Dataset: Trace-metals from CTD casts and underway water samples
Deployment: HRS1414

[The following methodology applies where dataset parameter "sample_source" is "UNDERWAY"]

Near-surface sample collection: Near-surface (~4 m depth) seawater was collected whilst underway at ~5 knots using a trace-metal clean towfish system [Sedwick et al., 2011]. The subsamples for analysis of DFe, NO3+NO2, PO4 were taken directly from the towfish line, after filtration through a 0.8/0.2 µm AcroPak Supor filter capsule (Pall), in acid-cleaned 125 mL low-density polyethylene bottles (Nalgene) for shore-based DFe determinations, and 60 mL polypropylene tubes (Falcon) for shipboard NO3+NO2, PO4 and NH4 analyses.

Near-surface underway measurements: Continuous underway measurements of near-surface seawater temperature, salinity and chlorophyll fluorescence were made using the ship's underway seawater supply, which is pumed from a water depth of ~1m. The data presented correspond to the approximate times when subsamples were collected from the towfish seawater outlet for measurements of dissolved iron and macronutrients (see above).

DFe: Filtered seawater samples were acidified at-sea to pH ~1.8 with Fisher Optima grade ultrapure hydrochloric acid, and then stored at room temperature until post-cruise analysis at Old Dominion University. Dissolved iron was determined by flow injection analysis with colorimetric detection after in-line preconcentration on resin-immobilized 8-hydroxyquinoline (Sedwick et al., 2015), using a method modified from Measures et al. (1995). Analyses were performed on a volumetric basis, so concentrations are reported in units of nanomole liter-1 (nM). Analytical precision is estimated from multiple (separate-day) determinations of the SAFe seawater reference materials, which yield uncertainties (expressed as one relative standard deviation on the mean, or one sigma) of ~15% at the concentration level of SAFe S seawater (0.090 nM), and ~10% at the concentration level of SAFe D2 seawater (0.90 nM). The analytical limit of detection is estimated as the DFe concentration equivalent to a peak area that is three times the standard deviation on the zero-loading blank (manifold blank), which yields an estimated detection limit below 0.04 nM (Bowie et al., 2004). Blank contributions from the ammonium acetate sample buffer solution (added on-line during analysis) and hydrochloric acid (added after collection) are negligible.

NO3+NO2: Dissolved nitrate and nitrite was determined at sea using an Astoria Pacific nutrient autoanalyzer using standard colorimetric methods with an estimated detection limit of 0.14 µM (Parsons et al., 1984; Price and Harrison, 1987). In surface waters, nitrate and nitrite were determined using the same autoanalyzer equipped with a liquid waveguide capillary cell (World Precision Instruments) (Zhang, 2000) to achieve an estimated detection limit of 0.02 µM.

PO4: Dissolved phosphate was determined at sea using an Astoria Pacific nutrient autoanalyzer using standard colorimetric methods with an estimated detection limit of 0.03 µM (Parsons et al., 1984; Price and Harrison, 1987).

NH4: Dissolved ammonium was determined at sea using the manual orthophthaldialdehyde method (Holmes et al., 1999), with an estimated detection limit of 10 nM.

Temperature: Underway temperature was measured using a conductivity-temperature-depth sensor (SBE 45, SeaBird Electronics).

Salinity: Underway salinity was calculated from in-situ conductivity, as measured using a conductivity-temperature-depth (CTD) sensor (SBE 45, SeaBird Electronics).

Fluorescence: Underway chlorophyll fluorescence was measured using a Turner AU10 fluorometer.

[The following methodology applies where dataset parameter "sample_source" is "CTD"]

Water column sample collection and in-situ measurements: Water-column samples for analysis of dissolved iron, nitrate plus nitrite, phosphate and ammonium, and continuous profiles of temperature, salinity and chlorophyll fluorescence were collected using a trace-metal clean conductivity-temperature-depth sensor (SBE 19 plus, SeaBird Electronics) mounted on a custom-built trace-metal clean carousel (SeaBird Electronics) fitted with custom-modified 5-L Teflon-lined external-closure Niskin-X samplers (General Oceanics), deployed on a Kevlar line. Upon recovery, the Niskin-X samplers were transferred into a shipboard Class-100 clean laboratory, where seawater was filtered through pre-cleaned 0.2-µm pore AcroPak Supor filter capsules (Pall) into acid-cleaned 125 mL low-density polyethylene bottles (Nalgene) for shore-based dissolved iron determinations, and 60 mL polypropylene tubes (Falcon) for shipboard nutrient analyses.

DFe: Filtered seawater samples were acidified at-sea to pH ~1.8 with Fisher Optima grade ultrapure hydrochloric acid, and then stored at room temperature until post-cruise analysis at Old Dominion University. Dissolved iron was determined by flow injection analysis with colorimetric detection after in-line preconcentration on resin-immobilized 8-hydroxyquinoline (Sedwick et al., 2015), using a method modified from Measures et al. (1995). Analyses were performed on a volumetric basis, so concentrations are reported in units of nanomole liter-1 (nM). Analytical precision is estimated from multiple (separate-day) determinations of the SAFe seawater reference materials, which yield uncertainties (expressed as one relative standard deviation on the mean, or one sigma) of ~15% at the concentration level of SAFe S seawater (0.090 nM), and ~10% at the concentration level of SAFe D2 seawater (0.90 nM). The analytical limit of detection is estimated as the DFe concentration equivalent to a peak area that is three times the standard deviation on the zero-loading blank (manifold blank), which yields an estimated detection limit below 0.04 nM (Bowie et al., 2004). Blank contributions from the ammonium acetate sample buffer solution (added on-line during analysis) and hydrochloric acid (added after collection) are negligible.

NO3+NO2: Dissolved nitrate and nitrite was determined at sea using an Astoria Pacific nutrient autoanalyzer using standard colorimetric methods with an estimated detection limit of 0.14 µM (Parsons et al., 1984; Price and Harrison, 1987). In surface waters, nitrate and nitrite were determined using the same autoanalyzer equipped with a liquid waveguide capillary cell (World Precision Instruments) (Zhang, 2000) to achieve an estimated detection limit of 0.02 µM.

PO4: Dissolved phosphate was determined at sea using an Astoria Pacific nutrient autoanalyzer using standard colorimetric methods with an estimated detection limit of 0.03 µM (Parsons et al., 1984; Price and Harrison, 1987).

NH4: Dissolved ammonium was determined at sea using the manual orthophthaldialdehyde method (Holmes et al., 1999), with an estimated detection limit of 10 nM.

Temperature: In-situ temperature was measured using a conductivity-temperature-depth sensor (SBE 19 plus, SeaBird Electronics).

Salinity: Salinity was calculated from in-situ conductivity, as measured using a conductivity-temperature-depth (CTD) sensor (SBE 19 plus, SeaBird Electronics).

Fluorescence: In-situ chlorophyll fluorescence was measured using a WET Labs ECO-FL(RT)D deep chlorophyll fluorometer with 125 μg L-1 range mounted on the CTD rosette.