Dataset: GN01 FIA Al Fe Mn Pump

Water samples (water column, surface water, water under sea-ice, sea-ice, snow, and melt pond) were collected at 28 stations from the USCG Healy during the GEOTRACES Western Arctic research expedition, which took place during the US GEOTRACES Arctic cruise aboard USCGC Healy (HLY1502) from August 9 to October 11, 2015 in the Arctic Ocean. This dataset contains data resulting from PUMP samples.

Surface water samples were collected from a surface pump when sea ice conditions permitted. ​Surface pump samples were collected by zodiac, and a trace metal clean peristaltic pump following the GEOTRACES Program Cookbook sampling recommendations, and in accordance with previous collection protocols (Bruland et al. 2005). The pump system consisted of: a Teflon coated Tygon tubing and a rotary pump with plastic wetted parts (IWAKI magnetic drive pump, model WMD-30LFY-115) deployed from one of the USCGC Healy Rigid Hull Inflatable Boats (26 ft (7.9 m)). Samples were collected into a pre-acid cleaned 20L carboy jug and they were filtered though 0.2uM Polycarbonate (PCTE) cartridge filters in the clean container on the ship.

Additional seawater samples were collected at nominal depths of 1, 5, and 20m from under the sea ice at 6 stations, using a portable pumping system (same as described above) deployed through a hole at the station's sea ice floe. The hole was made with an ice corer (Kovacs 9 cm diameter Mak II corer), and allowed to sit undisturbed for ~ 1hr under a canvas tent prior to sampling. At these same stations, samples of melted snow (6 samples), sea-ice (5 samples), and where available melt pond (5 samples) were also obtained. These latter samples were also filtered through the 0.2 uM Acropak filter. 

Samples were drawn into pre-numbered 125 ml PMP bottles after three rinses and were stored in plastic bags in the dark at room temperature before determination which was usually within 12-36 hours of collection.

Samples were analyzed shipboard for dissolved Al, Fe & Mn using flow injection analysis methods (Resing and Measures, 1994; Measures et al., 1995, Resing and Mottl, 1992 respectively). Prior to determination samples were acidified by the addition of 125 ul sub-boiling distilled 6N HCl and were microwaved in groups of 4 for 3 minutes in a 900 W microwave oven to achieve a temperature of 60 +/- 10 ˚C. Samples were allowed to cool for at least 1 hour prior to determination. Samples were determined in groups of 8.

For preparation for standard solutions: Shipboard mixed standards (Al and Fe, Mn) were prepared in the shore-based laboratory by serial dilution of commercial Al, Fe, and Mn standards (BDH Aristar) into distilled water which was acidified with the equivalent of 4 ml sub-boiled 6N HCl. Standards for instrument calibration were prepared daily from filtered seawater by acidifying 1 L of low Fe seawater from a previous cast with 1 ml of 6N HCl and microwaving for 5 minutes to reach a temperature of 60 +/- 10˚C. After 1 hour, 200 +/- 2 ml of the cooled seawater was added to each of three 250 ml PMP bottles each of which had been rinsed three times with the microwaved seawater and shaken dry. Working standards were prepared by adding 0, +100uL, +200uL spikes of the shipboard mixed standard to these bottles, to yield a standard curve of +10.58nM and +21.16nM for Al, +0.528nM and +1.057nM for Fe, +1.45nM and +2.90nM for Mn. The system blank from the addition of the acid and buffer to samples was determined by double spiking a replicate sample i.e. by adding 2 x 125 ul 6N HCl and 5 ml of sample buffer to the replicate bottle and comparing the resulting signal to the original sample.

For dissolved Al analysis: Dissolved Al was determined using a Flow Injection Analysis scheme with fluorometric detection. Major components were a Rabbit peristaltic pump, a Dynamax FL-1 flourometer, a Rainin A/D board and a Macintosh G3 computer running Rainin MacIntegrator v 1.4.3 to log and reduce data. The analytical scheme produces a complex between lumogallion and dissolved Al which when excited at 484 nm produces flourescence at 552 nm. Detailed description of the methodology is published in Resing and Measures (1994). A 3-minute pre-concentration of sample (~9 ml) onto an 8-hydroxyquinoline (8-HQ) resin column yielded a detection limit of 0.27 and a precision of 2.1% at 12.8 nM.

For dissolved Fe analysis: Dissolved Fe was determined using a Flow Injection Analysis scheme with spectrophotometric detection (Rainin Dynamax UV-C). Major components were a Rabbit peristaltic pump, a Rainin Dynamax UV-C, a Rainin A/D board and a Macintosh G3 computer running Rainin MacIntegrator v 1.4.3 to log and reduce data. The spectrophotometric detection of the iron eluted from the column is achieved through its catalytic effect on the oxidation of N,N-dimethylp-phenylenediamine dihydrochloride (DPD) the oxidized product is measured at 514 nm. Detailed description of the methodology is published in Measures et al (1995). A 3-minute pre-concentration of sample (~9 ml) onto an 8-hydroxyquinoline (8-HQ) resin column yielded a detection limit of 0.090 nM and a precision of 0.67% at 2.96nM.

For dissolved Mn analysis: Dissolved Mn was determined using a Flow Injection Analysis scheme with spectrophotometric detection (Rainin Dynamax UV-C). Major components were a Rabbit peristaltic pump, a Rainin Dynamax UV-C, a Rainin A/D board and a Macintosh G3 computer running Rainin MacIntegrator v 1.4.3 to log and reduce data. The spectrophotometric detection of the manganese eluted from the column is achieved through its catalytic effect on the formation of malachite green which is measured at 620 nm. Detailed description of the methodology is published in Resing and Mottl (1992). A 3-minute pre-concentration of sample (~9 ml) onto an 8-hydroxyquinoline (8-HQ) resin column yielded a detection limit of 0.55 nM and a precision of 1.16% at 2.7 nM.

Calculation of each dissolved trace element concentrations: Calculation of sample concentrations was by dividing the peak height derived from sample using the A/D software by the calculated slope of the standard curve. Variations in the slope of the standard curve during a day's run were corrected by the following procedure.

The change in the value of the slope of the standard curve between each run of standards was divided by the number of samples run between those standards to provide a calculated value for the slope of the standard curve at the point each sample was run. The value of the peak height for each sample was then recalculated by the estimated ratio of the standard curve slope at the point that sample was run. The estimate of the slope at each sample run is calculated by: (Initial slope + (incremental change per sample X # of samples run since initial standard was run)). The sample concentration is then calculated from the initial standard curve slope.

The analytical blanks of dissolved Fe and Mn were determined by the shore-based ICPMS data that was measured by co-PI Dr. J. Fitzsimmons (Texas A&M University). The ICPMS data and its metadata will be submitted separately. The blank corrected FIA data was obtained from the intercept of the correlation plot between the ICPMS data and FIA data on each of the days the FIA was run.

Intercalibration for dissolved Al: GEOTRACES standard seawater and internal standard seawater were analyzed periodically. A large batch of seawater was acidified prior to the cruise and used as a primary standard during measurements. This standard seawater was run along with each sample analysis. Our laboratory has participated the GEOTRACES intercalibration effort using this flow injection method.

We report our laboratory values for the GEOTRACES GS standard analyses using this flow injection method to be: GEOTRACES GS = 29.63±1.15nM (n=2). Using 1L=1.027kg, our Al value is calculated as 28.85±1.12 nmol/kg and it is within the error of the consensus value (27.5±0.2 nmol/kg).

These results are in good agreement with this from the GEOTRACES intercalibration effort for Al and demonstrate that the methodologies employed to produce this dataset detect concentrations within the standard deviation of current consensus values.

The Al data from the GEOTRACES Arctic Ocean cruise were compared with several published data set in the various basins in the Arctic Ocean (Makarov Basin, Middag et al., 2009), the Amundsen Basin (Middag et al., 2009), and the Canada Basin (Giesbrecht et al 2013) which all show very similar results throughout the water column.