Journal of Chromatography A, 1217 (2010) 2925–2932 Contents lists available at ScienceDirect Journal of Chromatography A journal homepage: www.elsevier.com/locate/chroma At-line microextraction by packed sorbent-gas chromatography–mass spectrometry for the determination of UV filter and polycyclic musk compounds in water samples Monika Moeder a,∗ , Steffi Schrader a , Ursula Winkler a , Rosario Rodil b a Helmholtz Centre for Environmental Research - UFZ, Department of Analytical Chemistry, Permoserstrasse 15, D-04318 Leipzig, Germany b Department of Analytical Chemistry, Nutrition and Food Science, IIAA-Institute for Food Analysis and Research, University of Santiago de Compostela, 15782-Santiago de Compostela, Spain article info Article history: Received 23 July 2009 Received in revised form 19 February 2010 Accepted 24 February 2010 Available online 3 March 2010 Keywords: Microextraction by packed sorbents (MEPSs) UV filters Polycyclic musk compounds Large volume injection-gas chromatography–mass spectrometry (LVI-GC–MS) abstract An at-line analysis protocol is presented that allows the determination of four UV filters, two polycyclic musk compounds and caffeine in water at concentration level of ng L -1 . The fully automated method includes analytes enrichment by Microextraction by packed sorbent (MEPS) coupled directly to large volume injection-gas chromatography–mass spectrometry. Two common SPE phases, C8 and C18, were examined for their suitability to extract the target substances by MEPS. The analytes were extracted from small sample volumes of 800 L with recoveries ranging from 46 to 114% for the C8-sorbent and 65–109% for the C18-sorbent. Limits of detection between 34 and 96 ng L -1 enable the determination of the analytes at common environmental concentration levels. Both sorbents showed linear calibration curves for most of the analytes up to a concentration level of 20 ng mL -1 . Carryover was minimized by washing the sorbents 10 times with 100 L methanol. After this thorough cleaning, the MEPS are re-used and up to 70 analyses can be performed with the same sorbent. The fully automated microextraction GC–MS protocol was evaluated for the influence of matrix substances typical for wastewater. Dilution of samples prior to MEPS is recommended when the polar caffeine is present at high concentration. Real water samples were analyzed by the MEPS-GC–MS method and compared to standard SPE. © 2010 Elsevier B.V. All rights reserved. 1. Introduction UV filters and polycyclic musk compounds, chosen as target analytes, are additives in personal care products and considered as chemicals of daily use. In addition, UV filters are used for protecting materials against disrupting UV radiation in industrial applications. Polycyclic musk compounds are produced as syn- thetic fragrances which substitute the “nitromusk” compounds phased out from application due to their persistence, potential bioaccumulation and toxicological effects found in in vitro experi- ments [1,2]. The UV filter compounds 4-methyl-benzylidene camphor (4-MBC), octocrylene (OC), and ethylhexyl methoxycinnamate (EHMC) shared 53, 35 and 81% of the market of sun-screen formu- lations in 2001 [3]. These compounds were detected in wastewater at concentrations between 0.1 and 19 gL -1 (raw wastewater) and <0.01–2.7 gL -1 in treated wastewater [4]. In lakes of recreation resorts the occurrence of UV filters such as 4-MBC, benzophenone- ∗ Corresponding author. Tel.: +49 341 2351413; fax: +49 341 2351443. E-mail address: monika.moeder@ufz.de (M. Moeder). 3 (BP-3), OC, and EHMC varies seasonally and concentrations between 5 and 250 ng L -1 were reported previously [5]. In 2000 the production of the two most frequently applied, polycyclic musk compounds, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8- hexamethylcyclopenta-gamma-2-benzopyrane (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (AHTN), raised to 1800 tons in Europe [6]. Today their input into the food chain is known and recent investigations indicated that HHCB can inhibit cellular detoxification processes [7]. Endocrine disrupting effects of musk compounds and UV filters such as 4-MBC have been proved in vitro [8–10] and their potential accumulation [9,11] and persistence turn the polycyclic musk com- pounds and UV filters into environmental pollutants that should be monitored [12]. The commonest procedure to separate and concentrate these pollutants from aqueous samples is solid phase extraction (SPE) [13], an often time- and labor-consuming procedure of limited automation grade particularly in combination with GC. Thus, miniaturization of extraction methods is a promising approach to reduce time and labor-effort in sample preparation. The small scale enables handling of very little sample volumes as needed for instance for the analysis of body fluids, save chemicals and sol- 0021-9673/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.chroma.2010.02.057