Published: April 11, 2011 r2011 American Chemical Society 3909 dx.doi.org/10.1021/es2004057 | Environ. Sci. Technol. 2011, 45, 3909–3916 ARTICLE pubs.acs.org/est Determination of Benzotriazole and Benzophenone UV Filters in Sediment and Sewage Sludge Zifeng Zhang, †,‡ Nanqi Ren, † Yi-Fan Li, †,§ Tatsuya Kunisue, ‡ Dawen Gao, † and Kurunthachalam Kannan †,‡, * † International Joint Research Center for Persistent Toxic Substances (IJRC-PTS), State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (HIT), Harbin 150090, People's Republic of China ‡ Wadsworth Center, New York State Department of Health, and Department of Environmental Health Sciences, School of Public Health, State University of New York at Albany, Empire State Plaza, PO Box 509, Albany, New York 12201-0509, United States § Science and Technology Branch, Environment Canada, Toronto, Ontario, M3H 5T4 Canada ’ INTRODUCTION A growing awareness of the risks associated with skin exposure to ultraviolet (UV) radiation over the past few decades has led to increased use of sunscreen agents, which can absorb the UV radia- tion and attenuate the negative effects; these chemicals are com- monly referred to as UV filters. Benzophenone-type UV filters are not only contained in increasing amounts in sunscreen products 1,2 but also in many products of daily use, such as cosmetics, skin creams, body lotions, hair sprays, hair dyes, and shampoos. These chemicals enter the aquatic environment either directly, via wash off from skin and clothes during water recreational activities, or indirectly, via discharge of sewage and swimming pool waters. Benzotriazole-type UV stabilizers are known to absorb a full spectrum of UV light, UV-A (320400 nm) and UV-B (280320 nm). 3 Some benzotriazole-type UV stabilizers are Received: February 3, 2011 Accepted: March 30, 2011 Revised: March 18, 2011 ABSTRACT: Benzophenones and benzotriazoles are widely used as ultraviolet (UV) light filters and stabilizers in cosmetics, skin creams, and body lotions and as corrosion inhibitors in building materials, automobile components, and automotive antifreeze cooling systems. Benzophenones and benzotriazoles have been reported to occur in the environment. Some of these UV filters have been reported to possess significant estrogenic activity. Despite this, very few studies have examined their occurrence and profiles in the environment. In this work, we determined five benzophenone-type UV filters and two benzo- triazole-type corrosion inhibitors, namely, 2-hydroxy-4-methoxy- benzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2 0 -dihydroxy-4-methoxybenzophenone (2,2 0 OH- 4MeO-BP), 2,2 0 ,4,4 0 -tetrahydroxybenzophenone (2,2 0 ,4,4 0 OH- BP), 4-hydroxybenzophenone (4OH-BP), 1H-benzotriazole (1H-BT), and 5-methyl-1H-benzotriazole (5Me-1H-BT), in se- diment and sewage sludge samples, using liquidliquid extrac- tion and liquid chromatography-tandem mass spectrometry (LCMS/MS). In addition, four benzotriazole-type UV stabilizers, namely, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), 2,4-di-t-butyl-6-(5-chloro-2H-benzotriazole-2- yl) phenol (UV-327), 2-(2H-benzotriazole-2yl)-4,6-di-t-pentylphenol (UV-328), and 2-(5-t-butyl-2-hydroxyphenyl) benzotriazole (TBHPBT) were determined by gas chromatography (GC)-mass spectrometry (MS). The limits of quantitation (LOQ) were in the ranges of 0.060.33 ng g 1 dry weight (dw) and 0.11.65 ng g 1 dw for sediment and sludge samples, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 70% to 116% (RSD: 3.3213.8%) and from 82% to 106% (RSD: 2.898.09%) for the compounds analyzed by LCMS/MS and GCMS, respectively. The methods were applied to the analysis of sediment samples from the Songhua, Saginaw, and Detroit Rivers; the sum concentrations of target compounds were 3.299.93, 5.8122.5, and 190389 ng g 1 dw, respectively. Five sludge samples collected from five wastewater treatment plants in northeastern China contained the sum concentrations of target compounds in the range of 1046370 ng g 1 dw. The concentration of UV-328 in sludge was the highest (mean: 1300 ng g 1 dw) among the target compounds. To our knowledge, this is the first work to report the occurrence of 2OH-4MeO-BP, 2,4OH-BP, 2,2 0 OH-4MeO-BP, 2,2 0 ,4,4 0 OH-BP, and 4OH-BP in sediment and sludge samples.