963 (2002) 159–167 Journal of Chromatography A, www.elsevier.com / locate / chroma Development of a solid-phase microextraction method for the determination of short-ethoxy-chain nonylphenols and their brominated analogs in raw and treated water a a, b * ´ Alfredo Dıaz , Francesc Ventura , M. Teresa Galceran a ¨ AGBAR, Aigues de Barcelona, Pg. Sant Joan, 39, 08009 Barcelona, Spain b ´ ` University of Barcelona, Department Analytical Chemistry, Martı i Franques,1 –11, 08028 Barcelona, Spain Abstract A direct solid-phase microextraction (SPME) procedure has been developed and applied for the simultaneous determination of nonylphenol, nonylphenol mono- and diethoxylates and their brominated derivatives in raw and treated 21 water at low mgl concentrations. Several parameters affecting the SPME procedure, such as extraction mode (headspace or direct-SPME), selection of the SPME coating, extraction time, addition of organic modifiers such as methanol and temperature were optimized. The divinylbenzene–carboxen–polydimethylsiloxane fiber was the most appropriate one for the determination of nonylphenol ethoxylates (NPEOs) and bromononylphenol ethoxylates (BrNPEOs) by SPME–GC–MS. The 21 optimized method was linear over the range studied (0.11–2.5 mgl ) and showed good precision, with RSD values 21 between 4 and 15% and detection limits ranging from 30 to 150 ng l depending on the compound. The SPME procedure was compared with a solid-phase extraction–GC–MS method (C cartridge) for the analysis of NPEO and BrNPEOs in 18 water samples. There was good agreement between the results from both methods but the SPME procedure showed some advantages such as lower detection limits, a shorter analysis time and the avoidance of organic solvents. The optimized SPME method was applied to determine nonylphenol and brominated metabolites in raw and treated water of Barcelona (NE Spain).  2002 Elsevier Science B.V. All rights reserved. Keywords: Solid-phase microextraction; Water analysis; Nonylphenols; Ethoxylates; Organobromine compounds; Halo- genated compounds 1. Introduction conditions [3]. Further oxidation of the ethoxylate chain produces carboxylated metabolites [4]. It has Nonylphenol ethoxylates (NPnEO n5number of also been shown that these metabolites can react ethoxy units) are widely used nonionic surfactants. during chlorination in water treatment plants produc- The biodegradation of the parent compound under ing mainly brominated derivatives if bromide is aerobic conditions leads mainly to the formation of present. Thus, brominated nonylphenols have been nonylphenol mono- and diethoxylate (NP1EO and identified in wastewater [5], tap water [6], sediments NP2EO) [1,2], whereas the fully deethoxylated [7] and sludge [8]. Fig. 1 displays the chemical nonylphenol (NP) is also produced under anaerobic structures and acronyms used. Concerns over the toxicity of NPEOs and their biodegradation products have restricted their use in *Corresponding author. Fax: 134-93-342-3666. E-mail address: fventura@agbar.es (F. Ventura). industrial applications in Europe. Recently, several 0021-9673 / 02 / $ – see front matter  2002 Elsevier Science B.V. All rights reserved. PII: S0021-9673(02)00542-3