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

<p>Competitive ligand exchange–adsorptive cathodic stripping voltammetry (CLE-AdCSV) is used to determine the conditional concentration ([<span class="inline-formula"><i>L</i></span>]) and the conditional binding strength (log<span class="inline-formula"><i>K</i>^cond</span>) 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, [<span class="inline-formula"><i>L</i></span>] and log<span class="inline-formula"><i>K</i>^cond</span> 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 is compared. The applications are (1) salicylaldoxime (SA) at 25 <span class="inline-formula">µ</span>M (SA25) and short waiting time, (2) SA at 5 <span class="inline-formula">µ</span>M (SA5), and (3) 2-(2-thiazolylazo)-<span class="inline-formula"><i>ρ</i></span>-cresol (TAC) at 10 <span class="inline-formula">µ</span>M, 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 (<span class="inline-formula"><i>D</i></span>) DTAC <span class="inline-formula">&gt;</span> DSA25 <span class="inline-formula">≥</span> SA5 (as log<span class="inline-formula"><i>D</i></span> values with respect to Fe<span class="inline-formula">³⁺</span>: 12.3 <span class="inline-formula">&gt;</span> 11.2 <span class="inline-formula">≥</span> 11).</p> <p>For the model ligands, there is no common trend in the results of log<span class="inline-formula"><i>K</i>^cond</span>. The values have a considerable spread, which indicates that the error in log<span class="inline-formula"><i>K</i>^cond</span> is large. The ligand concentrations of the nonhumic model ligands are 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 the application SA5 over- and underestimated the ligand concentration. The extent of overestimation and underestimation differed per model ligand, and the three applications showed the same trend between the nonhumic model ligands, especially for SA5 and SA25. The estimated ligand concentrations for the humic and fulvic acids differed approximately 2-fold between TAC and SA5 and another factor of 2 between SA5 and SA25.</p> <p>The use of SA above 5 <span class="inline-formula">µ</span>M suffers from the formation of the species Fe(SA)<span class="inline-formula"><i>x</i></span> (<span class="inline-formula"><i>x</i>&gt;1</span>) 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 [<span class="inline-formula"><i>L</i></span>] and could result in a false distinction into more than one ligand group.</p> <p>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.</p>