Successful adaption of a forensic toxicological screening workflow employing nontargeted liquid chromatography-tandem mass spectrometry to water analysis (original) (raw)
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Analytica Chimica Acta, 2011
Illicit drugs of abuse Ultrahigh pressure liquid chromatography Time-of-flight mass spectrometry MS E Wide-scope screening Urban wastewater a b s t r a c t This work illustrates the potential of hybrid quadrupole-time-of-flight mass spectrometry (QTOF MS) coupled to ultrahigh pressure liquid chromatography (UHPLC) to investigate the presence of drugs of abuse in wastewater. After solid-phase extraction with Oasis MCX cartridges, seventy-six illicit drugs, prescription drugs with potential for abuse, and metabolites were investigated in the samples by TOF MS using electrospray interface under positive ionization mode, with MS data acquired over an m/z range of 50-1000 Da. For 11 compounds, reference standards were available, and experimental data (e.g., retention time and fragmentation data) could be obtained, facilitating a more confident identification. The use of a QTOF instrument enabled the simultaneous application of two acquisition functions with different collision energies: a low energy (LE) function, where none or poor fragmentation took place, and a high energy (HE) function, where fragmentation in the collision cell was promoted. This approach, known as MS E , enabled the simultaneous acquisition of full-spectrum accurate mass data of both protonated molecules and fragment ions in a single injection, providing relevant information that facilitates the rapid detection and reliable identification of these emerging contaminants in the sample matrices analyzed. In addition, isomeric compounds, like the opiates, morphine and norcodeine, could be discriminated by their specific fragments observed in HE TOF MS spectra, without the need of reference standards. UHPLC-QTOF MS was proven to be a powerful and efficient technique for rapid wide-scope screening and identification of many relevant drugs in complex matrices, such as influent and effluent urban wastewater.
Rapid Communications in Mass Spectrometry, 2001
The present study describes a novel approach for utilizing liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) in qualitative screening analysis. An LC/TOFMS method was developed for screening toxicologically relevant substances in urine samples. After solid phase extraction and LC separation, the method included full spectrum acquisition followed by automatic internal calibration, searching against a target library, and reporting positive identifications. The target library, containing 433 toxicologically relevant substances in the mass range of 105±734 Da, was created simply by entering the elemental formulas of substances into the instrument software for the calculation of their respective monoisotopic masses. In addition to parent drugs, the library contained selected urinary drug metabolites, based on their structures available in the literature. Identification was based on the exact masses of the compounds. The LC/TOFMS method provided 5± 10 ppm mass accuracy for a majority of identified compounds in authentic urine samples. Compared with established thin-layer and gas chromatographic methods, the LC/TOFMS method produced similar findings in urine with the additional advantage of metabolite identification without actual reference substances.
Analytical and Bioanalytical Chemistry, 2014
The present work describes the development and validation of a highly sensitive analytical method for the simultaneous determination of 68 compounds, including illicit drugs (opiates, opioids, cocaine compounds, amphetamines, and hallucinogens), psychiatric drugs (benzodiazepines, barbiturates, anesthetics, antiepileptics, antipsychotics, antidepressants, and sympathomimetics), and selected human metabolites in influent and effluent wastewater (IWW and EWW) by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method involves a pre-concentration and cleanup step, carried out by solid-phase extraction (SPE) using the adsorbent Strata-XC, followed by the instrumental analysis performed by LC-MS/MS, using a Kinetex pentafluorophenyl (PFP) reversed-phase fused-core column and electrospray ionization (ESI) in both positive and negative modes. A systematic optimization of mobile phases was performed to cope with the wide range of physicochemical properties of the analytes. The PFP column was also compared with two reversed-phase columns: fused-core C18 and XB-C18 (with a cross-butyl C18 ligand). SPE optimization and critical aspects associated with the trace level determination of the target compounds (e.g., matrix effects) have been also considered and discussed. Fragmentation patterns for all the classes were proposed. The validated method provides absolute recoveries between 75 and 120% for most compounds in IWW and EWW. Low method limits of detection were achieved (between 0.04 and 10.0 ng/L for 87% of the compounds), allowing a reliable and accurate quantification of the analytes at trace level. The method was successfully applied to the analysis of these compounds in five wastewater treatment plants in Santorini, a touristic island of the Aegean Sea, Greece. Thirty-two out of 68 compounds were detected in all IWW samples in the range between 0.6 ng/L (for nordiazepam) and 6,822 ng/L (for carbamazepine) and 22 out of 68 in all EWW samples, with values between 0.4 ng/L (for 9-OH risperidone) and 2,200 ng/L (for carbamazepine). The novel methodology described herein maximizes the information on the environmental analysis of these substances and also provides a first profile of 68 drugs in a Greek touristic area.
Analytical and Bioanalytical Chemistry, 2015
The existence of pharmaceuticals and illicit drugs (PIDs) in environmental waters has led many analytical chemists to develop screening methods for monitoring purposes. Water samples can contain a huge number of possible contaminants, commonly at low concentrations, which makes their detection and identification problematic. Liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) has proven itself effective in the screening of environmental contaminants. The present work investigates the use of the most popular HRMS instruments, quadrupole time-offlight and linear trap quadrupole-Orbitrap, from two different laboratories. A suspect screening for PIDs was carried out on wastewater (influent and effluent) and surface water samples from Castellón, Eastern Spain, and Cremona, Northern Italy, incorporating a database of 107 PIDs (including 220 fragment ions). A comparison between the findings of both instruments and of the samples was made which highlights the advantages and drawbacks of the strategies applied in each case. In total, 28 compounds were detected and/or identified by either/both instruments with irbesartan, valsartan, benzoylecgonine and caffeine being the most commonly found compounds across all samples.
Analytica Chimica Acta, 2003
In contrast to GC–MS, many factors are influencing mass spectra of organic compounds when analyzed by LC–MS. In-source or transport collision-induced dissociation by electrospray ionization or atmospheric pressure chemical ionization demonstrate the need for experimental condition standardization when building-up a library of reference spectra. Magnetic sector, quadrupole, ion trap or time-of-flight filters placed on single or multiple mass spectrometry instruments coupled with HPLC deliver unique mass intensities pattern from the same molecules that are most often not readily comparable between each other. This makes it very difficult or even impossible to rely on any collections of reference data whatever comparison algorithm is applied for library search or manual comparison when full confirmation of identity is required. Typical areas of expertise are very sensitive to sound and complete package procedures to withstand administrative or court’s scrutiny. In this paper, this problem is referred to the specific field of forensic toxicology and doping control in sports. Several official guidelines have been released recently and await confrontation with concrete cases. Closely related areas like residues in living animals and meat products are regulating these aspects with detailed procedures. Basically, they all propose the accumulation of a finite quantity of information about the unknown molecule and the reference substance. These confirmatory packages are briefly exposed, compared and evaluated for their future application to the newest LC–MS techniques that are more frequently used within these critical fields of expertise.
Analytical and Bioanalytical Chemistry, 2009
The simultaneous analysis of nine drugs of abuse (DOAs) and their metabolites (amphetamine, methamphetamine, methylenedioxymethamphetamine, methadone, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine, cocaine, benzoylecgonine, ecgonine methyl ester and 6-monoacetylmorphine) in wastewater based on hydrophilic interaction liquid chromatography (HILIC) coupled to tandem mass spectrometry (MS/MS) was optimised and validated. For each analyte, the deuterated analogue was used for quantification. The separation by HILIC showed good performance for all compounds, especially for the hydrophilic compounds, which elute early (amphetamine-like stimulants) or show no retention (ecgonine methyl ester) in reversed-phase liquid chromatography. Sample preparation based on solid-phase extraction was optimised by comparing Oasis HLB and Oasis MCX sorbents for various parameters such as sample pH, amount of sorbent bed and washing solvent.
Mass spectrometric strategies for the investigation of biomarkers of illicit drug use in wastewater
Mass spectrometry reviews, 2016
The analysis of illicit drugs in urban wastewater is the basis of wastewater-based epidemiology (WBE), and has received much scientific attention because the concentrations measured can be used as a new non-intrusive tool to provide evidence-based and real-time estimates of community-wide drug consumption. Moreover, WBE allows monitoring patterns and spatial and temporal trends of drug use. Although information and expertise from other disciplines is required to refine and effectively apply WBE, analytical chemistry is the fundamental driver in this field. The use of advanced analytical techniques, commonly based on combined chromatography-mass spectrometry, is mandatory because the very low analyte concentration and the complexity of samples (raw wastewater) make quantification and identification/confirmation of illicit drug biomarkers (IDBs) troublesome. We review the most-recent literature available (mostly from the last 5 years) on the determination of IDBs in wastewater with pa...
Advances in the Use of Mass Spectral Libraries for Forensic Toxicology
Journal of Analytical Toxicology, 2002
Gas chromatography in combination with mass spectrometry (GC-MS) plays an important role in the field of analytical toxicology. The identification of unknown compounds is very frequently undertaken with GC-MS and utilizing mass spectral libraries. Currently available libraries for analytical toxicology were compared for overlapping and uniqueness of their entries. Furthermore, the widely known Pfleger-Maurer-Weber-Drugs-and-Pesticides-Library for toxicology (PMW_tox2) was used to compare the search algorithms PBM (Probability Based Matching, Agilent Technologies), INCOS (Finnigan/Thermoquest), and MassLib (Max Planck Institute). To our knowledge, direct comparisons of mass spectral libraries and search programs for analytical toxicology have not been published previously. The capabilities and necessities of modern MS technology in the field of general unknown analysis are revealed, and some of the potential pitfalls are described.