Effects of organic matter and alkalinity on the ozonation of antiviral purine derivatives as exemplary micropollutant motif

Ozonation of micropollutants strongly depends on the water matrix. Natural organic matter is known to highly affect the hydroxyl radical exposure due to radical promoting and inhibiting effects. Other important matrix components in ozonation are carbonate species which scavenge hydroxyl radicals. However, additional factors such as the formation of other radicals might also play a role but are generally not covered in research or considered in modelling of micropollutant degradation. Hence, the ozonation of purine derivatives, the basic structure of various antiviral micropollutants, in different artificial water matrices is investigated in this study with focus on the impact of natural organic matter and increasing alkalinity on the degradation and product formation. The degradation of purine and adenine is inhibited by bicarbonate in the water matrix due to the anion's scavenging of hydroxyl radicals. This effect is already observed for low bicarbonate concentrations of 0.3 mM. However, formed carbonate radicals contribute to the compounds' degradation and also affect the stability of transformation products. This effect gains in relevance with increasing alkalinity and needs consideration in evaluating ozonation of very hard waters. Three ozonation products are evaluated in detail, which are affected by the matrix due to impacts on ozone stability, hydroxyl radical yield and carbonate radical formation. One product of adenine with the mass 147 was reported for the first time and only occurs in presence of matrix components. Under typical water treatment conditions rough predictions of pollutants' degradation are possible by the Rct concept using ozone and hydroxyl radical exposures. However, other reactive species such as car-bonate radicals are not considered leading to deviations between modelled and experimental data at extreme conditions such as industrial wastewater. A general correlation between the Rct and the fraction f of hydroxyl radicals scavenged by bicarbonate (ln(Rct) = -5.9 x f -16.3) calculated from the concentration of organic matter and alkalinity was observed for various water samples allowing the estimation of micropollutant degradation during ozone treatment at moderate conditions by simple organic and inorganic carbon measurements.

Automated summary

The ozonation of micropollutants is greatly influenced by the composition of water, particularly the presence of natural organic matter and carbonate species. In this study, the degradation and product formation of purine derivatives, which are common antiviral micropollutants, were investigated in different artificial water matrices, with a focus on the impact of natural organic matter and alkalinity. It was found that the presence of bicarbonate in the water matrix inhibited the degradation of purine and adenine due to the scavenging of hydroxyl radicals. However, the formation of carbonate radicals contributed to the degradation of compounds and affected the stability of transformation products, especially in high alkalinity conditions.