Picolinic acid promotes organic pollutants removal in Fe(III)/periodate process: Mechanism and relationship between...

The application of Fe-catalyzed periodate (PI) processes is often limited by both the narrow applicable pH range and weak reaction between Fe(III) and oxidant. Here, the biodegradable picolinic acid (PICA) was used as one kind of chelating ligands (CLs) to enhance the removal of organic pollutants (OPs) at initial pH 3.0-8.0, which displayed superior properties than the other CLs in Fe(III)/PI process. The dominant reactive species produced in the Fe(III)-PICA/PI process turned out to be high-valent iron-oxo (Fe^IV=O) species and hydroxyl radical (^•OH) by quenching, sulfoxide probe transformation, and ¹⁸O isotope-labeling tests. The relative contribution of Fe^IV=O and ^•OH was dependent on OPs ionization potential (IP) and energy gap (ΔE). The degradation of OPs was also directly associated with their structure, the apparent rate constants correlated well with the highest occupied molecular orbital energy (E_HOMO), IP, and ΔE, and among them ΔE had a greater effect. Furthermore, Fe(III)-PICA complexes displayed excellent long-term effectiveness for OPs removal in actual water matrixes, along with the non-toxic conversion of PI, indicating a broad application perspective of Fe(III)-PICA/PI process. This study provides an efficient method to improve the performance of Fe(III)/PI process and reveals the mechanism and relationship between removal efficiency and pollutant structure.