Synthetic Musks in the Environment. Part 2: Enantioselective Transformation of the Polycyclic Musk Fragrances HHCB, AHTN, AHDI, and ATII in Freshwater Fish

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.

Removal of polycyclic musks by anaerobic membrane bioreactor: Biodegradation, biosorption, and enantioselectivity

“…PCMs are commonly 56 used ingredients in personal care and household cleaning products. They have been reported to be 57 resistant to biodegradation under aerobic conditions, which has led to their detection at high 58 concentrations in wastewater treatment plant effluents and in effluent impacted water bodies ( (Gatermann et al, 2002). Consistent with this, only two 65 enantiomers of ATII were detected in analytical standards and in environmental samples.…”

Chirality as an Environmental Forensics Tool

“…This observation suggests the possibility of in vivo enantioselective processing of a-HCH by this species [137]. Likewise, other studies have found nonracemic amounts of a-HCH [111], PCBs [66,196], a-HBCDD [193], and the musks HHCB, AHTN, ATII, and AHDI [197] in several species of bivalves: blue mussel, Mytilus edulis; the freshwater clam, Corbicula sp. ; the clams Mya truncate and Serripes groenlandica; and zebra mussel, Dreissena polymorpha, respectively.…”

“…No correlation was observed between fish lipid levels and enantiomer composition. Crucian carp has the most nonracemic amounts of trans-HHCB and trans-ATII [197]. Enantiomer compositions of musks were speciesspecific, most likely due to biotransformation, which may have been responsible for lower concentrations in carp compared to tench [197].…”

Globale Destillation

“…In 396 Fischproben aus Flüssen in Holland, Deutschland und Italien lag der gemessene Gehalt an Moschusverbindungen zudem sehr nahe der Nachweisgrenze von < 0,02 mg/kg Frischgewicht (OSPAR, 2004b). Kallenborn et al (2002) untersuchten SMV in der Nähe von Oslo, Larvik, Trondheim und Tromsø. In Tromsø und Trondheim wurden die Proben in ummittelbarer Nähe einer Klär-anlage und im Hafengebiet genommen, da hier die höchsten Belastungen vermutet wurden.…”

“…Dies steht im Widerspruch zu den bereits diskutierten Ergebnissen des OSPAR-Dokumentes (OSPAR, 2004b). Ebenso konnten Gatermann et al (2002) nachweisen, dass auch polycyclische Moschusverbindungen mit chiralem Zentrum in Süßwasserfischen enantiomerenselektiv metabolisiert werden und dabei eine Art Fingerabdruck für die jeweilige Fischart entsteht.…”