Publications

During the last years there has been an increasing concern for polybrominated diphenyl ethers (PBDEs) as environmental pollutants. These compounds are used as additive flame retardants in a wide range of materials1 and have been found in sediments, sewage sludge and marine biota as well as in human blood and mothers milk2. The use of the fully brominated BDE-209 has been increasing while the use of the less brominated congeners is decreasing. Even though the BDE-209 is one of the most commonly used PBDE commercially only a few number of determinations have been reported, for instance in human blood3 and in air4, 5.
Gas chromatography is today the method of choice for the separation of PBDE due to high resolution and low detection limits using either the electron capture detector (ECD) or mass spectrometry (MS). Splitless is the most commonly used injection technique for GC separation of PBDE6. However, both the septum equipped temperature programmable injector (SPI) and the programmable temperature vaporising (PTV), injector as well as on-column has been successfully used6. Large volume injections (LVI) using either the PTV in solvent elimination mode or the loop type interface have also been used4, 7, 8. The injection of PBDE into the GC system is a critical and important part of the chromatographic analysis. Thus, a careful selection and optimization the injection techniques have to be performed in order to reduce the discrimination of theses compounds. In this paper we present an evaluation and optimisation of the most commonly used injection techniques for PBDE.

New separation/detection procedures by reversed-phase HPLC coupled with UV and fluorescence detection have been developed for the determination of organic admixtures of the sulphonated melamines-formaldehyde condensates (SMFC) and lignosulphonates (LS) type in environmental samples (drinking and ground waters), as well as in concrete leachates. The developed method permitted to reach detection limits in the 0.05-0.3 µg range (as injected amount). An extraction/enrichment method from the titled environmental samples based on solid-phase-extraction (SPE) has been developed for SMFC by using polystyrene-divinylbenzene (PS-DVB, Envichrom-P) resin as sorbent. SMFC were extracted (recovery: ca . 70%) from aqueous samples at starting concentrations down to 10 µg/L. A structural confirmation of SMFC in aqueous samples was established by HPLC/Mass Spectrometry with electrospray interface (HPLC-ESI-MS) by using collision-induced ion fragmentation (in source-CID mode). The developed analytical procedures were applied to the determination of SMFC and LS in commercial blends, in drinking and ground waters, as well as in industrial effluents and liquors from leaching test experiments. Only shorter SMFC and LS components were identified as result of the leaching from concrete specimen.

A large volume injection fast-GC–MS method has been developed, optimized and evaluated for the determination of polybrominated diphenyl ethers, including the decabrominated diphenyl ether (BDE-209). The programmed-temperature vaporiser injection parameters, temperature programming of the GC oven, and the physical dimensions of the narrow bore GC column were investigated to find the optimal operating conditions for the analysis. Depending on parameter settings the yield of the PBDEs and particularly BDE-209, varies significantly. Volumes up to 125 microL were successfully injected and a fast GC separation was performed, with retention times as short as 6.4 min for the last eluting compound, BDE-209. In a pilot study an air sample, collected at an electronics dismantling facility, was analyzed. Low-resolution mass spectrometry in electron capture negative ion mode was used for detection. Nine BDE congeners, including BDE-209, were identified and quantified.