Hydrogen Peroxide Formation during Ozonation of Olefins and Phenol: Mechanistic Insights from Oxygen Isotope Signatures

Mitigation of undesired byproducts from ozonation of dissolved organic matter (DOM) such as aldehydes and ketones is currently hampered by limited knowledge of their precursors and formation pathways. Here, the stable oxygen isotope composition of H2O2 formed simultaneously with these byproducts was studied to determine if it can reveal this missing information. A newly developed procedure, which quantitatively transforms H2O2 to O2 for subsequent 18O/16O ratio analysis, was used to determine the 618O of H2O2 generated from ozonated model compounds (olefins and phenol, pH 3-8). A constant enrichment of 18O in H2O2 with a 618O value of similar to 59%o implies that 16O-16O bonds are cleaved preferentially in the intermediate Criegee ozonide, which is commonly formed from olefins. H2O2 from the ozonation of acrylic acid and phenol at pH 7 resulted in lower 18O enrichment (618O = 47-49%o). For acrylic acid, enhancement of one of the two pathways followed by a carbonyl-H2O2 equilibrium was responsible for the smaller 618O of H2O2. During phenol ozonation at pH 7, various competing reactions leading to H2O2 via an intermediate ozone adduct are hypothesized to cause lower 618O in H2O2. These insights provide a first step toward supporting pH -dependent H2O2 precursor elucidation in DOM.