Fully automated determination of macrocyclic musk fragrances in wastewater by microextraction by packed sorbents and large volume injection gas chromatography–mass spectrometry

A fully automated method has been developed for the determination of eight macrocyclic musk fragrances in urban wastewater. The procedure includes the enrichment of the analytes by microextraction by packed sorbent (MEPS) followed by large volume injection–gas chromatography–mass spectrometry (LVI–GC–MS). The main factors in the MEPS technique were optimized. For all of the analytes, the highest enrichment factors were achieved when 4 mL samples were extracted by using C18 MEPS-sorbent and 50 μL of ethyl acetate were used for desorption. The eluate was directly analysed by GC–MS. Detection limits were found to be between 5 ng L−1 and 10 ng L−1, depending on the target analytes. In addition, under optimized conditions, the method gave good levels of intra-day and inter-day repeatability in wastewater samples with relative standard deviation (RSD) (n = 3, 1000 ng L−1) less than 5% and 9%, respectively. The applicability of the method was tested with wastewater samples from two influent and effluent urban wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the macrocylic musks at concentrations higher than the method quantification limits (MQLs), being the most abundant analyte ambrettolide at 9.29 μg L−1. In addition, the analyses of effluent urban wastewater showed a decrease in the concentrations with macrocyclic musk concentrations of between not detected (n.d.) and 2.26 μg L−1 being detected.

► The work was focused on the determination of 8 macrocyclic musk in urban wastewater.
► MEPS instead of SPE have been used to preconcentrate the target analytes.
► Large volume injection permitted the automation of the whole analytical method.
► Method detection and quantification limits were found in the low ng L−1.
► Good values of intra-day and inter-day repeatabilities have been obtained.