Dissolved iron (DFe) concentrations determined by flow injection analysis (FIA) in Peter Sedwick’s lab at Old Dominion University were used in the data interpretation to calculate ligand concentrations and conditional stability constants from the sample titrations. The DFe values used for this dataset are provided in the speciation submission for reference, please see Sedwick et al. (2015) for the complete dissolved iron data and methods.

Titration data was interpreted with a combination of Scatchard (Scatchard 1949) and van den Berg-Ruzic (Ruzic 1982; van den Berg 1982) linearization techniques, as has been described previously (Buck et al. 2012, 2015, 2016). An inorganic side reaction coefficient, a_Fe_¢, of 10¹⁰ was used in the iron speciation calculations (Buck et al. 2012). Ligand concentrations and conditional stability constants determined from each linearization of a titration dataset were then combined for a final ligand concentration and conditional stability constant for each sample. When available, results from replicate titration analyses were averaged together and the average with standard deviations of all sample titrations were then reported for each parameter in the spreadsheet.

The detection limit for the electroactive Fe-SA complex has been found to be 0.01 nM (Buck et al. 2007), calculated as three times the standard deviation of measured peak height from a 0.05 nM Fe addition to UV-oxidized and chelexed seawater with a 900 s deposition time. For a 90 s deposition time, the detection limit for Fe-SA is ~0.1 nM. Two stations from the US GTNA cruises (2010-Stn5 and 2010-Stn 9) were analyzed in triplicate complete titrations, typically two conducted shipboard and one in the laboratory after storing frozen (-20 ºC). Over the full water column from both stations, the average standard deviation from the triplicate titrations of each sample was 0.11 nM (n = 36 samples, 108 titrations), and three times this standard deviation estimates a detection limit for ligand concentrations of 0.33 nM. For log K₁ values of this ligand class, from the same profiles, the average standard deviation was 0.15 (log units).

Related files and references:

Buck, K. N., L. J. A. Gerringa, and M. J. A. Rijkenberg. 2016. An intercomparison of dissolved iron speciation at the Bermuda Atlantic Time-series Station (BATS): Results from the GEOTRACES Crossover Station A. Frontiers in Marine Biogeochemistry 3: article 262.

Buck, K. N., M. C. Lohan, C. J. M. Berger, and K. W. Bruland. 2007. Dissolved iron speciation in two distinct river plumes and an estuary: Implications for riverine iron supply. Limnology and Oceanography 52: 843-855.

Buck, K. N., K. E. Selph, and K. A. Barbeau. 2010. Iron-binding ligand production and copper speciation in an incubation experiment of Antarctic Peninsula shelf waters from the Bransfield Strait, Southern Ocean. Marine Chemistry 122: 148-159.

Buck, K. N., J. W. Moffett, K. A. Barbeau, R. M. Bundy, Y. Kondo, and J. Wu. 2012. The organic complexation of iron and copper: an intercomparison of competitive ligand exchange- adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques. Limnology and Oceanography: Methods 10: 496-515.

Buck, K. N., B. Sohst, and P. N. Sedwick. 2015. The organic complexation of dissolved iron along the U.S. GEOTRACES (GA03) North Atlantic Section. Deep-Sea Research 116: 152-165.

Rue, E. L., and K. W. Bruland. 1995. Complexation of iron(III) by natural organic ligands in the Central North Pacific as determined by a new competitive ligand equilibration adsorptive cathodic stripping voltammetric method. Marine Chemistry 50: 117-138.

Ružić, I. 1982. Theoretical aspects of the direct titration of natural waters and its information yield for trace metal speciation. Analytica Chimica Acta 140: 99-113.

Scatchard, G. 1949. The attractions of proteins for small molecules and ions. Annals of the New York Academy of Sciences 51: 660-672.

Sedwick, P. N., B. M. Sohst, S. J. Ussher, and A. R. Bowie. 2015. A zonal picture of the water column distribution of dissolved iron(II) during the U.S. GEOTRACES North Atlantic transect cruise (GEOTRACES GA03). Deep-Sea Research II 116: 166-175.

van den Berg, C. M. G. 1982. Determination of copper complexation with natural organic ligands in sea water by equilibrium with MnO2: I. Theory. Marine Chemistry 11: 307-322.

FLAG: The standard Ocean Data View qualifying flags were used (reference all flags at https://www.bodc.ac.uk/data/codes_and_formats/odv_format/):

1: Good Value: Good quality data value that is not part of any identified malfunction and has been verified as consistent with real phenomena during the quality control process. [Used when data were shown to be reproducible]

2: Probably Good Value: Data value that is probably consistent with real phenomena but this is unconfirmed or data value forming part of a malfunction that is considered too small to affect the overall quality of the data object of which it is a part. [Used when the reported value reflects analysis of a single or unverified replicate]

3: Probably Bad Value: Data value recognized as unusual during quality control that forms part of a feature that is probably inconsistent with real phenomena. [Not used]

4: Bad Value: An obviously erroneous data value. [Not used]

5: Changed Value: Data value adjusted during quality control. [Not used]

6: Value Below Detection Limit: The level of the measured phenomenon was too small to be quantified by the technique employed to measure it. The accompanying value is the detection limit for the technique or zero if that value is unknown. [We report “not_detected” rather than zero or a detection limit value for this case]

7: Value in Excess: The level of the measured phenomenon was too large to be quantified by the technique employed to measure it. The accompanying value is the measurement limit for the technique. [Not used]

8: Interpolated Value: Tis value has been derived by interpoloation from other values in the data object. [Not used]

9: Missing Value: The data value is missing. Any accompanying value will be a magic number representing absent data. [Any missing data reflect samples that were not analyzed; “nd” = “no data” used for these parameters]

A: Value Phenomenon Uncertain: There is uncertainty in the description of the measured phenomenon associated with the value such as chemical species or biological entity. [Not used]

BCO-DMO Processing:
- added conventional header with dataset name, PI name, version date
- column names reformatted to comply with BCO-DMO or GEOTRACES standards
- joined submitted data with master event data: depth_GEOTRC_CTD, event_GEOTRC, instr, cast_GEOTRC, sample_GEOTRC, sample_bottle_GEOTRC, bottle_GEOTRC.
- changed 95%CI to stdev (standard deviation) in headers as per email 2016-12-007 from KB
- changed latitude and longitude for GeoFish samples from 'towfish position' to 'nd' (no data)
- converted longitude to negative degrees

Fe_spec_v6_fish_btl_joined.csv