Effects of NOM on oxidative reactivity of manganese dioxide in binary oxide mixtures with goethite or hematite

MnO2 typically coexists with iron oxides as either discrete particles or coatings in soils and sediments. This work examines the effect of Aldrich humic acid (AHA), alginate, and pyromellitic acid (PA) as representative natural organic matter (NOM) analogues on the oxidative reactivity of MnO2, as quantified by pseudo-first-order rate constants of triclosan oxidation, in mixtures with goethite or hematite. Adsorption studies showed that there was low adsorption of the NOMs by MnO2, but high (AHA and alginate) to low (PA) adsorption by the iron oxides. Based on the ATR-FTIR spectra obtained for the adsorbed PA on goethite or goethite + MnO2, the adsorption of PA occurred mainly through formation of outer-sphere complexes. The Fe oxides by themselves inhibited MnO2 reactivity through intensive heteroaggregation between the positively charged Fe oxides and the negatively charged MnO2; the low solubility of the iron oxides limited surface complexation of soluble Fe(3+) with MnO2. In ternary mixtures of MnO2, Fe oxides, and NOM analogues, the reactivity of MnO2 varied from inhibited to promoted as compared with that in the respective MnO2 + NOM binary mixtures. The dominant interaction mechanisms include an enhanced extent of homoaggregation within the Fe oxides due to formation of oppositely charged patches within the Fe oxides but an inhibited extent of heteroaggregation between the Fe oxide and MnO2 at [AHA] < 2-4 mg-C/L or [alginate/PA] < 5-10 mg/L, and an inhibited extent of heteroaggregation due to the largely negatively charged surfaces for all oxides at [AHA] > 4 mg-C/L or [alginate/PA] > 10 mg/L.