Aqueous ozonation of furans: Kinetics and transformation mechanisms leading to the formation of α,β-unsaturated dicarbonyl compounds

Abstract

Despite the widespread occurrence of furan moieties in synthetic and natural compounds, their fate in aqueous ozonation has not been investigated in detail. Reaction rate constants of seven commonly used furans with ozone were measured and ranged from kO3 = 8.5 × 104 to 3.2 × 106 M−1 s−1, depending on the type and position of furan ring substituents. Transformation product analysis of the reaction of furans with ozone focusing on the formation of toxic organic electrophiles using a novel amino acid reactivity assay revealed the formation of α,β-unsaturated dicarbonyl compounds, 2-butene-1,4-dial (BDA) and its substituted analogues (BDA-Rs). Their formation can be attributed to ozone attack at the reactive α-C position leading to furan ring opening. The molar yields of α,β-unsaturated dicarbonyl compounds varied with the applied ozone concentration reaching maximum values of 7% for 2-furoic acid. The identified α,β-unsaturated dicarbonyls are well-known toxicophores that are also formed by enzymatic oxidation of furans in the human body. In addition to providing data on kinetics, transformation product analysis and proposed reaction mechanisms for the ozonation of furans, this study raises concern about the presence of α,β-unsaturated dicarbonyl compounds in water treatment and the resulting effects on human and environmental health.