Comparing CLE-AdCSV applications using SA and TAC to determine the Fe binding characteristics of model ligands in seawater Version 12

Competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-AdCSV) is used to determine the conditional concentration ([L]) and the conditional binding strength (logKcond) of dissolved organic Fe-binding ligands, which together influence the solubility of Fe in seawater. Electrochemical applications of Fe speciation measurements vary predominantly in the choice of the added competing ligand. Although different applications show the same trends, [L] and logKcond differ between the applications. In this study, binding of two added ligands in three different common applications to three known types of natural binding ligands are compared. The applications are: 1) Salicylaldoxime (SA) at 25 micromol (SA25) and short waiting time, 2) SA at 5 micromol (SA5) and 3)2-(2-thiazolylazo)-rho-cresol (TAC) at 10 micromol, the latter two with overnight equilibration. The three applications were calibrated under the same conditions, although having different pH values, resulting in the detection window centers (D) DTAC > DSA25 >/= SA5 (as log D values with respect to Fe3+: 12.3>11.2>/= 11). For the model ligands, there is no common trend in the results of logKcond. The values have a considerable spread, which indicates that the error in logKcond is large. The ligand concentrations of the non humic model ligands are underestimated by TAC and overestimated by SA25 which we attribute to the lack of equilibrium between Fe-SA species in the SA25 application. The application TAC more often underestimated the ligand concentrations and Application the application SA5 was best in estimating over and under estimated the ligand concentration correctly. The trends between these model ligand concentrations were similar for all three applications. The estimated ligand concentrations for the humic and fulvic acids differed approximately by a factor 22 fold between TAC and SA5 and another factor of 2 between SA5 and SA25. The use of SA above 5 micromol suffers from the formation of the species Fe(SA)x (x>1) that is not electro-active as already suggested by Abualhaija and Van den Berg (2014). Moreover, we found that the reaction between the electro-active and non-electro-active species is probably irreversible. This undermines the assumption of the CLE principle, causes overestimation of [L] and could result in a false distinction into more than one ligand group. For future electrochemical work it is recommended to take the above limitations of the applications into account. Overall, the uncertainties arising from the CLE-AdCSV approach mean we need to search for new ways to determine the organic complexation of Fe in seawater.