Described is a solid-phase microextraction-gas chromatography-mass spectrometric procedure for the determination of three polycyclic musk fragrances (galaxolide, tonalide, celestolide) and a nitro musk fragrance (musk ketone) in natural river water. Both classes of the musk fragrances could be extracted reproducibly from water samples with a recovery in the range of 45-50% and relative standard deviation of 11-18% for fragrances at 25-260 ng/l levels. Detection limits were between 14 and 22 ng/l. To achieve this reproducibility it was necessary to use an internal standard, pentachloronitrobenzene, for all substances. Best recoveries were achieved with polydimethylsiloxane (PDMS)-divinylbenzene fibers (compared to recoveries obtained with PDMS, polyacrylate or carboxen fibers) and extraction times of 45 min at 30 degrees C, with no need for attainment of equilibrium conditions. The latter was achieved at about 2 h. For Elbe River water, in the vicinity of Magdeburg, no matrix effects were observed. While the average levels of celestolide and musk ketone for samples investigated were below the detection limits, 14 and 22 ng/l, respectively, and for tonalide below the limit of quantification, 22 ng/l, the ambient levels of galaxolide in the Elbe River were 117 ng/l.