Renewable sorbent material for solid phase extraction with direct coupling of sequential injection analysis-bead injection to liquid chromatography-electrospray ionization tandem mass spectrometry (original) (raw)
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Journal of Chromatography B, 2021
An on-line solid phase extraction using a lab-made restricted access media (RAM) was developed as sample preparation procedure for determination of the pharmaceutical compounds caffeine (CAF), carbamazepine (CBZ), norfloxacin (NOR), ciprofloxacin (CIP), fluoxetine (FLX) and venlafaxine in wastewater treatment plant samples by liquid chromatography-tandem mass spectrometry (LC-MS/MS). This method is suitable for use in routine of analysis, avoiding cross-contamination and requiring only a small sample volume (50 µL), with minimal handling. The method was validated according to international guidelines. The chromatographic efficiency was evaluated using peak resolution and asymmetry parameters. Carryover was also evaluated, in order to ensure reliability of the analysis and the ability to reuse the cartridge. Satisfactory linearity (r2 > 0.99) was obtained for all the compounds. The intra- and inter-day precision values were lower than 5.79 and 14.1%, respectively. The limits of detection ranged from 0.01 to 3 µg L-1 and the limits of quantification were from 0.1 to 5 µg L-1. The method was applied to 20 environmental wastewater samples, with caffeine being the most widely detected compound, at the highest concentration of 392 µg L-1, while other compounds were detected in fewer samples at lower concentrations (up to 9.60 µg L-1). The lab-made modification is a cheaper option for on-line sample preparation, compared to commercially available on-line SPE cartridges and RAM columns. Moreover, a high-throughput procedure was achieved, with an analysis time of 16 min including sample preparation and chromatographic separation. The same RAM column was applied over 200 injections including method optimization, validation and application in wastewater samples without loss of analytical response.
Journal of Chromatography A, 2011
The present work describes the development and validation of a method for the determination of five non-steroidal anti-inflammatory drugs (NSAIDs: clofibric acid, ibuprofen, naproxen, diclofenac and ketoprofen) in water samples. The fully automated method includes in situ aqueous derivatization followed by analyte enrichment by microextraction by packed sorbent (MEPS) coupled directly to programmed temperature vaporizer-gas chromatography-mass spectrometry (PTV-GC-MS). The MEPS variables, such as sample volume, elution solvent, elution volume, fill and injection speed and washing steps were optimized. It was possible to use the MEPS polymer (silica-C18) 250 times. Ibuprofen-d3 was used as internal standard. The reproducibility of the method, calculated as the relative standard deviation (RSD), was below 10% for all compounds. Detection limits in ultrapure water were between 3.0 and 110 ng L −1 for ibuprofen and ketoprofen, respectively. External calibration was used in the determination of NSAIDs in several types of water samples, including tap, river, sea and influent and effluent wastewater. The results obtained revealed the presence of ibuprofen and naproxen in the influent wastewater sample and of naproxen in the effluent wastewater sample.
The aim of the present work was to develop a novel in-house mixed-mode SPE sorbent to be used for the HPLC-Ion TrapMS determination of 16 basic drugs in urine. By using a computational modelling, a virtual monomer library was screened identifying three suitable functional monomers, methacrylic acid (MAA), itaconic acid (IA) and 2-acrylamide-2-methylpropane sulfonic acid (AMPSA), respectively. Three different sorbents were then synthetized based on these monomers, and using as cross-linker trimethylolpropane trimethacrylate (TMPTMA). The sorbent characterization analyses brought to the selection of the AMPSA based phase. Using this novel in-house sorbent, a SPE-HPLC-Ion TrapMS method for drug analysis in urine was validated proving to be selective and accurate and showing a sensitivity adequate for toxicological urine analysis. The comparison of the in-house mixed-mode SPE sorbent with two analogous commercial mixed-mode SPE phases showed that the first one was better not only in terms of process efficiency, but also in terms of quality-price rate. To the best of our knowledge, this is the first time in which an in-house SPE procedure has been applied to the toxicological analysis of a complex matrix, such as urine.
Journal of chromatography. A, 2017
To follow the twelve "green analytical chemistry" (GAC) principles, it is necessary to continuously develop analytical extraction and determination methodologies to assess the presence of micropollutants, such as pharmaceuticals, in environmental samples. A reduction in the analysis time and solvent quantity, which is one of the GAC principles, has been achieved through a simplified solid-phase extraction (SPE) procedure combined with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the determination of twenty-three pharmaceuticals in liquid environmental samples using N-vinylpyrrolidone-divinylbenzene copolymer (OASIS HLB) cartridges. The optimal SPE conditions were studied. In these optimized conditions, 82.6% of the data have a median recovery above 70% for all compounds in each sample. The relative standard deviations (RSDs) were below 14.4% and 22.0% for intra- and inter-day repeatability, respectively. Method detection limits (MDLs) and ...
Analytica Chimica Acta, 2013
Two new commercially available polar coatings for stir bar sorptive extraction (SBSE), consisting of polyacrylate (PA) with a proportion of polyethyleneglycol (PEG) (Acrylate Twister ®) and PEG modified silicone (EG Silicone Twister ®), were evaluated and compared with the classic coating based on polydimethylsiloxane (PDMS Twister ®) for the extraction of a group of pharmaceuticals and personal care products (PPCPs) from wastewater samples. The SBSE parameters, such as sample pH, agitation speed, extraction temperature, extraction time, desorption solvent and time, were optimised in order to achieve suitable sorption of the target analytes. The EG Silicone coating enabled more efficient extraction of some polar compounds as well as improving the sorption of apolar compounds, in comparison with the other two coatings. Finally, the method of SBSE followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) using the EG Silicone coating was validated achieving good linearity (r 2 > 0.994, except for CBZ (r 2 > 0.989)), precision (%RSD < 17%) and low limits of quantification (LOQs) (20-40 ng L −1). The SBSE/LC-MS/MS methodology was applied for the determination of PPCPs in wastewater samples.
Journal of Chromatography A, 2014
The aim of this study was to develop and optimise an analytical method for the quantification of a bactericide and 13 pharmaceutical products, including 8 antibiotics (fluoroquinolones, tetracyclines, sulfonamides, macrolide), in various aqueous environmental samples: soil water and aqueous fractions of pig slurry, digested pig slurry and sewage sludge. The analysis was performed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS). The main challenge was to minimize the matrix effects observed in mass spectrometry, mostly due to ion suppression. They depended on the dissolved organic carbon (DOC) content and its origin, and ranged between −22% and +20% and between −38% and −93% of the signal obtained without matrix, in soil water and slurry supernatant, respectively. The very variable levels of these matrix effects suggested DOC content cut-offs above which sample purification was required. These cut-offs depended on compounds, with concentrations ranging from 30 to 290 mg C/L for antibiotics (except tylosine) up to 600-6400 mg C/L for the most apolar compounds. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure was therefore optimised using an experimental design methodology, in order to purify samples with high DOC contents. Its performance led to a compromise, allowing fluoroquinolone and tetracycline analysis. The QuEChERS extraction salts consisted therefore of sodium acetate, sodium sulfate instead of magnesium sulfate, and sodium ethylenediaminetetraacetate (EDTA) as a ligand of divalent cations. The modified QuEChERS procedure employed for the extraction of pharmaceuticals in slurry and digested slurry liquid phases reduced the matrix effects for almost all the compounds, with extraction recoveries generally above 75%. The performance characteristics of the method were evaluated in terms of linearity, intra-day and inter-day precision, accuracy and limits of quantification, which reached concentration ranges of 5-270 ng/L in soil water and sludge supernatant, and 31-2400 ng/L in slurry and digested slurry supernatants, depending on the compounds. The new method was then successfully applied for the determination of the target compounds in environmental samples.
Journal of Chromatography A, 2014
In this study, two materials are presented with strong cation-exchange (SCX) behaviour synthesised by two different approaches and then crushed for their application as sorbents for solid-phase extraction (SPE) to extract a group of pharmaceuticals and illicit drugs selectively from wastewater samples. The first SCX polymer was obtained by copolymerisation of three monomers: 2-acrylamido-2-methylpropane sulphonic acid (AMPSA), 2-hydroxyethyl methacrylate (HEMA) and pentaerythritol triacrylate (PETRA), while the second was obtained by post-modification with sulphuric acid (H 2 SO 4) of a copolymer based on HEMA and divinylbenzene (DVB). After their syntheses, both polymers were evaluated as SPE sorbents, with all parameters affecting SPE being optimised, such as sample pH, washing and elution solvents and volumes. Thanks to the sulphonic groups present in the structure of the polymers, all of the compounds with basic functionalities were retained on the sorbents after the washing step, removing the acidic analytes and other interfering compounds, providing successful results in terms of ion suppression/enhancement (-12% and 21%) when wastewater samples were analysed. However, AMPSA/HEMA/PETRA (20/60/20) failed to retain the analytes after loading wastewater samples (25 or 50 mL), decreasing analyte recovery values significantly, whereas the sulphonated HEMA/DVB (50/50) enabled good SPE performance with recovery values between 70% and 98%, except for ranitidine and EDDP (39% and 43%, respectively). Therefore, this polymer was selected for further method validation and quantification of wastewater samples, providing low method detection limits (MDLs) in this matrix (from 2 to 40 ng L −1). Finally, most of the studied compounds were detected and quantified in wastewater samples, especially atenolol, ranitidine, cocaine and its metabolite benzoylecgonine.
Journal of the Chilean Chemical Society
A variety of organic compounds and their metabolites used in pharmaceutical and personal care products (PPCP´s) are continuously introduced into the environment by domestic or industrial wastewater. Solid phase extraction (polymeric dinivylbenzene cartridge) and stir bar sorptive extraction (polydimethylsiloxane phase) methodologies were optimized for the determination of some selected PPCP´s in aqueous matrices. Carbamazepine, β estradiol, 3-(4-methylbenzylidene) champhor, benzophenone-1 and ibuprofen were extracted from aqueous samples and methanol was used as conditioning/eluting solvent. The variables involved in the extraction of the analytes in the original sample were studied, pH between 3 and 6 and sample volume between 50 and 500 mL were considered. Three concentration levels were extracted at the optimal conditions of pH 5 and 500 mL of sample volume with a recovery up to 89%. The determination was performed in a GC-MS, and a derivatization step using BSTFA+TMCS (99:1) was needed previous to the injection. Real samples from Maipo River and Villarrica Lake were analyzed with the optimized method, and concentrations below the detection limit were detected.
Journal of Chromatography A, 2004
Seven polymeric solid-phase extraction (SPE) sorbents were evaluated with regard to their ability to extract acidic, neutral and basic pharmaceuticals and estrogens simultaneously from water at neutral pH. Highest recoveries (70–100%) for the majority of the analytes were obtained with styrene–methacrylate and styrene–N-vinylpyrrolidone co-polymers. The latter one (Oasis HLB) was chosen for further refinement of an extraction method for the quantitative determination of acidic and neutral drugs in surface water samples at detection limits below 1 ng/l. A sequential elution protocol was applied for clean-up and separation of the extracted analytes into fractions suitable for further compound specific processing. The neutral analytes as well as the acidic compounds after derivatisation were quantified by GC–MS. Caffeine, ibuprofen, its metabolites and diclofenac were detected in river water samples in the 1–100 ng/l range.