Transformation and stable isotope fractionation of the urban biocide terbutryn during biodegradation, photodegradation and abiotic hydrolysis

Terbutryn is a widely used biocide in construction materials like paint and render to prevent the growth of microorganisms, algae and fungi. Terbutryn is released from the facades into the environment during rainfall, contaminating surface waters, soil and groundwater. Knowledge of terbutryn dissipation from the facades to aquatic ecosystems is scarce. Here, we examined in laboratory microcosms degradation half-lives, formation of transformation products and carbon and nitrogen isotope fractionation during terbutryn direct (UV light with lambda = 254 nm and simulated sunlight) and indirect (simulated sunlight with nitrate) photodegradation, abiotic hydrolysis (pH = 1, 7 and 13), and aerobic biodegradation (stormwater pond sediment, soil and activated sludge). Biodegradation half-lives of terbutryn were high (> 80 d). Photodegradation under simulated sunlight and hydrolysis at extreme pH values indicated slow degradability and accumulation in the environment. Photodegradation resulted in a variety of transformation products, whereas abiotic hydrolysis lead solely to terbutryn-2-hydroxy in acidic and basic conditions. Biodegradation indicates degradation to terbutryn-2-hydroxy through terbutryn-sulfoxide. Compound-specific isotope analysis (CSIA) of terbutryn holds potential to differentiate degradation pathways. Carbon isotope fractionation values (epsilon C) ranged from-3.4 +/- 0.3 parts per thousand (hydrolysis pH 1) to +0.8 +/- 0.1 parts per thousand (photodegradation under UV light), while nitrogen isotope fractionation values ranged from-1.0 +/- 0.4 parts per thousand (simulated sunlight photodegradation with nitrate) to +3.4 +/- 0.2 parts per thousand (hydrolysis at pH 1). In contrast, isotope fractionation during biodegradation was insignificant. lambda(N/C) values ranged from-1.0 +/- 0.1 (hydrolysis at pH 1) to 2.8 +/- 0.3 (photodegradation under UV light), allowing to differentiate degradation pathways. Combining the formation of transformation products and stable isotope fractionation enabled identifying distinct degradation pathways. Altogether, this study highlights the potential of CSIA to follow terbutryn degradation in situ and differentiate prevailing degradation pathways, which may help to monitor urban biocide remediation and mitigation strategies.