An improved microdesulphonation/gas liquid chromatography procedure for the determination of linear alkylbenzene sulphonates in U.K. rivers

Abstract

An improved microdesulphonation/gas liquid chromatography (GLC) procedure is described for the specific determination of μg l −1 levels of linear alkylbenzene sulphonates (LAS) in aqueous environmental samples including sewage, sewage effluent and surface waters. The LAS is concentrated from samples as its methylene blue complex by a large-scale solvent extraction and is then freed from potential interferences by a series of clean-up steps, i.e. ion-exchange chromatography, hydrolysis and solvent extraction, prior to its desulphonation with a concentrated phosphoric acid reagent. The resulting alkylbenzene hydrocarbons are recovered and quantitatively determined by a capillary GLC technique with the aid of internal standards (primary and secondary alkylbenzene sulphonate isomers) added at the initial concentration stage. The introduction of the clean-up stages, particularly a selective extraction of the LAS as the l-methylheptyl amine salt into hexane, has resulted in GLC traces that are free from major interferences and in which it is possible to readily identify LAS isomers on the basis of the relative retention times. The procedure has a limit of detection of less than 10 μg l −1 LAS in a sample and allows the quantification of sub-μg l −1 levels of individual isomers (C 9–C 15 homologues). The mean recovery of a C 12 LAS internal standard through the complete procedure is 91% for the environmental samples analysed. This procedure, together with a non-specific methylene blue colorimetric method (for determining anion surface active material), has been used in a monitoring exercise to establish the levels of LAS and methylene blue active substances (MBAS) in U.K. rivers and the River Rhine. A mean MBAS level of 0.15 mg l −1 was found at the U.K. river sites selected (35 samples), of which only 26% on average was attributable to LAS by microdesulphonation/GLC analysis. However, the levels of LAS and its contribution to the total MBAS in rivers was found to vary with the nature of the sampling location, i.e. depending whether it was above, below or in the vicinity of a sewage effluent discharge. The distribution of the LAS isomers at these sites also showed differences that could be explained in terms of their relative biodegradabilities.