Enantiomeric analysis of drugs of abuse in wastewater by chiral liquid chromatography coupled with tandem mass spectrometry.
The manuscript concerns the development and validation of a method for enantiomeric analysis of structurally related amphetamines (amphetamine, methamphetamine, 4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA) and 3,4-methylenedioxy-N-ethylamphetamine (MDEA)), ephedrines (ephedrine, pseudoephedrine and norephedrine) and venlafaxine in wastewater by means of chiral chromatography coupled with tandem mass spectrometry. Solid-phase extraction on Oasis HLB sorbent used for sample clean-up and concentration of analytes resulted in very good recoveries accounting for >70%. Signal suppression during MS analysis was negligible for most studied analytes. Resolution of enantiomers of chiral drugs was found to be higher than 1. Preliminary assay validation was undertaken. The mean correlation coefficients of the calibration curves, which were on average higher than 0.997 for all studied analytes, showed good linearity of the method in the studied range. Intra- and inter-day repeatabilities were on average less than 5%. The method quantification limits in wastewater were at low ppt levels and varied from 2.25 to 11.75ng/L. The method was successfully applied for the analysis of raw and treated wastewater samples collected from four wastewater treatment plants. A common occurrence of 1R,2S (-)-ephedrine, 1S,2S (+)-pseudoephedrine and venlafaxine in both raw and treated wastewater samples was observed. Amphetamine, methamphetamine, MDMA and MDEA were also detected in several wastewater samples. The study of enantiomeric fractions of these chiral drugs proved their variable non-racemic composition. The influence of wastewater treatment processes on the enantiomeric composition of chiral drugs was also noted and might indicate enantioselective processes occurring during treatment, although more comprehensive research has to be undertaken to support this hypothesis.
University of Huddersfield, Department of Chemical and Biological Sciences, School of Applied Sciences, Queensgate, Huddersfield HD1 3DH, UK. b.kasprzyk-hordern@hud.ac.uk
Barbara
B
Kasprzyk-Hordern
Vishnu V R
VV
Kondakal
David R
DR
Baker
D000662:Amphetamines / Q000032:analysis / Q000737:chemistry*; D002853:Chromatography, Liquid / Q000379:methods*; D003511:Cyclohexanols / Q000032:analysis / Q000737:chemistry; D013287:Illicit Drugs / Q000032:analysis / Q000737:chemistry*; D016014:Linear Models; D011412:Propanolamines / Q000032:analysis / Q000737:chemistry*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D052616:Solid Phase Extraction; D013237:Stereoisomerism; D053719:Tandem Mass Spectrometry / Q000379:methods*; D000069470:Venlafaxine Hydrochloride; D014866:Waste Products; D014874:Water Pollutants, Chemical / Q000032:analysis / Q000737:chemistry
D000662:Amphetamines; D003511:Cyclohexanols; D013287:Illicit Drugs; D011412:Propanolamines; D014866:Waste Products; D014874:Water Pollutants, Chemical; D000069470:Venlafaxine Hydrochloride