Accelerated oxidation of microcystin-LR by Fe(II)-tetrapolyphosphate/oxygen in the presence of magnesium and calcium ions

Fe(II)-tetrapolyphosphate complexes are known to activate molecular oxygen (Fe(II)-TPP/O₂) to produce reactive oxidants (most likely, Fe(IV)-TPP complexes) that are capable of degrading refractory organic contaminants in water. This study found that magnesium and calcium ions (Mg²⁺ and Ca²⁺) accelerate the degradation of micfrocystin-LR (MC-LR), the most toxic and abundant cyanotoxin, by the Fe(II)-TPP/O₂ system. The addition of Mg²⁺ and Ca²⁺ increased the observed rate constant of MC-LR degradation by up to 4.3 and 14.8 folds, respectively. Mg²⁺ and Ca²⁺ accelerated the MC-LR degradation in the entire pH range, except for the alkaline region with pH > ca. 10. The addition of Mg²⁺ and Ca²⁺ also reshaped the pH-dependency of the MC-LR degradation, greatly increasing the rate of MC-LR degradation at neutral pH. It was found that Mg²⁺ and Ca²⁺ accelerate the reaction of Fe(II)-TPP complexes with oxygen, resulting in faster production of reactive oxidants. The findings from cyclic voltammetry and potentiometric titration suggest that Mg²⁺ and Ca²⁺ form ternary complexes with Fe(II)-TPP, which exhibit higher reactivity with oxygen. Due to the effects of Mg²⁺ and Ca²⁺, the rate of MC-LR degradation by the Fe(II)-TPP/O₂ system was even higher in natural water than in deionized water.