Bioaccumulation of polycyclic musks (HHCB, AHTN) and nitro musks (musk xylene, musk ketone, and their amino metabolites) in aquatic biota was investigated by analyzing 18 fish samples (rudd, tench, crucian carp, eel) and 1 pooled zebra mussel sample from the pond of a municipal sewage treatment plant. Furthermore, water samples taken at the effluent of the sewage plant as well as water samples and two series of semipermeable membrane devices (SPMDs) from the pond were included. This comprehensive data set allowed the determination of species-dependent bioaccumulation factors on a lipid basis (BAF(L)), e.g., for HHCB the BAF(L) in tench were more than 20 times higher than in eel. The BAF(L) for HHCB and AHTN in biota were lower than the partition coefficients K(SPMD/W) obtained from SPMD samples, which are assumed to represent model bioconcentration values. This stresses that metabolism of these compounds in fish must not be neglected.

Blood plasma samples were collected from wild bream (Abramis brama L.) in the Elbe River, Germany, and analyzed for the yolk protein precursor vitellogenin (VTG), a biomarker for estrogen exposure, and the sex steroids 11-ketotestosterone (11KT), testosterone (T), and 17beta-estradiol (E2) to investigate for evidence of endocrine modulation. In addition, the gonadal status and the prominence of spawning tubercles were investigated. Nine riverine sites were investigated on the Elbe that were influenced by different sources of endocrine-active substances. Bream were collected from a lake that received no domestic or industrial discharges as a control. Plasma VTG concentrations were significantly higher in male bream from the Czech border to the middle Elbe, with the highest concentrations in fish sampled at the locations near Magdeburg and downstream of Dresden (between 20 and 100 times higher than in the controls), regions that are characterized by high levels of effluent discharges into the river. Following the Elbe from this site to the sea, the concentrations of plasma VTG in males were lower than at Meissen but were still elevated above the controls. 11KT and E2 titers showed suppressions in their normal concentrations at some locations (those receiving the greatest industrial discharges). There were reciprocal relationships between inhibitory effects on gonadal growth, maturation, and plasma sex steroids and exposure to pollutants, such as organotins, pesticides, or metals. However, there was no single chemical that alone could explain the observed inhibitory effects on sexual development. The results indicate that the endocrine system in wild bream is disrupted in stretches of the Elbe River.

No abstract

A method for the enantioselective separation of the chiral polycyclic musks HHCB, AHTN, AHDI, and ATII is presented. Eighteen fish samples (rudd, tench, crucian carp, eel) and one pooled zebra mussel sample from the pond of a municipal sewage treatment plant were investigated with regard to their concentrations and the enantiomeric ratios (ERs) of polycyclic musks. In addition, three water samples taken at the effluent of the sewage plant, as well as two water samples and two series of semipermeable membrane devices (SPMDs) consisting of six samples each from the pond were included in the present study. This comprehensive data set allowed a reliable evaluation of species-dependent metabolization processes. The pattern of the polycyclic musks in the chromatograms obtained by enantioselective gas chromatography seems to be typical of each species, like a fingerprint. The highest deviations from the racemic ER were found for trans-HHCB and trans-ATII in crucian carp with values of or below 0.1. Calculations showed that enantioselective transformation seems to be the most important process, resulting in the observed lower concentrations in crucian carp compared to tench. Consequences for a risk assessment are discussed.