Polymeric Cartridges Research Articles

Trace analysis of antibacterial tylosin A, B, C and D in honey by liquid chromatography-electrospray ionization-mass spectrometry

A new LC-ESI-MS method was developed for the determination of residues of the antibacterial tylosins A, B, C and D in honey. The procedure employed an SPE on polymeric cartridges for the isolation of tylosins from diluted honey. Chromatographic separation of the tylosins was performed on a C18 column (150 x 4.60 mm2 ID, 5 microm) using a ternary gradient made of formic acid 1% in water (solvent A), methanol (solvent B) and ACN (solvent C) as mobile phase, at 30 degrees C and at a flow rate of 0.8 mL/min. Average analyte recoveries for the studied compounds ranged from 89 to 106% in replica sets of fortified honey samples. The detection limits for the four drugs studied were between 2 and 3 microg/kg. The developed method has been applied to the analysis of tylosin residues in honey from veterinarian treated beehives fed with the technical product, which contains the four compounds and is a new candidate antibiotic to treat American foulbrood disease of honey bee colonies.

Determination of omeprazole, hydroxyomeprazole and omeprazole sulfone using automated solid phase extraction and micellar electrokinetic capillary chromatography

A sensitive method for the determination of omeprazole and its metabolites has been developed. It involves an automated solid phase extraction (SPE) procedure and capillary electrophoresis with UV detection. Omeprazole, hydroxyomeprazole and omeprazole sulfone could be separated by micellar electrokinetic capillary chromatography using a background electrolyte composed of 20 mM borate buffer and 30 mM sodium dodecyl sulfate, pH 9.5. The isolation of omeprazole and its metabolites from plasma was automatically accomplished with an original SPE procedure using surface-modified styrene–divinylbenzene polymer cartridges. Good recovery data and satisfactory precision values were obtained. Responses were linear for the three analytes, from 0.08 to 2.0 μg/mL of plasma. Intra- and inter-day precision values of about 1.6% R.S.D. ( n = 10) and 2.5% R.S.D. ( n = 36), respectively, were obtained. The method is highly robust and no breakdown of the current or capillary blockages were observed during several weeks of operation. The validated method was applied to the determination of omeprazole in pharmaceutical preparations and for the analysis of plasma samples obtained from three volunteers who received oral doses of omeprazole.

A new simply and effective fractionation method for cylindrospermopsin analyses

A new simply and effective fractionation method for cylindrospermopsin (CYN) analyses was developed. The extract from cells of Cylindrospermopsis raciborskii was resuspended with 0.1 M carbonate buffer at pH 10.5, and pass through the double-cartridges column which was consisted of a styrene polymer cartridge and an anion exchange cartridge. CYN and deoxy-CYN were adsorbed with the anion exchange cartridge. After separation of the anion exchange cartridge, adsorbed compounds were eluted from the cartridge with 50% methanol containing 1% formic acid solution. CYN and deoxy-CYN were selectively condensed in the eluted solution. When CYN was analyzed by LC-photodiode array or LC/MS, only two peaks of CYN and deoxy-CYN were detected quantitatively. The results suggest that the fractionation method is a useful method for CYN analyses and must be utilized for CYN purification.

Monitoring and toxicity of sulfonated derivatives of benzene and naphthalene in municipal sewage treatment plants

Monitoring benzenesulfonates (BS) and naphthalenesulfonates (NS) took place in five municipal sewage treatment plants (STP). A previously optimized method based on solid phase extraction with polymeric cartridges followed by ion-pair liquid chromatography-electrospray-mass spectrometry (SPE-IPC-ESI-MS) was used. This work confirmed the little or no effect of primary settlement on total organic carbon (TOC) and monosulfonated compounds removal, whereas the main reduction is obtained at the biological stage. However, the most polar compounds, such as naphthalenedisulfonates (NDS), were not effectively removed using the biological treatment. An aromatic sulfonated compound is suggested to be used as a tracer of the origin of industrial pollutants discharged into STPs. A bioluminescence inhibition test, Microtox® assay, allowed toxicity determination of the most relevant aromatic sulfonated compounds detected and toxicity comparison between primary and secondary effluents.

Determination of azolic fungicides in wine by solid-phase extraction and high-performance liquid chromatography–atmospheric pressure chemical ionization–mass spectrometry

A method for simultaneous analysis of eight azolic fungicides: cyproconazole, diniconazole, tetraconazole, thiabendazole, flusilazole, triadimenol, triadimefon, carbendazim and the degradation product 2-aminobenzimidazole in wine samples is described. The compounds are isolated from the samples and concentrated by solid-phase extraction on polymeric cartridges. The determination is carried out by liquid chromatography with mass spectrometric detection in positive ionization and selected ion monitoring modes. The influence of parameters such as the mobile phase composition, column temperature, corona current and fragmentor voltage is studied and the proposed method is validated. Recoveries of the nine compounds added to wine samples range from 83 to 109%, with relative standard deviations below 10%. The quantitation limits are between 9 and 31 μg/L. Real wine samples are analyzed by the proposed method, also.

Determination of Tetracyclines in Water Samples Using Liquid Chromatography with Fluorimetric Detection

A liquid chromatographic method with fluorimetric detection is proposed for the determination of trace levels of oxytetracycline, tetracycline, chlortetracycline and doxycycline in water samples. The analytes are preconcentrated by solid phase extraction using reversed phase polymeric cartridges and acetonitrile as eluent. Preconcentration factors up to 125 can be obtained. The chromatographic separation is performed on a polymeric column with a gradient elution program using mobile phases based on mixtures of acetonitrile and 0.01 mol L−1 oxalic acid aqueous solution at a flow rate of 1.2 mL min−1. Tetracyclines are post-column derivatized with a reagent solution consisting of 0.1 mol L−1 Mg(II) at pH 9 at a flow rate of 0.6 mL min−1. The highly fluorescent Mg(II) chelates are detected at λ ex = 374 nm and λ em = 499 nm. The detection limits of the whole process are in the low μg L−1 level. The proposed method has been applied to the analysis of spiked natural water samples, and recovery rates higher than 80% have been obtained.

Analysis of herbicides in water using temperature-responsive chromatography and an aqueous mobile phase

A simple and rapid method has been developed for herbicides in water using temperature-responsive liquid chromatography (LC) and a column packed with poly( N-isopropylacrylamide) (PNIPAAm), a polymer anchored on the stationary-phase surface of modified silica. PNIPAAm reversibly changes its hydrophilic/hydrophobic properties in water in response to temperature. The method was used to determine five sulfonylurea and three urea herbicides. Separation was achieved with a 10 mM ammonium acetate (pH 3.0) isocratic aqueous mobile phase, and by changing the column temperature. The analytes were extracted from water by off-line solid-phase extraction (SPE) with an N-vinyl-pyrrolidone polymer cartridge. The average recoveries of the eight herbicides from spiked pure water, tap water and river water were 70–130% with relative standard deviations (RSDs) of <10%. The limits of quantitation (LOQ) of the eight herbicides were between 1 and 4 μg l −1.

Analytical procedure for the determination of chlortetracycline and 4-epi-chlortetracycline in pig kidneys

A liquid chromatography-diode array detection (LC-DAD) procedure has been developed for assaying chlortetracycline (CTC) and its 4-epimer (4-epi-CTC) residues in pig kidneys. The procedure involved extraction with 0.1 M oxalic buffer followed by protein precipitation with trichloroacetic acid. Further solid-phase extraction (SPE) clean-up on a Strata X polymeric cartridge was allowed to obtain an extract suitable for LC analysis. Chromatographic separation was carried out on a C 8 analytical column, using isocratic elution with methanol–acetonitrile–0.01 M oxalic acid (15:15:70, v/v/v) at ambient temperature. The flow-rate was 1.2 ml/min and the eluate was analysed at 365 nm. The whole procedure was evaluated according to the requirements of the European Union regulation 2002/657/EC determining specificity, decision limit (CCα), detection capacity (CCβ), trueness, precision and robustness during validation process. The decision limit (CCα) was 674.8 μg/kg for CTC and 683.6 μg/kg for 4-epi-CTC. The detection capacity (CCβ) was 683.6 and 696.3 μg/kg for CTC and 4-epi-CTC, respectively. The recoveries of CTC and 4-epi-CTC from spiked samples at the levels of 300, 600 and 900 μg/kg (0.5 × MRL, 1 × MRL and 1.5 × MRL) were higher than 70%. This method has higher throughput than reported previously extraction method with oxalic acid and acetonitrile used for dechelation and deproteinization.

Use of quadrupole time‐of‐flight mass spectrometry in the elucidation of unknown compounds present in environmental water

Target compound monitoring is often not sufficient to assess the quality of water, as many of the unknown micro-contaminants present might be a threat to the environment and human health. In this work, the potential of hybrid quadrupole time-of-flight mass spectrometry (QTOF-MS) coupled to liquid chromatography (LC) in the elucidation of unknown compounds in environmental water samples has been explored. Based on accurate mass measurement, possible elemental compositions for the precursor ions were calculated. Using model compounds, a useful strategy was developed, enabling determination and evaluation of potential molecular formulae for the detected unknowns. The possibility of performing tandem mass spectrometric (MS/MS) acquisitions to obtain product ion spectra in accurate mass mode also helped to elucidate the structures of these unknowns or to detect some functional groups, to further evaluate potential formulae. The remaining formulae were searched against available databases such as the Merck Index and the NIST library. Where standards were commercially available, retention time and MS/MS data were both also used as confirmatory tools. The approach developed was applied for the identification of unknown compounds in different types of water. To improve sensitivity, environmental water samples were preconcentrated on-line in a polymeric cartridge by direct injection of 2 mL water into the SPE-LC/MS/MS system. For three unknowns, structures were proposed and confirmed with standards. Although other compounds could not be unequivocally identified based on the data available within this study, details about the possible structures of some are given.

Solid-phase extraction of methadone enantiomers and benzodiazepines in biological fluids by two polymeric cartridges for liquid chromatographic analysis

The aim of this work was to present the advantages of two polymeric cartridges (Oasis HLB from Waters and Abselut Nexus from Varian) for the solid-phase extraction of methadone enantiomers and its major metabolite, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) and of some benzodiazepines (diazepam, flunitrazepam, nitrazepam, oxazepam) in serum and urine in comparison with classical C18-bonded-silica cartridges or liquid extraction. After addition of serum or urine samples, these two cartridges were washed with a water–methanol mixture (95:5, v/v) and eluted with diethylether. After rapid evaporation, the residue was regenerated with mobile phase and injected either in a chiral column (Cyclobond I-2000 RSP) for methadone enantiomers and its metabolite or in a reversed-phase column (Symmetry Shield RP8) for benzodiazepines. The results showed that the chromatograms of blank serum and urine were cleaner than those obtained from classical solid-phase extraction or liquid extraction. The recoveries from these two polymeric cartridges were higher (95–102%) than those obtained by the two previous classical methods and the total time for extraction and solvent evaporation was also shorter (about 6–7 min). For methadone and benzodiazepine extraction, the use of acidic or alkaline buffer was not necessary.

Multiresidue determination of pesticides in malt beverages by capillary gas chromatography with mass spectrometry and selected ion monitoring.

A method was developed to determine pesticides in malt beverages using solid phase extraction on a polymeric cartridge and sample cleanup with a MgSO4-topped aminopropyl cartridge, followed by capillary gas chromatography with electron impact mass spectrometry in the selected ion monitoring mode [GC-MS(SIM)]. Three GC injections were required to analyze and identify organophosphate, organohalogen, and organonitrogen pesticides. The pesticides were identified by the retention times of peaks of the target ion and qualifier-to-target ion ratios. GC detection limits for most of the pesticides were 5-10 ng/mL, and linearity was determined from 50 to 5000 ng/mL. Fortification studies were performed at 10 ng/mL for three malt beverages that differ in properties such as alcohol content, solids, and appearance. The recoveries from the three malt beverages were greater than 70% for 85 of the 142 pesticides (including isomers) studied. The data showed that the different malt beverage matrixes had no significant effect on the recoveries. This method was then applied to the screening and analysis of malt beverages for pesticides, resulting in the detection of the insectide carbaryl and the fungicide dimethomorph in real samples. The study indicates that pesticide levels in malt beverages are significantly lower than the tolerance levels set by the United States Environmental Protection Agency for malt beverage starting ingredients. The use of the extraction/cleanup procedure and analysis by GC-MS(SIM) proved effective in screening malt beverages for a wide variety of pesticides.

Determination of free molecular phenolics and catechins in wine by solid phase extraction on polymeric cartridges and liquid chromatography with diode array detection☆

The use of HLB Oasis polymeric cartridges to extract phenolic acids and aldehydes from red wines has been assayed and compared with the combination of ODS and SAX cartridges. The recoveries on the polymeric cartridges resulted to be notably higher with good precisions. The best operation conditions (cartridge conditioning, sample volume, clean-up and elution) for these latter were selected by experiments carried out on a synthetic wine sample spiked with 14 compounds and on red wine samples. A matrix-matched calibration was advisable to reduce the influence of the matrix in the quantification of the analytes as it was verified from the application of standard addition calibrations on several wine samples. Determination of the analytes in the extracts was performed by reversed-phase HPLC using mobile-phase and flow gradients and detection at 250, 280 and 340 nm.

Determination of free molecular phenolics and catechins in wine by solid phase extraction on polymeric cartridges and liquid chromatography with diode array detection

The use of HLB Oasis polymeric cartridges to extract phenolic acids and aldehydes from red wines has been assayed and compared with the combination of ODS and SAX cartridges. The recoveries on the polymeric cartridges resulted to be notably higher with good precisions. The best operation conditions (cartridge conditioning, sample volume, clean-up and elution) for these latter were selected by experiments carried out on a synthetic wine sample spiked with 14 compounds and on red wine samples. A matrix-matched calibration was advisable to reduce the influence of the matrix in the quantification of the analytes as it was verified from the application of standard addition calibrations on several wine samples. Determination of the analytes in the extracts was performed by reversed-phase HPLC using mobile-phase and flow gradients and detection at 250, 280 and 340 nm.

Liquid–liquid extraction followed by solid-phase extraction for the determination of lipophilic pesticides in beeswax by gas chromatography–electron-capture detection and matrix-matched calibration

Analytical methods for the simultaneous analysis of lindane, chlorpyriphos, z-chlorfenvinphos, endosulfan A and B, 4,4′-DDE, 4,4′-TDE, acrinathrine, bromopropylate, tetradifon, coumaphos and fluvalinate in pure beeswax samples are studied. For the analysis of bleached beeswaxes, a liquid–liquid extraction with acetonitrile followed by a clean-up on polymeric cartridges is the best option in terms of recovery and precision. However, some interferences that hinder the identification and quantification of important varroacides are found when non-bleached beeswaxes are analyzed. The analysis of all compounds in the latter samples require a clean-up by coupling an ODS cartridge before the polymeric cartridge. Considerations about the influence of the matrix in the quantitative analysis by a classical external standard calibration are also made and the use of a matrix-matched calibration is advised. Recoveries resulted to be about 100% with coefficients of variation between 10% and 20% ( n = 5) for concentrations of 0.5 and 5 mg/kg.

Ultrasonic extraction of veterinary antibiotics from soils and pig slurry with SPE clean-up and LC–UV and fluorescence detection

A simple and rapid analytical method is presented in which the three veterinary antibiotics oxytetracycline (OTC), sulfachloropyridazine (SCP) and tylosin (TYL) are simultaneously extracted and determined in four different soils. Extractions were carried out by a combination of ultrasonic agitation and vortex mixing using a mixture of methanol, EDTA and McIlvaine buffer at pH 7 as the extractant solution. The extracts were then cleaned-up by a tandem solid phase extraction (SPE) method using an Isolute SAX anion exchange cartridge to remove natural organic matter and an Oasis HLB polymeric cartridge to retain the study compounds. Analysis was by HPLC–UV with additional fluorescence detection for SCP. Recoveries were in the range 68–85% for SCP in all soil types, 58–75% for OTC in sandy soils, 27–51% for OTC in clay containing soils, 74–105% for TYL and 47–61% in a clay soil. OTC and SCP were also extracted from liquid pig manure using a mixture of EDTA and McIlvaine buffer at pH 7 with ultrasonic agitation and vortex mixing with SPE clean-up and HPLC–UV analysis. Recoveries were greater than 77% and 58% for OTC and SCP, respectively. Limits of detection were 18 μg kg −1 for OTC and SCP and 40 μg kg −1 for TYL in soils and 70 μg L −1 for OTC and 140 μg L −1 for SCP in pig slurry.

Fast and robust simultaneous determination of three veterinary antibiotics in groundwater and surface water using a tandem solid-phase extraction with high-performance liquid chromatography–UV detection

A simple and robust analytical method is presented in which the three veterinary antibiotics oxytetracycline (OTC), sulfachloropyridazine (SCP) and tylosin (TYL) were simultaneously determined in surface water and groundwater. The three compounds were simultaneously extracted from the water samples using a mixture of methanol, EDTA and McIlvaine buffer (citric acid and sodium orthophosphate) and then cleaned-up and pre-concentrated by solid-phase extraction using sacrificial Isolute strong anion-exchange cartridges, to remove interfering organic material, and Waters Oasis hydrophilic–liphophilic balance polymer cartridges, to retain the compounds, in tandem. Analysis was performed using liquid chromatography with ultraviolet detection. Recoveries for river water samples spiked at 10 and 1 μg l −1 were respectively 99.6±4.6 and 99.4±8.4% for OTC; 99.9±2.2 and 105.0±5.7% for SCP; and 94.9±2.4 and 71.6±8.2% for TYL. Overall limits of detection based on pre-concentrating 400 ml of sample were 0.35 μg l −1 for OTC and TYL and 0.25 μg l −1 for SCP.

Monitoring of pesticides and polycyclic aromatic hydrocarbons in water from Paraíba do Sul River, Brazil

The Paraíba do Sul River, in the State of Rio de Janeiro, was studied for its water quality, by determining the levels of selected polycyclic aromatic hydrocarbons (PAHs) and pesticides from six sites in two cities, Resende and Campos dos Goytacazes, as they have industrial and agricultural activities. This study was carried out between July 2001 and March 2002. The method involved 200 mL samples taken by off-line, solid phase extraction by OASIS polymeric cartridges followed by gas chromatography-mass spectrometry (GC-MS). Recoveries and standard deviation of pesticides in non polluted real water sample spiked with a standard mixture were 82-119% and less then 20%. For PAH, recoveries and standard deviation were 56-78% and less then 18%, respectively, with exception to acenaphthylene, 23% and 2.7%. Atrazine was detected in the average concentration of 0.231 µg L-1 in two sites in Campos dos Goytacazes, near the sugar-cane power plants and plantations area, while no detection was observed in Resende. Irgarol was observed in Campos dos Goytacazes downtown at 0.138 µg L-1, an area of small boating activities. Benzo[a]pyrene was detected at 0.255 µg L-1 in Resende, near the Presidente Dutra highway. PAHs were not detected in the water samples from Campos dos Goytacazes.

Determination and quantitation of sulfonylurea and urea herbicides in water samples using liquid chromatography with electrospray ionization mass spectrometric detection

A multianalyte method has been developed for the confirmation and quantitation of five sulfonylureas, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, flazasulfuron and halosulfuron-methyl, and for three ureas, siduron, dymron (daimuron) and diuron (DCMU) in water. Samples were extracted from water by off-line solid-phase extraction (SPE) with a polystyrene polymer cartridge (PS2), an ODS C 18-bonded silica cartridge (C 18) and an N-vinylpyrrolidone polymer cartridge (Oasis). Analyte determination and quantitation were performed by liquid chromatography with mass spectrometry (LC–MS). Extraction efficiency experiments demonstrated the ability of this method to extract sulfonylureas and ureas from water samples. Confirmatory analysis was carried out by LC-electrospray mass spectrometry (LC–ESI–MS) instrumentation equipped with a single-quadrupole mass filter. MS data acquisition was performed by a single or two-ion selected ion monitoring (SIM) program. It is required for confirmation that LC–MS retention times of the analytes are within 1% of the retention times of the standards, and that the molecular ion or characteristic fragment ion is present for each analyte. Fragment ions from distinctive structures must be obtained to identify and characterize specific herbicide molecules. These were obtained by controlled decomposition of sulfonylurea and urea adduct ions after suitably adjusting the electrical field in the desolvation chamber. The eight herbicides were also measured in fortified pure water (water purified by a milli-Q system), tap water and river water. Average recoveries of the eight analytes from water samples were in the range of 70–120% with relative standard deviations (R.S.D.s) of <20%. The limit of quantitation (LOQ) for each of the eight herbicides was between 10 and 100 ng l −1.

Determination of nitrate in environmental water samples by conversion into nitrophenols and solid phase extraction−spectrophotometry, liquid chromatography or gas chromatography–mass spectrometry

Conversion of nitrate into a nitro-phenol derivative by reaction with 2-methylphenol or 2,6-dimethylphenol allowed at least 100-fold enrichment of the derivative on Lichrolut EN polymeric cartridge, and it is stable for up to 1 month on the cartridge. The derivative could be eluted with ammonia–methanol mixture. This reaction for nitrate determination has permitted a choice of final measurement by UV-Vis spectrophotometry, liquid chromatography or gas chromatography–mass spectrometry when the limits of detection were 10, 6 and 3 μg l −1, respectively, and the calibration range 20 μg to 10 mg l −1 nitrate. The method has been validated by spiking natural water samples, when the recovery of nitrate was 98.5–108.4% (relative standard deviation 2.5–6.1%).

Multiresidue pesticide analysis in wines by solid-phase extraction and capillary gas chromatography-mass spectrometric detection with selective ion monitoring.

A method was developed to determine pesticides in wines. The pesticides were extracted from the wine using solid-phase extraction on a polymeric cartridge, and the coextractives were removed with an aminopropyl-MgSO(4) cartridge. Analysis was performed using capillary gas chromatography with electron impact mass spectrometric detection in selective ion monitoring mode (GC-MSD/SIM). Three injections are required to analyze all 153 organohalogen, organonitrogen, organophosphate, and organosulfur pesticides and residues. Pesticides were confirmed by retention times of the target ions and three qualifier-to-target ion ratios. Detection limits for most of the pesticides were less than 0.005 mg/L, and quantitation was determined from approximately 0.01 to 5 mg/L. Spike recoveries were performed by fortifying red and white wines at 0.01 and 0.10 mg/L. At the 0.01 ppm level, the spike recoveries were greater than 70% for 116 and 124 pesticides (out of 153) in red and white wines, respectively, whereas at the higher spike concentration of 0.10 mg/L, the recoveries were greater than 70% for 123 and 128 pesticides in red and white wines, respectively. The recoveries of less than 70% were most likely from pesticide polarity or lability, resulting in the inefficient adsorption of the pesticide to the polymeric sorbent, ineffective elution of the pesticide from the sorbent, or thermal degradation of the pesticide under GC-MSD conditions.