Carbonate Alkalinity Enhances Triclosan Photolysis

Abstract

Triclosan (TCS) is an antimicrobial compound found in many household products used across the world. TCS is not completely removed in wastewater systems, resulting in trace-level concentrations present ubiquitously in surface waters. The direct photodegradation of TCS has been widely studied, with results indicating that TCS breaks down to chlorophenols and dioxins. To date, no studies have specifically investigated the effects of alkalinity on the photolysis of the acidic form of TCS. This study assessed the effect of carbonate/bicarbonate alkalinity, which is ubiquitous in natural waters, on the photolysis rate of TCS. Results indicate that bicarbonate enhances the photodegradation of TCS at pH values well below the pK_a of TCS (7.9), with direct photolysis reaction kinetics that are very slow in the absence of buffers, but significant in the presence of bicarbonate (0.711 h⁻¹ at pH 6.55). At pH values well above its pK_a, both unbuffered- and buffered-mediated photolysis increased dramatically (1.92 h⁻¹ for direct photolysis and 2.86 h⁻¹ in buffered water) and is attributable to the increased photoreactivity of TCS by its conjugate base. Photolysis of methyl triclosan (MeTCS), a non-acidic analog of TCS, demonstrated the importance of TCS’s acidic functionality as MeTCS did not degrade at any pH. The observed influence of alkalinity on the acidic form of TCS photolysis was attributed to both a decrease in its excited state pK_a, coupled with TCS deprotonation through an excited state proton transfer to a base (bicarbonate and to a lesser degree hydrogen phosphate) resulting in the more photo-labile conjugate base form of TCS.