Environmental Context. Aquatic life requires access to sufficient nutrients and trace metals in the surrounding waters. Measuring the speciation (in solution or precipitated, free ionic or complexed) of trace metals is a traditional procedure to assess the potential of waters for life. Iron, an important nutrient, is relatively insoluble, and metal–ligand complexes are required to keep the iron in solution and bioavailable. Sunlight often degrades these metal–ligand complexes, and the subsequently released iron can outcompete other (trace) metals for their ligands. A ‘domino’ effect on weaker metal–ligand complexes will occur which complicates the actual dynamic speciation and its measurements.

Abstract. The effect of photodegradation of iron(iii)-EDTA on the chemical speciation of both iron and cobalt has been tested both in a simple medium and in a more complex algal growth medium. In both media, the photodegradation of iron(iii)-EDTA caused iron(iii) to be released as a free ionic species. Released iron(iii) could be modelled as engaged in precipitation and in competition with cobalt, initially also bound to EDTA. Cobalt appeared as free ionic species after a certain lag. The length of this lag phase was proportional to the amount of EDTA added to the media, which indicated that the surplus of EDTA was first targetted by iron(iii)-EDTA photodegradation, after which iron(iii) out-competed cobalt for the EDTA in the metal–EDTA pool. All data were fitted, using a model on speciation kinetics for cobalt-EDTA and iron(iii)-EDTA, taking into account photodegradation rates of iron(iii)-EDTA and precipitation of free iron(iii). The modelled rate of iron(iii)-EDTA photodegradation was compared to direct HPLC measurements of the disappearance of iron(iii)-EDTA due to photodegradation, the latter, however, with a different iron(iii)-EDTA concentration regime. The results suggest that photodegradation is a complex process which is greatly influenced by experimental conditions (e.g. light intensity/spectrum, iron(iii), and EDTA concentrations). Iron(iii)-desferrioxamine B (DFO-B) was suggested as a possible alternative for EDTA in experimental media: photostability was shown for prolonged experimental periods.