetic Sector ICP-MS, equipped with a high-performance Interface pump (Jet Pump Aridus I™), and specially designed sample (Jet) and skimmer (X) cones to ensure the highest possible sensitivity. All measurements were made in low resolution mode (∆m/M≈300), peak jumping in Escan mode across the central 5% of the flat-topped peaks. Measurements were made on a MasCom™ SEM; Th-229, Th-230, Pa-231, and Pa-233 were measured in Counting mode, while the Th-232 signals were large enough that they were measured in Analog mode. Two solutions of SRM129, a natural U standard, were run multiple times throughout each run. One solution was in a concentration range where U-238 and U-235 were both measured in Counting mode, allowing us to determine the mass bias/amu (typical values varied from -0.6%/amu to 0.3%/amu). In the other, more concentrated solution, U-238 was measured in Analog mode and U-235 was measured in Counting mode, yielding a measurement of the Analog/Counting Correction Factor (typical values varied from 0.9 to 1.3). These corrections assume that the mass bias and Analog/Counting Correction Factor measured on U isotopes can be applied to Th and Pa isotope measurements. Each sample measurement was bracketed by measurement of an aliquot of the run solution (0.16 M HNO3/0.026 M HF), which was used to correct for the instrumental background count rates. To correct for tailing of Th-232 into the minor Th and Pa isotopes, a series of Th-232 standards were run at concentrations bracketing the expected Th-232 concentrations in the samples. The analysis routine for these standards was identical to the analysis routine for samples, so we could see the changing beam intensities at the minor masses as we increased the concentration of the Th-232 standards. The Th-232 count rates in our Pa fractions were quite low after separation of Pa from Th during anion-exchange chromatography, reflecting mainly reagent blanks, compared to the Th-232 signal intensity in the Th fraction. The regressions of Th-229, Th-230, Pa-231, and Pa-233 signals as a function of the Th-232 signal in the standards was used to correct for tailing of Th-232 in samples. Only in rare cases was a tail correction of Th-232 on Pa-231 and Pa-233 necessary, while it was always the case that tail corrections of Th-232 on Th-229 and Th-230 were performed.

"Small particulate" samples (0.8-51 µm particle size class, "suspended" size fraction) were analyzed in batches of 15. Analysis of the paired Supor filters represents a particle size class approximating 0.45-51 µm (Bishop et al., 2012), while the top filter alone represents 0.8-51 µm and it is this size class referred to here as "small particulate". A selection of 14 top and bottom Supor filters were measured separately for radionuclides and it was found that the bottom filters had radionuclide levels that were indistinguishable from procedural blanks ("dipped" filter blanks). Therefore, whether or not samples were analyzed as paired Supor filters, or the top Supor filter alone, the "small particulate" data was inferred to represent the 0.8-51 µm particle size class or "suspended" size fraction. "Small particulate" samples were analyzed as top Supor filter alone and procedural blanks ("dipped" filter blanks) were analyzed as top or bottom Supor filter alone (top and bottom "dipped" filter blanks had radionuclide levels that were indistinguishable from one another). Procedural blanks were determined by analyzing "dipped" filter blanks, mentioned above, which represent the total blank associated with sample collection and handling in addition to the laboratory procedure. An aliquot of two intercalibrated working standard solutions of Th-232, Th-230, and Pa-231, SW STD 2010-1 referred to by Anderson et al. (2012) and SW STD 2015-1 which has ~6 times lower Th-232 activity, were added to separate acid-cleaned Teflon beakers along with weighed aliquots of Th-229 and Pa-233 spike. Spikes and SW STD were equilibrated for at least 1 day. They were then dried down and dissolved in concentrated (12 M) HCl (Fisher Scientific OPTIMA grade) for a series of anion-exchange chromatography and processed like a sample with each batch. Samples were corrected using the pooled average of all procedural blanks ("dipped" filter blanks) analyzed during processing of HLY1502 particulate samples. The average procedural blanks ("dipped" filter blanks) for the "small particulate" data from HLY1502 for a quarter filter cut of top (or bottom) Supor filters for Th-232, Th-230, and Pa-231 were 18.78 ± 7.42 pg, 0.89 ± 0.49 fg, and 0.04 ± 0.03 fg, respectively. The limit of detection (LOD) is the smallest quantity of each isotope in samples that can reliably be detected or that can be statistically distinguished from a procedural blank. The LOD was considered to be 2 standard deviations above the average of the procedural blanks. Our LOD for Th-232, Th-230, and Pa-231 were 33.61 pg, 1.86 fg, and 0.09 fg, respectively, or about 1.8x, 2.1x, and 2.5x greater than the blank amount, respectively.

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

Analytical Methods at UMN:
Eighth filter cuts of the paired (top and bottom) Supor filters ("small particulate", 0.8-51 µm particle size class, "suspended" size fraction) and the Sefar prefilters ("large particulate", >51 µm particle size class, "sinking" size fraction) were folded into 30 mL Teflon beaker and weighed aliquots of the artificial isotope yield monitors Th-229 (1 pg) and Pa-233 (0.2-0.6 pg) were added to the filters. Filters were then completely submerged in 20-25 mL of 7 M HNO3 combined with 10 drops of concentrated HF, tightly covered with a Teflon threaded cap and heated for 10 hours at ~90°C so that the particulate sample was dissolved/leached under pressure. The leachate and the rinse solution (rinsed twice with ICP-MS solution, 0.16 M HNO3/0.026 M HF) were then transferred to a second acid-cleaned Teflon beaker separate from the residual filter. Five drops of concentrated HClO4 were then added to the leach solution in the second beaker. The original beaker walls and caps were washed with small amounts of weak HNO3 and the resulting solution added to the second beaker. The solution was then dried down and taken up in dilute (2 M) HCl and transferred to 15 mL centrifuge tubes along with a dilute (2 M) HCl rinse. About 0.5 mg of dissolved Fe (one drop of FeCl3 solution with Fe3+ concentration at ~1%) and six to nine drops of concentrated NH4OH were added to raise the pH to 8.0-8.5 at which time iron (oxy)hydroxide precipitated. This precipitate was then centrifuged, decanted, washed with deionized H2O (>18 MΩ), centrifuged, dissolved in 14 M HNO3, and transferred to a Teflon beaker.

It was then dried down and taken up in 7 M HNO3 for anion-exchange chromatography using Bio-rad resin (AG1-X8, 100-200 mesh size) and a polyethylene frit. Initial separation was done on Teflon columns (internal diameter ~0.35 cm) with a 0.55 mL column volume (CV). The sample was loaded in 0.55 mL (1 CV) of 7 M HNO3, followed by 0.825 mL (1.5 CV) of 7 M HNO3 (to wash Fe and other undesired elements off the resin), 1.65 mL (3 CV) of 8 M HCl (to collect Th fraction), and 1.65 mL (3 CV) of 8 M HCl combined with 0.015 M HF (to collect Pa fraction). The Pa and Th fractions were then dried down in the presence of 2 drops of concentrated HClO4 and taken up in 7 M HNO3. They were each passed through second and third columns (each with 0.55 mL column volumes) using similar elution schemes. The final Pa and Th fractions were then dried down in the presence of 2 drops of concentrated HClO4 and dissolved in weak nitric acid for analysis on the mass spectrometer.

Concentrations of Th-232, Th-230, and Pa-231 were calculated by isotope dilution using nuclide ratios determined on a Thermo-Finnigan Neptune Multicollector ICP-MS. All measurements were done using a peak jumping routine in ion Counting mode on the discreet dynode multiplier behind the retarding potential quadrupole. A solution of U-233-U-236 tracer 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 (weak nitric acid) used to correct for the instrument background count rates on the masses measured.

"Small particulate" (0.8-51 µm particle size class, "suspended" size fraction) and "large particulate" (>51 µm particle size class, "sinking" size fraction) samples were analyzed in batches of 37-39. Analysis of the paired Supor filters represents a particle size class approximating 0.45-51 µm (Bishop et al., 2012), while the top filter alone represents 0.8-51 µm and it is this size class referred to here as "small particulate". A selection of 14 top and bottom Supor filters were measured separately for radionuclides at LDEO and it was found that the bottom filters had radionuclide levels that were indistinguishable from procedural blanks ("dipped" filter blanks). Therefore, whether or not samples were analyzed as paired Supor filters, or the top Supor filter alone, the "small particulate" data was inferred to represent the 0.8-51 µm particle size class or "suspended” size fraction. "Small particulate" samples and procedural blanks ("dipped" filter blanks) were analyzed as paired Supor filters. Procedural blanks were determined by analyzing "dipped" filter blanks, mentioned above, which represent the total blank associated with the sample collection and handling in addition to the laboratory procedure. An aliquot of one of two intercalibrated working standard solutions of Th-232, Th-230, and Pa-231, SW STD 2010-1 referred to by Anderson et al. (2012) and SW STD 2015-1 which has ~6 times lower Th-232 activity, was added to a separate acid-cleaned Teflon beaker along with weighed aliquots of Th-229 and Pa-233 spike. Spikes and SW STD were equilibrated for 3 days. They were then dried down and taken up in 7 M HNO3 for anion-exchange chromatography and processed like a sample with each batch. Samples were corrected using the pooled average of all procedural blanks ("dipped" filter blanks) analyzed during processing of HLY1502 particulate samples. The average procedural blanks ("dipped" filter blanks) for the HLY1502 "small particulate" dataset for an eighth filter cut of paired Supor filters for Th-232, Th-230, and Pa-231 were 11.36 ± 3.20 pg, 0.64 ± 0.30 fg, and 0.01 ± 0.01 fg, respectively. The average procedural blanks ("dipped" filter blanks) for the HLY1502 "large particulate" dataset for an eighth filter cut of Sefar prefilters for Th-232, Th-230, and Pa-231 were 12.55 ± 8.26 pg, 0.35 ± 0.15 fg, and 0.01 ± 0.01 fg, respectively. The limit of detection (LOD) is the smallest quantity of each isotope in samples that can reliably be detected or that can be statistically distinguished from a procedural blank. The LOD was considered to be 2 standard deviations above the average of the procedural blanks. For the HLY1502 "small particulate" dataset, our LOD for Th-232, Th-230, and Pa-231 were 17.76 pg, 1.23 fg, and 0.02 fg, respectively, or about 1.6x, 1.9x, and 1.9x greater than the blank amount, respectively. For the HLY1502 "large particulate" dataset, our LOD for Th-232, Th-230, and Pa-231 were 29.07 pg, 0.65 fg, and 0.04 fg, respectively, or about 2.3x, 1.8x, and 2.9x greater than the blank amount, respectively.

Further details on Pa and Th analysis at University of Minnesota are given in Shen et al. (2002, 2003, 2012), and Cheng et al. (2000, 2013).

Notes on Derived Parameters:
Th_230_SPT_XS_CONC_PUMP:
The small particulate excess Th-230 refers to the measured small particulate Th-230 corrected for a contribution of Th-230 originating from U-bearing minerals or lithogenic Th-230. Some of this lithogenic Th-230 will be still intact within minerals and some after partial dissolution will have adsorbed to particle surface to contribute in part to the total adsorbed Th-230. Using the measured small particulate Th-232 and a lithogenic Th-230/Th-232 ratio of 4.0e-6 (atom ratio) as determined by Roy-Barman et al. (2002), and not taking into account the fact that some of the measured particulate Th-232 is adsorbed, corrects for all of the lithogenic Th-230 whether it be adsorbed or within intact minerals. This excess Th-230 is what should be used in scavenging or particle flux studies where it is desired to compare particulate Th-230 concentrations to Th-230 production by decay of uranium dissolved in seawater. An additional conversion factor converts picomoles to micro-Becquerels.

Th_230_SPT_XS_CONC_PUMP = Th_230_SPT_CONC_PUMP – 4.0e-6 * 1.7473e5 * Th_232_SPT_CONC_PUMP

Pa_231_SPT_XS_CONC_PUMP:
The small particulate excess Pa-231 refers to the measured small particulate Pa-231 corrected for a contribution of Pa-231 originating from U-bearing minerals or lithogenic Pa-231. Some of this lithogenic Pa-231 will be still intact within minerals and some after partial dissolution will have adsorbed to particle surface to contribute in part to the total adsorbed Pa-231. Using the measured small particulate Th-232 and a lithogenic Pa-231/Th-232 ratio of 8.8e-8 (atom ratio) which is derived from assuming an average upper continental crustal U/Th ratio (Taylor and McClennan, 1995) and secular equilibrium between Pa-231 and U-235 in the lithogenic material, and not taking into account the fact that some of the measured particulate Th-232 is adsorbed, corrects for all of the lithogenic Pa-231 whether it be adsorbed or within intact minerals. This excess Pa-231 is what should be used in scavenging or particle flux studies where it is desired to compare particulate Pa-231 concentrations to Pa-231 production by decay of uranium dissolved in seawater. An additional conversion factor converts picomoles to micro-Becquerels.

Pa_231_SPT_XS_CONC_PUMP = Pa_231_SPT_CONC_PUMP – 8.8e-8 * 4.0370e5 * Th_232_SPT_CONC_PUMP

Th_230_LPT_XS_CONC_PUMP:
The large particulate excess Th-230 refers to the measured large particulate Th-230 corrected for a contribution of Th-230 originating from U-bearing minerals or lithogenic Th-230. Some of this lithogenic Th-230 will be still intact within minerals and some after partial dissolution will have adsorbed to particle surface to contribute in part to the total adsorbed Th-230. Using the measured large particulate Th-232 and a lithogenic Th-230/Th-232 ratio of 4.0e-6 (atom ratio) as determined by Roy-Barman et al. (2002), and not taking into account the fact that some of the measured particulate Th-232 is adsorbed, corrects for all of the lithogenic Th-230 whether it be adsorbed or within intact minerals. This excess Th-230 is what should be used in scavenging or particle flux studies where it is desired to compare particulate Th-230 concentrations to Th-230 production by decay of uranium dissolved in seawater. An additional conversion factor converts picomoles to micro-Becquerels.

Th_230_LPT_XS_CONC_PUMP = Th_230_LPT_CONC_PUMP – 4.0e-6 * 1.7473e5 * Th_232_LPT_CONC_PUMP

Pa_231_LPT_XS_CONC_PUMP:
The large particulate excess Pa-231 refers to the measured large particulate Pa-231 corrected for a contribution of Pa-231 originating from U-bearing minerals or lithogenic Pa-231. Some of this lithogenic Pa-231 will be still intact within minerals and some after partial dissolution will have adsorbed to particle surface to contribute in part to the total adsorbed Pa-231. Using the measured large particulate Th-232 and a lithogenic Pa-231/Th-232 ratio of 8.8e-8 (atom ratio) which is derived from assuming an average upper continental crustal U/Th ratio (Taylor and McClennan, 1995) and secular equilibrium between Pa-231 and U-235 in the lithogenic material, and not taking into account the fact that some of the measured particulate Th-232 is adsorbed, corrects for all of the lithogenic Pa-231 whether it be adsorbed or within intact minerals. This excess Pa-231 is what should be used in scavenging or particle flux studies where it is desired to compare particulate Pa-231 concentrations to Pa-231 production by decay of uranium dissolved in seawater. An additional conversion factor converts picomoles to micro-Becquerels.

Pa_231_LPT_XS_CONC_PUMP = Pa_231_LPT_CONC_PUMP – 8.8e-8 * 4.0370e5 * Th_232_LPT_CONC_PUMP

Th_230_SPT_ADS_CONC_PUMP:
The small particulate adsorbed Th-230 concentration refers to the measured small particulate Th-230 corrected for a contribution of Th-230 locked within mineral lattices. To estimate the particulate Th-230 supported by decay of U within mineral lattices, we use measured small particulate Th-232 and a lithogenic Th-230/Th-232 ratio of 4.0e-6 (atom ratio) as determined by Roy-Barman et al. (2002). However, because some fraction of the Th-232 is also adsorbed (and not merely found within mineral lattices), we use the dissolved Th-232/Th-230 ratio to estimate the fraction of the small particulate Th-232 that is adsorbed and furthermore to calculate the correction for adsorbed Th-230. Conversion factors are also necessary to convert picomoles to micro-Becquerels. When dissolved Th data do not exist at the same depth as the particulate samples, we linearly interpolated the dissolved data onto the depths of the particulate samples. See Hayes et al. (2015) for more details.

Th_230_SPT_ADS_CONC_PUMP = [ Th_230_SPT_CONC_PUMP – 4.0e-6 * 1.7473e5 * Th_232_SPT_CONC_PUMP ] / [ 1 – 4.0e-6 * 1.7473e5 * Th_232_D_CONC_BOTTLE / Th_230_D_CONC_BOTTLE ]

Pa_231_SPT_ADS_CONC_PUMP:
The small particulate adsorbed Pa-231 concentration refers to the measured small particulate Pa-231 corrected for a contribution of Pa-231 locked within mineral lattices (as opposed to adsorbed onto particle surfaces). To estimate the particulate Pa-231 supported by decay of U within mineral lattices, we use measured small particulate Th-232 and a lithogenic Pa-231/Th-232 ratio of 8.8e-8 (atom ratio) which is derived from assuming an average upper continental crustal U/Th ratio (Taylor and McClennan, 1995) and secular equilibrium between Pa-231 and U-235 in the lithogenic material. However, because some fraction of the Th-232 is also adsorbed (and not merely found within mineral lattices), we use the dissolved and particulate Th-232/Th-230 ratio to estimate what fraction of the small particulate Th-232 is adsorbed and furthermore to calculate the correction for adsorbed Pa-231. Conversion factors are also necessary to convert picomoles to micro-Becquerels. When dissolved Pa data do not exist at the same depth as the particulate samples, we linearly interpolate the dissolved data onto the depths of the particulate samples. See Hayes et al. (2015) for more details.

Pa_231_SPT_ADS_CONC_PUMP = Pa_231_SPT_CONC_PUMP – 8.8e-8 * 4.0370e5 * ( Th_232_SPT_CONC_PUMP – Th_232_D_CONC_BOTTLE * [ ( Th_230_SPT_CONC_PUMP – 4.0e-6 * 1.7473e5 * Th_232_SPT_CONC_PUMP ) / ( Th_230_D_CONC_BOTTLE – 4.0e-6 * 1.7473e5 * Th_232_D_CONC_BOTTLE ) ] )

Th_230_LPT_ADS_CONC_PUMP:
The large particulate adsorbed Th-230 concentration refers to the measured large particulate Th-230 corrected for a contribution of Th-230 locked within mineral lattices. To estimate the particulate Th-230 supported by decay of U within mineral lattices, we use measured large particulate Th-232 and a lithogenic Th-230/Th-232 ratio of 4.0e-6 (atom ratio) as determined by Roy-Barman et al. (2002). However, because some fraction of the Th-232 is also adsorbed (and not merely found within mineral lattices), we use the dissolved Th-232/Th-230 ratio to estimate what fraction of the large particulate Th-232 is adsorbed and furthermore to calculate the correction for adsorbed Th-230. Conversion factors are also necessary to convert picomoles to micro-Becquerels. When dissolved data do not exist at the same depth as the particulate samples, we linearly interpolated the dissolved data onto the depths of the particulate samples. See Hayes et al. (2015) for more details.

Th_230_LPT_ADS_CONC_PUMP = [ Th_230_LPT_CONC_PUMP – 4.0e-6 * 1.7473e5 * Th_232_LPT_CONC_PUMP ] / [ 1 – 4.0e-6 * 1.7473e5 * Th_232_D_CONC_BOTTLE / Th_230_D_CONC_BOTTLE ]

Pa_231_LPT_ADS_CONC_PUMP:
The large particulate adsorbed Pa-231 concentration refers to the measured large particulate Pa-231 corrected for a contribution of Pa-231 locked within mineral lattices (as opposed to adsorbed on to particle surfaces). To estimate the particulate Pa-231 supported by decay of U within mineral lattices, we use measured large particulate Th-232 and a lithogenic Pa-231/Th-232 ratio of 8.8e-8 (atom ratio) which is derived from assuming an average upper continental crustal U/Th ratio (Taylor and McClennan, 1995) and secular equilibrium between Pa-231 and U-235 in the lithogenic material. However, because some fraction of the Th-232 is also adsorbed (and not merely found within mineral lattices), we use the dissolved and particulate Th-232/Th-230 ratio to estimate what fraction of the large particulate Th-232 is adsorbed and furthermore to calculate the correction for adsorbed Pa-231. Conversion factors are also necessary to convert picomoles to micro-Becquerels. When dissolved Pa data do not exist at the same depth as the particulate samples, we linearly interpolate the dissolved data onto the depths of the particulate samples. See Hayes et al. (2015) for more details.

Pa_231_LPT_ADS_CONC_PUMP = Pa_231_LPT_CONC_PUMP – 8.8e-8 * 4.0370e5 * ( Th_232_LPT_CONC_PUMP – Th_232_D_CONC_BOTTLE * [ ( Th_230_LPT_CONC_PUMP – 4.0e-6 * 1.7473e5 * Th_232_LPT_CONC_PUMP ) / ( Th_230_D_CONC_BOTTLE – 4.0e-6 * 1.7473e5 * Th_232_D_CONC_BOTTLE ) ] )

Data Processing Description

Dataset Processing Description

Data Processing:
The reported errors for radionuclide concentrations represent the propagation of one sigma errors based on the standard isotope ratios collected by ICP-MS, estimated error in the Th-229 or Pa-233 spike concentration, and the blank correction of the individual isotopes. For each laboratory (LDEO and UMN), samples were corrected for blanks using the pooled average of all procedural blanks (or "dipped" filter blanks) analyzed during processing of HLY1502 seawater particulate samples.

Individual uncertainties for protactinium and thorium were calculated to include contributions from (a) blank correction using the variance of the blanks measured over the course of the analyses, (b) standard error of the ratios of the analysis (typically close to counting statistics) and (c) spike calibration. For protactinium we also included assessment of the correction from the yield correction, mass bias and instrument background. In order to assess the reproducibility of the procedure, repeat analyses were performed on the GEOTRACES 2010-1 and 2015-1 standards. For standards run alongside GN01 particulate samples at LDEO, the reproducibility for each isotope was 1.04% for Th-232, 0.88% for Th-230, and 1.97% for Pa-231 on SW STD 2010-1, and was 3.52% for Th-232, 0.82% for Th-230, and 2.32% for Pa-231 on SW STD 2015-1. At UMN, the reproducibility for each isotope was 1.09% for Th-232, 0.86% for Th-230, and 1.44% for Pa-231 on SW STD 2010-1, and was 0.34% for Th-232, 0.35% for Th-230, and 1.17% for Pa-231 on SW STD 2015-1.

Quality Flags:
SeaDataNet quality flags have been assigned to all measured and derived parameters. More information on SeaDataNet quality flags is available from GEOTRACES at https://www.geotraces.org/geotraces-quality-flag-policy/ and from SeaDataNet at https://www.seadatanet.org/Standards/Data-Quality-Control. In summary:

0 = no quality control;
1 = good value;
2 = probably good value;
3 = probably bad value;
4 = bad value;
5 = changed value;
6 = value below detection;
7 = value in excess;
8 = interpolated value;
9 = missing value;
A = value phenomenon uncertain.

The SeaDataNet quality flags assigned to the derived parameters are based on the SeaDataNet quality flags assigned to the measured parameters and are defined as:

1 = good value = both Th-230 (Pa-231) and Th-232 are flagged as good (1);

2 = probably good value = either Th-230 (Pa-231) is flagged as good (1) and Th-232 is flagged as probably good (2), probably bad (3), or bad (4), or Th-230 (Pa-231) is flagged as probably good (2) and Th-232 is flagged as good (1), probably good (2), probably bad (3), or bad (4);

3 = probably bad value = Th-230 (Pa-231) is flagged as probably bad (3) and Th-232 is flagged as good (1), probably good (2), probably bad (3), or bad (4);

4 = bad value = Th-230 (Pa-231) is flagged as bad (4) and Th-232 is flagged as good (1), probably good (2), probably bad (3), or bad (4);

6 = value below detection = either or both Th-230 (Pa-231) and Th-232 are flagged as below detection (6) and neither are flagged as missing (9);

9 = missing value = either or both Th-230 (Pa-231) and Th-232 are flagged as missing (9).

Concentrations below the limit of detection (LOD) are indicated as "nd" and flagged with "6". The missing data identifier, "nd", also refers to no data available when flagged with "9" (i.e., no analysis).

BCO-DMO Processing:
- modified parameter names to conform with BCO-DMO naming conventions (replaced "::" with an underscore and changed "1SD" to "SD1").

Version History:
- 2020-12-30: version 1 published.
- 2021-02-23: replaced with data file received 2021-01-28 (version 2); includes changes to some data values.
- 2021-08-25; replaced with data file received 2021-08-01 (version 3); includes the following changes:

End_Date_UTC for:
Event 6454 from “nd” to “04/10/2015”

End_Time_UTC for:
Event 6454 from “nd” to “13:00”

End_ISO_DateTime_UTC for:
Event 6454 from “nd” to “2015-10-04T13:00Z”

More information about this dataset deployment

Funding

Award Number	Funding Source
OCE-1434479	NSF Division of Ocean Sciences
OCE-1434886	NSF Division of Ocean Sciences

Instruments

Centrifuge

Supplied Description:

Instrument Type

Generic Name: Centrifuge

Generic Description:

A machine with a rapidly rotating container that applies centrifugal force to its contents, typically to separate fluids of different densities (e.g., cream from milk) or liquids from solids.

Inductively Coupled Plasma Mass Spectrometer

Supplied Name: Thermo-Finnigan ELEMENT XR Single Collector Magnetic Sector ICP-MS; Thermo-Finnigan Neptune Multicollector ICP-MS

Supplied Description:

A Thermo-Finnigan ELEMENT XR Single Collector Magnetic Sector ICP-MS, equipped with a high-performance Interface pump (Jet Pump Aridus I™), and specially designed sample (Jet) and skimmer (X) cones to ensure the highest possible sensitivity in the Lamont Doherty Earth Observatory - American Museum of Natural History ICP-MS Lab at the Lamont-Doherty Earth Observatory of Columbia University was used.

A Thermo-Finnigan Neptune Multicollector ICP-MS, equipped with a high-performance Interface pump (Jet Pump Aridus II™), and specially designed sample (Jet) and skimmer (X) cones to ensure the highest possible sensitivity in the Newton Horace Winchell School of Earth and Environmental Sciences at the University of Minnesota was used.

Instrument Type

Generic Name: Inductively Coupled Plasma Mass Spectrometer

Acronym: ICP Mass Spec

Community Identifier: http://vocab.nerc.ac.uk/collection/L05/current/LAB15/

Generic Description:

An ICP Mass Spec is an instrument that passes nebulized samples into an inductively-coupled gas plasma (8-10000 K) where they are atomized and ionized. Ions of specific mass-to-charge ratios are quantified in a quadrupole mass spectrometer.

McLane Large Volume Pumping System WTS-LV

Supplied Name: Dual-flow McLane Research in-situ pumps (WTS-LV)

Supplied Description:

PUMP: McLane in-situ pumps (McLane WTS-LV) used to collect in-situ water column small and large particulate samples.

Instrument Type

Generic Name: McLane Large Volume Pumping System WTS-LV

Acronym: WTS-LV

Generic Description:

The WTS-LV is a Water Transfer System (WTS) Large Volume (LV) pumping instrument designed and manufactured by McLane Research Labs (Falmouth, MA, USA). It is a large-volume, single-event sampler that collects suspended and dissolved particulate samples in situ.

Ambient water is drawn through a modular filter holder onto a 142-millimeter (mm) membrane without passing through the pump. The standard two-tier filter holder provides prefiltering and size fractioning. Collection targets include chlorophyll maximum, particulate trace metals, and phytoplankton. It features different flow rates and filter porosity to support a range of specimen collection. Sampling can be programmed to start at a scheduled time or begin with a countdown delay. It also features a dynamic pump speed algorithm that adjusts flow to protect the sample as material accumulates on the filter. Several pump options range from 0.5 to 30 liters per minute, with a max volume of 2,500 to 36,000 liters depending on the pump and battery pack used. The standard model is depth rated to 5,500 meters, with a deeper 7,000-meter option available. The operating temperature is -4 to 35 degrees Celsius.

The WTS-LV is available in four different configurations: Standard, Upright, Bore Hole, and Dual Filter Sampler. The high-capacity upright WTS-LV model provides three times the battery life of the standard model. The Bore-Hole WTS-LV is designed to fit through a narrow opening such as a 30-centimeter borehole. The dual filter WTS-LV features two vertical intake 142 mm filter holders to allow simultaneous filtering using two different porosities.

Parameters

Supplied Name	Supplied description	Supplied Units	Standard Name
Cruise_ID	Cruise identifier	unitless	cruise_id
Station_ID	Station number	unitless	station
Event_ID	GEOTRACES event number	unitless	event
Cast_ID	Cast number	unitless	cast
Start_Date_UTC	Date (UTC) at start of sample collection; format: DD/MM/YYYY	unitless	date
Start_Time_UTC	Time (UTC) at start of sample collection; format: hh:mm	unitless	time
Start_ISO_DateTime_UTC	Date and time (UTC) at start of sample collection formatted to ISO 8601 standard; format: YYYY-MM-DDThh:mmZ	unitless	ISO_DateTime_UTC
End_Date_UTC	Date (UTC) at end of sample collection; format: DD/MM/YYYY	unitless	date
End_Time_UTC	Time (UTC) at end of sample collection; format: hh:mm	unitless	time
End_ISO_DateTime_UTC	Date and time (UTC) at end of sample collection formatted to ISO 8601 standard; format: YYYY-MM-DDThh:mmZ	unitless	ISO_DateTime_UTC
Start_Latitude	Latitude at start of sample collection	decimal degrees North	lat
Start_Longitude	Longitude at start of sample collection	decimal degrees East	lon
End_Latitude	Latitude at end of sample collection	decimal degrees North	lat
End_Longitude	Longitude at end of sample collection	decimal degrees East	lon
Pump_ID	Pump number	unitless	instrument
Flag_Pump_ID	SeaDataNet quality flag for Pump_ID	unitless	q_flag
Sample_ID	GEOTRACES sample number	unitless	sample
Lab_ID_SPT	Lab identifier for small particulate (SPT) sample analysis	unitless	laboratory
Lab_ID_LPT	Lab identifier for large particulate (LPT) sample analysis	unitless	laboratory
Sample_Pressure	Sample pressure	decibars (dbar)	press
Sample_Depth	Sample depth	meters (m)	depth
Th_232_SPT_CONC_PUMP_kbuaoq	Concentration of small particulate Th-232 in seawater collected using a McLane large volume in situ pump	picomoles per kilogram (pmol/kg)	Th-232
SD1_Th_232_SPT_CONC_PUMP_kbuaoq	One standard deviation of Th_232_SPT_CONC_PUMP_kbuaoq	picomoles per kilogram (pmol/kg)	Th-232
Flag_Th_232_SPT_CONC_PUMP_kbuaoq	SeaDataNet quality flag for Th_232_SPT_CONC_PUMP_kbuaoq	unitless	q_flag
Th_230_SPT_CONC_PUMP_qmzytn	Concentration of small particulate Th-230 in seawater collected using a McLane large volume in situ pump	micro-Becquerel per kilogram (µBq/kg)	Th-230
SD1_Th_230_SPT_CONC_PUMP_qmzytn	One standard deviation of Th_230_SPT_CONC_PUMP_qmzytn	micro-Becquerel per kilogram (µBq/kg)	Th-230
Flag_Th_230_SPT_CONC_PUMP_qmzytn	SeaDataNet quality flag for Th_230_SPT_CONC_PUMP_qmzytn	unitless	q_flag
Pa_231_SPT_CONC_PUMP_6pkszt	Concentration of small particulate Pa-231 in seawater collected using a McLane large volume in situ pump	micro-Becquerel per kilogram (µBq/kg)	Pa-231
SD1_Pa_231_SPT_CONC_PUMP_6pkszt	One standard deviation of Pa_231_SPT_CONC_PUMP_6pkszt	micro-Becquerel per kilogram (µBq/kg)	Pa-231
Flag_Pa_231_SPT_CONC_PUMP_6pkszt	SeaDataNet quality flag for Pa_231_SPT_CONC_PUMP_6pkszt	unitless	q_flag
Th_232_LPT_CONC_PUMP_zg488c	Concentration of large particulate Th-232 in seawater collected using a McLane large volume in situ pump	picomoles per kilogram (pmol/kg)	Th-232
SD1_Th_232_LPT_CONC_PUMP_zg488c	One standard deviation of Th_232_LPT_CONC_PUMP_zg488c	picomoles per kilogram (pmol/kg)	Th-232
Flag_Th_232_LPT_CONC_PUMP_zg488c	SeaDataNet quality flag for Th_232_LPT_CONC_PUMP_zg488c	unitless	q_flag
Th_230_LPT_CONC_PUMP_o2lqui	Concentration of large particulate Th-230 in seawater collected using a McLane large volume in situ pump	micro-Becquerel per kilogram (µBq/kg)	Th-230
SD1_Th_230_LPT_CONC_PUMP_o2lqui	One standard deviation of Th_230_LPT_CONC_PUMP_o2lqui	micro-Becquerel per kilogram (µBq/kg)	Th-230
Flag_Th_230_LPT_CONC_PUMP_o2lqui	SeaDataNet quality flag for Th_230_LPT_CONC_PUMP_o2lqui	unitless	q_flag
Pa_231_LPT_CONC_PUMP_slruxz	Concentration of large particulate Pa-231 in seawater collected using a McLane large volume in situ pump	micro-Becquerel per kilogram (µBq/kg)	Pa-231
SD1_Pa_231_LPT_CONC_PUMP_slruxz	One standard deviation of Pa_231_LPT_CONC_PUMP_slruxz	micro-Becquerel per kilogram (µBq/kg)	Pa-231
Flag_Pa_231_LPT_CONC_PUMP_slruxz	SeaDataNet quality flag for Pa_231_LPT_CONC_PUMP_slruxz	unitless	q_flag
Th_230_SPT_XS_CONC_PUMP	Concentration of small particulate excess Th-230 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Th-230
SD1_Th_230_SPT_XS_CONC_PUMP	One standard deviation of Th_230_SPT_XS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Th-230
Flag_Th_230_SPT_XS_CONC_PUMP	SeaDataNet quality flag for Th_230_SPT_XS_CONC_PUMP	unitless	q_flag
Pa_231_SPT_XS_CONC_PUMP	Concentration of small particulate excess Pa-231 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Pa-231
SD1_Pa_231_SPT_XS_CONC_PUMP	One standard deviation of Pa_231_SPT_XS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Pa-231
Flag_Pa_231_SPT_XS_CONC_PUMP	SeaDataNet quality flag for Pa_231_SPT_XS_CONC_PUMP	unitless	q_flag
Th_230_LPT_XS_CONC_PUMP	Concentration of large particulate excess Th-230 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Th-230
SD1_Th_230_LPT_XS_CONC_PUMP	One standard deviation of Th_230_LPT_XS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Th-230
Flag_Th_230_LPT_XS_CONC_PUMP	SeaDataNet quality flag for Th_230_LPT_XS_CONC_PUMP	unitless	q_flag
Pa_231_LPT_XS_CONC_PUMP	Concentration of large particulate excess Pa-231 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Pa-231
SD1_Pa_231_LPT_XS_CONC_PUMP	One standard deviation of Pa_231_LPT_XS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Pa-231
Flag_Pa_231_LPT_XS_CONC_PUMP	SeaDataNet quality flag for Pa_231_LPT_XS_CONC_PUMP	unitless	q_flag
Th_230_SPT_ADS_CONC_PUMP	Concentration of small particulate adsorbed Th-230 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Th-230
SD1_Th_230_SPT_ADS_CONC_PUMP	One standard deviation of Th_230_SPT_ADS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Th-230
Flag_Th_230_SPT_ADS_CONC_PUMP	SeaDataNet quality flag for Th_230_SPT_ADS_CONC_PUMP	unitless	q_flag
Pa_231_SPT_ADS_CONC_PUMP	Concentration of small particulate adsorbed Pa-231 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Pa-231
SD1_Pa_231_SPT_ADS_CONC_PUMP	One standard deviation of Pa_231_SPT_ADS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Pa-231
Flag_Pa_231_SPT_ADS_CONC_PUMP	SeaDataNet quality flag for Pa_231_SPT_ADS_CONC_PUMP	unitless	q_flag
Th_230_LPT_ADS_CONC_PUMP	Concentration of large particulate adsorbed Th-230 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Th-230
SD1_Th_230_LPT_ADS_CONC_PUMP	One standard deviation of Th_230_LPT_ADS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Th-230
Flag_Th_230_LPT_ADS_CONC_PUMP	SeaDataNet quality flag for Th_230_LPT_ADS_CONC_PUMP	unitless	q_flag
Pa_231_LPT_ADS_CONC_PUMP	Concentration of large particulate adsorbed Pa-231 in seawater collected using a McLane large volume in situ pump (see metadata for full explanation)	micro-Becquerel per kilogram (µBq/kg)	Pa-231
SD1_Pa_231_LPT_ADS_CONC_PUMP	One standard deviation of Pa_231_LPT_ADS_CONC_PUMP	micro-Becquerel per kilogram (µBq/kg)	Pa-231
Flag_Pa_231_LPT_ADS_CONC_PUMP	SeaDataNet quality flag for Pa_231_LPT_ADS_CONC_PUMP	unitless	q_flag

Database

Contribute Data

Dataset: GN01 Particulate Thorium and Protactinium
Deployment: HLY1502

Dataset acquisition description

Dataset Processing Description

Database

Contribute Data

Dataset: GN01 Particulate Thorium and ProtactiniumDeployment: HLY1502

Dataset acquisition description

Dataset Processing Description

Dataset: GN01 Particulate Thorium and Protactinium
Deployment: HLY1502