Photochemical cycling of iron mediated by dicarboxylates: special effect of malonate

Photochemical redox cycling of iron coupled with oxidation of malonate (Mal) ligand has been investigated under conditions that are representative of atmospheric waters. Malonate exhibited significantly different characteristics from oxalate and other dicarboxylates (or monocarboxylates). Both strong chelating ability with Fe(III) and strong molar absorptivities, but much low efficiency of Fe(II) formation (Φ_Fe(II) = 0.0022 ± 0.0009, 300−366 nm) were observed for Fe(III)−Mal complexes (FMCs). Fe(III) speciation calculation indicated that Mal is capable of mediating the proportion between two photoactive species of Fe(III)−OH complexes and FMCs by changing the Mal concentration. Spin-trapping electron spin resonance (ESR) experiments proved the formation of both the ^·CH₂COOH and ^·OH radicals at lower total Mal concentration ([Mal]_T), but only ^·CH₂COOH at higher concentrations of malonate, providing strong evidence for competition between malonate and OH⁻ and subsequent different photoreaction pathways. Once FMCs dominate the Fe(III) speciation, both photoproduction and photocatalyzed oxidation of Fe(II) will be greatly decelerated. There exists an induction period for both formation and decay of Fe(II) until Fe^III(OH)²⁺ species become the prevailing Fe(III) forms over FMCs as Mal ligand is depleted. A quenching mechanism of Mal in the Fe(II) photoproduction is proposed. The present study is meaningful to advance our understanding of iron cycling in acidified carbon-rich atmospheric waters.