Barren ground is a phenomenon associated with the depletion of seaweed in coastal areas. The development of barren ground has been attributed to a lack of soluble Fe (<1 nM), 1 which is an essential micronutrient for the growth of algae. 2,3 In macroalgae, the uptake of soluble iron is required for the gametophyte to produce an oogonium or an antheridium, 4-7 and a sporophyte is formed from the matured gametophyte. 3 Thus, a lack of dissolved Fe in coastal area seawater can lead to seaweed depletion. It is known that natural organic matter plays an important role in the mobility, solubility and bioavailability of trace metals in terrestrial and aquatic environments. 2,[8][9][10][11][12] In seawater, the majority of dissolved ferric (Fe(III)) and ferrous (Fe(II)) species are present in the form of complexes with dissolved organic matter. 2,[13][14][15] Based on this, a fertilizer comprised of a steel slag and compost was tested for its ability to supply dissolved Fe to barren coastal areas, and this attempt was successful and resulted in the restoration of seaweed beds. 16 In this technique, seawater extractable organic matter (SWEOM) from the compost serves as a chelator of Fe and allows for its elution from the steel slag. 17,18 Fe(III)-oxides are found on the surface of the steel slag, 19 and can be reduced to soluble Fe(II) species in the presence of dissolved organic matter. 20 It has been reported that all of the reduced Fe(II) species are complexed with dissolved organic matter. 21 Therefore, the nature of the complex produced between SWEOM and Fe(II) need to be evaluated to better understand the performance of such fertilizers.On the other hand, estimating the bioavailability of a metal to aquatic biota is an important approach. 22,23 The kinetic stability of complexes is a key factor in determining the bioavailability of metal species. 2,3,22,24,25 Readily dissociable complexes (labile species) are the likely primary source of soluble iron for algae. 2,19,[26][27][28] A key factor in the uptake of Fe(II) involves ligand-exchange reactions between dissolved organic matter and receptor proteins on the cell-membrane. 2 The kinetics of ligand-exchange reactions of Fe(II)-humic acid complexes have been investigated using ortho-phenanthroline or ferrozine (FZ) as models of receptor proteins, 17,29 although the conditions (pH 3.6 or 5, I = 0.02) were far from those for seawater (pH 8, I = 0.7). To investigate the contribution of SWEOM as a chelator of Fe, it should be examined that the complexation ability under the conditions of seawater. However, it is difficult to determine both free and complex species of Fe(II) at higher pH and ionic strength levels because Fe(II) is readily oxidized to insoluble Fe(III)-hydroxides, which precipitates from the solution. 30 Indeed, pH and ionic strength both have a dramatic 2013 © The Japan Society for Analytical Chemistry † To whom correspondence should be addressed.
Experimental
MaterialsAmmonium iron(II) sulfate hexahydrate (Fe(SO4)2(NH4)2·6H2O), tris(hydroxymethyl)ami...