A multi-residue method by supercritical fluid chromatography coupled with tandem mass spectrometry method for the analysis of chiral and non-chiral chemicals of emerging concern in environmental samples

Abstract

This manuscript presents the development, validation and application of a multi-residue supercritical fluid chromatography coupled with tandem mass spectrometry method for the analysis of 140 chiral and non-chiral chemicals of emerging concern in environmental samples, with 81 compounds being fully quantitative, 14 semi-quantitative and 45 qualitative, validated according to European Medicine Agency (EMA) guidelines (European Medicines Agency 2019). One unified LC-MS method was used to analyse all analytes, which were split into three injection methods to ensure sufficient peak resolution. The unified method provided an average of 113% accuracy and 4.5% precision across the analyte range. Limits of detection were in the range of 35 pg L −1-0.7 μg L −1 , in both river water and wastewater, with an average LOD of 33 ng L −1. The method was combined with solid-phase extraction and applied in environmental samples, showing very good accuracy and precision, as well as excellent chromatographic resolution of a range of chiral enantiomers including beta-blockers, benzodiazepines and antidepressants. The method resulted in quantification of 75% of analytes in at least two matrices, and 56% in the trio of environmental matrices of river water, effluent wastewater and influent wastewater, enabling its use in monitoring compounds of environmental concern, from their sources of origin through to their discharge into the environment.

Interpol Review of Drug Analysis 2019-2022

“…2019 electrochemical sensor for the determination of clonazepam [ 500 ]; electrochemical sensor for the determination of five benzodiazepines (clonazepam, diazepam, alprazolam, chiordiazepoxide, oxazepam) with poly dopamine-poly folic acid (P(DA-FA)) nanocomposite modified glassy carbon electrode (P(DA-FA)-GCE) [ 501 ]; HPLC method for the simultaneous determination of three benzodiazepines [ 502 ]; Air-assisted liquid-liquid microextraction (AALLME) as an extraction method for three benzodiazepines (chlordiazepoxide, alprazolam, and lorazepam) followed by HPLC-UV for separation and determination [ 503 ]; simultaneous detection of a ternary mixture of the benzodiazepines diazepam, lorazepam, and flunitrazepam using an array of voltammetric sensors [ 504 ]; review of electrochemical-based approaches for the determination of the benzodiazepine class of drugs [ 505 ]; synthesis of flubromazepam positional isomers for forensic analysis [ 506 ]; analytical properties (LC-QTOF-MS, GC-MS and NMR) of the designer benzodiazepine 8-chloro-6-(2-fluorophenyl)-1-methyl-4H- [1,2,4]triazolo[4,3-a] [1,4]benzodiazepine (flualprazolam) seized in an anesthesia robbery case [ 507 ]; review provides a summary of sample preparation techniques (solid-phase extraction and Liquid-liquid phase extraction) and the methods for the detection and quantification of BZDs molecules [ 508 ]; liquid-chromatography high-resolution mass spectrometry method for the detection of 15 non-FDA approved BZDs [ 509 ]; 2020 spectrophotometric-reverse flow injection analysis (rFIA) method for the determination of Nitrazepam in pure and pharmaceutical preparations [ 510 ]; RP-HPLC method for the simultaneous determination of Clonazepam and metronidazole in pharmaceutical tablets [ 511 ]; microsolid-phase extraction for the preconcentration of Nitrazepam and Oxazepam before HPLC-DAD analysis [ 512 ]; FTIR and Raman spectroscopy method supported by Differential Scanning Calorimetry (DSC) for the screening and detection of benzodiazepine [ 513 ]; TD-DART-MS for the rapid and sensitive detection of a suite of 19 benzodiazepines [ 514 ]; sensor for detecting nitro-containing BZDs in beverages at DFSA crime scenes [ 515 ]; batch and cloud point extraction kinetic spectrophotometric method for determination of Nitrazepam and Clonazepam in pharmaceutical preparations [ 516 ]; MALDI-TOF-MS methodology for the quick and qualitative detection of benzodiazepines [ 517 ]; supercritical fluid chromatography coupled with tandem mass spectrometry method for the analysis of 140 chiral and non-chiral chemicals of emerging concern in environmental samples including benzodiazepines [ 518 ]; pipette-tip micro-solid phase extraction (PT-mu SPE) with corona discharge ionization-IMS (CD-IMS) for on-site fast detection of benzodiazepines in dietary supplements [ 519 ]; electrochemical sensor for measuring lorazepam in various matrices [ ...…”

Supercritical Fluid Chromatography for Chiral Analysis, Part 2: Applications

“…Pharmacological active compounds (PACs) are increasingly seen as major pollutants within ecological systems. However, despite the known concerns of these drug stereoisomers, research on their ecotoxicological effect is still limited (32).…”

Progress in the Enantioseparation of β-Blockers by Chromatographic Methods

“…It turns out that all β-blockers generated inverted U shape curves for the selectivity factor vs additive concentration. Recently, a multi-residue method by SFC coupled with tandem mass spectrometry method were adopted by Rice et al [ 118 ] for the analysis and enantiosepration of 140 chiral and non-chiral chemicals in environmental samples, including β-blockers, using 2.1 μm particle size. It turns out that SFC is an excellent technique for combined achiral-chiral analysis due to the combined use of supercritical CO 2 , non-biological chiral selectors, and smaller-UHPLC-size particles.…”