Occurrence and behaviour of 4-nonylphenol in river water of Germany

An analytical method composed of solid-phase-extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed to investigate the occurrence and the behaviour of the endocrine disruptor 4-nonylphenol (4-NP) in river water of Germany. 16 Para-isomers of the complex mixture of 4-NP isomers have been resolved in the SPE-extracts of river water samples. The mass spectra indicate the presence of four distinct groups of isomers. The different groups are characterised by different base peaks of the mass spectra dependent on the substitution of the alpha-carbon on the alkyl chain. The different isomers show (i) alpha-methyl, alpha-ethyl (base peak 149), (ii) alpha-dimethyl (base peak 135), (iii) alpha-methyl, alpha-propyl, alpha-butyl (base peak 121) and (iv) alpha-methyl, alpha-propyl, alpha-butyl (base peak 107) configuration of the alkyl chain. The recovery of the unbranched compound 4-n-NP was > or = 90%. Detection limit and determination limit of the whole analytical procedure were 6 ng L(-1) and 25 ng L(-1), respectively with a relative standard deviation of 11.7%. The concentration of the sum of the 4-NP isomers in all samples of river water ranged from 28 ng L(-1) (Elbe River) to 1220 ng L(-1)(Oder River). In a period of a higher river water level, a higher amount of 4-NP was detected in the Oder River than in a period of a lower water level. Therefore dilution was not the determinant factor of the 4-NP concentration in river water. The diurnal dynamics of the sewage treatment works (STWs) have to be considered as an influencing factor for the presence of 4-NP in river water.