Synthetic iron complexes as models for natural iron-humic compounds: Synthesis, characterization and algal growth experiments

A series of monomeric and dimeric Fe^III complexes with O,O-; O,N-; O,S-coordination motifs has been prepared and characterized by standard analytical methods in order to elucidate their potential to act as model compounds for aquatic humic acids. Due to the postulated reduction of iron in humic acids and following uptake by microorganisms, the redox behavior of the models was investigated with cyclic voltammetry. Most of the investigated compounds showed iron reduction potentials accessible to biological reducing agents. Additionally, observed reduction processes were predominantly irreversible, suggesting that subsequent reactions can take place after reduction of the iron center. Also the stability of the synthesized complexes in pure water and artificial seawater was monitored from 24 h up to 21 days by means of UV–Vis spectrometry. Several complexes remained stable even after 21 days, showing only partially precipitation but some of them showed changes in UV–Vis spectra already after 24 h which were connected to protonation/deprotonation processes as well as redox processes and degradation of the complexes. The ability to act as an iron source for primary producers was tested in algal growth experiments with two marine algae species Chlorella salina and Prymnesium parvum. Some of the compounds showed effects on the algal cultures, which are comparable with natural humic acids and better as for the samples kept under ideal conditions. Those findings help to understand which functional groups of humic acids could be responsible for the reversible iron binding and transport in aquatic humic substances. - Highlights: • synthesis and characterization of a series of model complexes for aquatic humic acids providing different coordination motifs. • characterization of the complexes regarding their stability in artificial seawater and redox properties. • investigations on the impact of the synthesized model compounds on growth of the marine algae species C. salina and P. parvum. • iron complex with thiomaltol showed positive impact on the culture of C. salina and P.parvum even though thiomaltol was found to be highly cytotoxic. • catechol-based iron complexes are found to be excellent models for aquatic humic acids due to their remarkable ability to supply algae with iron.