Dataset: 2019 BAIT Particulate Metals
Deployment: EN631

Water column samples were collected by the Bermuda Atlantic Iron Timeseries (BAIT) sampling team from 12 trace metal clean modified 6-liter (L) Niskin-X samplers (General Oceanics Inc.) deployed on a clean CTD rosette system (Sedwick et al. 2005). Water was decanted from Niskin-X bottles in a trace metal van, transferred to trace metal bubble, and passed through 25-millimeter (mm) 0.45-micrometer (um) Supor (Pall Gelman) membranes via positive pressure from 0.2-um filtered air. Between 2.4-4.1L (mean = 3.6L) were passed through each filter membrane. Membranes were frozen at -20 degrees Celsius (C) until processing and analysis.

All digestion steps were performed in a Class-100 clean room using standard clean techniques. Filters were cut in half using a ceramic blade, using a cutting template and a light table to aid precision. One half was digested following the protocol of Berger et al. (2008) to obtain labile particulate concentrations; the other was digested using a 4M HCl, 4M HNO3, and 4M HF mixture as described in Ohnemus et al. (2014) to obtain total particulate element concentrations. Labile particulate filter halves were leached in a solution of 25% Optima-grade acetic acid and 0.02 M hydroxylamine hydrochloride following the protocol of Berger et al. (2008). One milliliter (mL) of this solution was added to the filter stored in a 1.7 mL polypropylene vial. Following the recommendation of Berger et al. (2008), the solution was heated to 95°C in a water bath for 10 minutes and then allowed to cool to room temperature. The filter was in contact with the acetic acid leach for a total of two hours, after which the filter was removed from the polypropylene vial and the acetic acid/hydroxylamine leachate was centrifuged at 14,000 rotations per minute (rpm) for 10 minutes to sediment all particles. Without disturbing particles on the bottom of the tube, approximately 0.8 mL of leachate was transferred into an acid-cleaned 7 mL PFA digestion vial. Optima-grade HNO3 was added (100 microliters (uL)) to the digestion vial, which was subsequently heated uncapped at 110ºC to near dryness. Vial contents were redissolved with 2% HNO3 (Optima grade).

Total particulate metals were determined by digestion of the second filter half. The filter was transferred to a rigorously cleaned 22-mL PFA vial, 2 mL of a solution containing 4M HCl, 4M HNO3, and 4M HF (all Optima grade) was added to completely cover the filter piece, and the vial was tightly capped and heated to 110°C for 4 hours. This procedure has been determined to be adequate for digestion of all particulate material, while allowing the Supor filter to remain intact (Ohnemus et al. 2014). Following heating, the acid solution in the bomb was poured into a second PFA vial, leaving the filter piece behind. To ensure complete transfer of acid, the bombs were thoroughly rinsed with 3 × 0.5 mL aliquots of ultrapure water which were poured into the secondary vial. The secondary vial was then heated to dryness and the contents redissolved with 2 mL of a 50% Optima-grade HNO3 + 15% Optima-grade H2O2 (v/v of concentrated reagents) solution. This solution was again dried down and the contents redissolved with 2% HNO3.

All digests were analyzed using a Thermo Element2 HR-ICP-MS at the University of Maine following the protocols outlined in Twining et al. (2011). The instrument is equipped with a cyclonic nebulizer, an autosampler contained under a HEPA filter, and nickel cones. Quantification was performed by external calibration, and In-115 was used as an internal standard to correct for variations in instrumental sensitivity during analyses.

Cs-133, spiked during the initial sample digestions, was used as a process recovery monitor, but no samples were discarded or corrected using the Cs recoveries, as typical Cs recoveries were 95-105%.