On-line Solid-phase Extraction Liquid Research Articles

Trace determination of priority pesticides in water by means of high-speed on-line solid-phase extraction–liquid chromatography–tandem mass spectrometry using turbulent-flow chromatography columns for enrichment and a short monolithic column for fast liquid chromatographic separation

An integrated on-line SPE–HPLC–MS/MS system has been developed for the rapid analysis of various trace level priority pesticides in surface and drinking water. Eleven pesticides were included in this study, with various phenylureas, triazines and organophosphorous species among them. Use of turbulent-flow chromatography columns (TFC, 50×1 mm, 30–50 μm particle size) as extraction cartridges enables fast on-line SPE at high sampling flow-rate (5 ml/min). Polymeric and carbon based TFC columns (Oasis HLB, Cyclone, Hypercarb) allow complete extraction with good recoveries from water volumes up to 50 ml. On-line coupling to HPLC is performed with re-mixing of the organic TFC eluate with water in front of the analytical column to ensure efficient band focussing. For fast HPLC analysis, a short monolithic column is applied in combination with highly selective API–MS/MS detection. Matrix effects on the APCI–MS/MS signal were found to be reduced by the system to an acceptable minimum. Limits of detection, determined for 10-ml samples of river water were in the range between 0.4 and 13 ng/l typically, except trifluralin (approximately 280 ng/l), which is less susceptible to ionization under atmospheric pressure conditions. At an enriched water volume of 10 ml, the whole SPE–HPLC–MS/MS procedure requires less than 14 min. The method was successfully applied to the analysis of drinking and surface water samples taken from several sampling sites around the city of Leipzig, Germany. Concentrations measured (maximum: 16 ng/l simazine in river water) were far below the concentration limits scheduled by law.

Monitoring of antifouling agents in water samples by on-line solid-phase extraction–liquid chromatography–atmospheric pressure chemical ionization mass spectrometry

An automatic method for determining diuron, irgarol 1051, folpet and dichlofluanid in seawater samples have been developed. This method is based on the on-line coupling of solid-phase extraction (SPE) with a highly crosslinked polymeric sorbent, LiChrolut EN, to liquid chromatography followed by atmospheric pressure chemical ionization (APCI) and mass spectrometry. The operational parameters affecting the APCI interface have been studied in both positive and negative ionization modes. The use of LiChrolut EN in the SPE produced recoveries of over 85% for all the compounds when 100 ml of seawater sample was preconcentrated. Calibration was carried out in both ionization modes and in full-scan and selected-ion monitoring (SIM). The method allowed all the analytes to be detected at 5 ng l −1 in SIM acquisition mode except folpet, which, because of its low response, could only be detected at 250 ng l −1. The method was used to analyse water samples taken from five different marina and fishing ports along the coast of Tarragona, Catalonia (Spain), over a 5-month period. Diuron and irgarol 1051 were detected and quantified in most samples at concentration levels ranging from 27 to 420 ng l −1 for diuron and from 15 to 511 ng l −1 for irgarol 1051.

Determination of quaternary ammonium pesticides by liquid chromatography–electrospray tandem mass spectrometry

A method for the direct determination of paraquat, diquat, chlormequat and difenzoquat in water samples, using an on-line solid-phase extraction–liquid chromatography–tandem mass spectrometry system was developed. No sample preparation was required and the detection limits were below the European Union maximum residue levels. The chromatographic separation was performed using an XTera MS C 8 column. The concentration of the ion pair reagent, the pH and the gradient elution were optimized to give high recoveries and good chromatographic resolution between quats. The detection was carried out using an ion trap as mass analyzer. Parameters such as the magnitude and duration of the resonant excitation voltage and the magnitude of the trapping RF voltage for full scan tandem mass spectrometry (MS–MS) experiments were studied to establish the optimal experimental conditions. Moreover, the accurate optimization of these parameters allowed MS–MS experiments of low mass ions, below m/z 200, providing unambiguous peak identification. Finally, the reproducibility of the proposed method was shown by good run-to-run and day-to-day precision values and its applicability to the determination of quats in drinking water was evaluated using spiked samples.

Determination of steroid sex hormones and related synthetic compounds considered as endocrine disrupters in water by fully automated on-line solid-phase extraction–liquid chromatography–diode array detection

In this study, a procedure for the simultaneous determination in water of six estrogens (estradiol, estriol, estrone, ethynyl estradiol, mestranol, and diethylstilbestrol) and three progestogens (progesterone, norethindrone, and levonorgestrel), selected based on their abundance in the human body, their estrogenic potency, and the extent of their use in contraceptive pills, was developed. The procedure, based on the on-line solid-phase extraction (SPE) of the water sample and subsequent analysis by liquid chromatography/diode array detection (LC/DAD), allows for the monitoring of up to 16 samples in a completely automated, unattended way. The SPE experimental conditions were optimized and the polymeric cartridge PLRP-S selected out of four different cartridges evaluated. The chromatographic separation was carried out on a LiChrospher 100 RP-18 and detection was performed at 200, 225, and 240 nm. The applicability of the method to the analysis of various environmental water samples, including drinking water, groundwater, surface water and sewage treatment plant effluents, was evaluated. Method detection limits were in the range 10–20 ng/l. The method precision and accuracy were satisfactory with recovery percentages ranging from 96 to 111% and relative standard deviations lower than 3%. The technique is also considerably cheap, fast, and easy, and, therefore, very adequate for routing monitoring. To the authors’ knowledge it constitutes the first work describing a fully automated, on-line methodology for the continuous monitoring of these compounds in water.

Determination of retigabine and its acetyl metabolite in biological matrices by on-line solid-phase extraction (column switching) liquid chromatography with tandem mass spectrometry

A HPLC assay with tandem mass spectrometric detection in the positive-ion atmospheric pressure chemical ionisation (APCI) mode for the sensitive determination of retigabine [( I), D-23129] and its acetyl metabolite [( II), ADW 21-360] in plasma was developed, utilising the structural analogue (D-10328), ( III), as internal standard. Automated on-line solid-phase extraction of diluted plasma samples, based on 200-μl plasma aliquots, at pH 6.5, allowed a reliable quantification of retigabine and the acetyl metabolite down to 1 ng/ml. Injection of 500 μl of diluted plasma onto a C 2 stationary phase-based column switching system in combination with a 75 mm×4 mm reversed-phase analytical column at a flow-rate of 0.5 ml/min provided cycle times of 4 min per sample. The standard curves were linear from 1 to 1000 ng/ml using weighted linear regression analysis (1/ x 2). The method is accurate (mean accuracy ≤±10%), precise (RSD <±15%) and sensitive, providing lower limits of quantification in plasma of 1 ng/ml for retigabine ( I), and 2.5 ng/ml for the metabolite ( II) with limits of detection of 0.5 ng/ml for both analytes. Up to 200 unknowns may be analysed each 24 h per analyst.

Determination of naphthalenesulfonates in water by on-line ion-pair solid-phase extraction and ion-pair liquid chromatography with fast-scanning fluorescence detection

A fast analytical method for quantifying a mixture of 12 naphthalenesulfonates and naphthalenedisulfonates has been developed. This method consists of on-line ion-pair solid-phase extraction with PLRP-s sorbent and ion-pair liquid-chromatography using fast-scanning fluorescence spectrometer as a detection system and multivariate calibration. As complete separation is unnecessary, the compounds were analysed in isocratic conditions and the chromatographic analysis took only 25 min. Three-way partial least-squares (PLS) was used to carry out multivariate calibration for spiked tap water. In these conditions, quantification limits were between 0.01 and 3 μg l −1. Repeatability was also evaluated and relative standard deviations ( n=3) were between 0.5 and 4, depending on the compound. Finally, spiked tap and Ebro river waters were analysed to evaluate prediction capability of the method.

Quantitation of nifedipine in human plasma by on-line solid-phase extraction and high-performance liquid chromatography

An analytical methodology for nifedipine quantitation in plasma by on-line solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) is described. The SPE cartridges contain C 2 and the analytes nifedipine and nitrendipine (internal standard) are separated on a C 18 column with a mobile phase consisting of acetonitrile–13 m M phosphate buffer pH 7 (65:35, v/v) followed by UV detection at 338 nm. Validation of the method demonstrated good recoveries (>90%), sensitivity (limit of quantification, 2 ng/ml), based on a 500 μl sample volume, accuracy and precision (<5.5% in concentrations greater than the limit of quantitation). This methodology has been used for bioequivalence studies.

Characterization of photodegradation products of alachlor in water by on-line solid-phase extraction liquid chromatography combined with tandem mass spectrometry and orthogonal-acceleration time-of-flight mass spectrometry.

On-line solid-phase extraction liquid chromatography in combination with mass spectrometry (MS), i.e. MS/MS and orthogonal-acceleration time-of-flight MS, was used for the characterization of photodegradation products of alachlor in river water. Various MS/MS scan functions were used, in particular the precursor-ion and the daughter-ion modes, to screen for degradation products with structures closely related to that of alachlor and to obtain information on characteristic fragments of the degradation products. Elemental compositions of compounds found and some of their fragments were calculated from the accurate mass information obtained with orthogonal-acceleration time-of-flight MS. Some ten degradation products could be characterized by combining various types of mass spectral information. Since quite a number of isomers were identified, structures of the degradation products were proposed by considering the most likely fragmentation patterns in MS/MS experiments. Degradation products of alachlor found in the current study were compared with those reported in the literature.

Piroxicam quantitation in human plasma by high-performance liquid chromatography with on- and off-line solid-phase extraction

A comparative study of two analytical methodologies for piroxicam quantitation in plasma by off-line and on-line solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) is described. The SPE cartridges contained C 8 for both extraction methods. The analytes piroxicam and tenoxican (internal standard) were separated on a C 18 column with a mobile phase consisting of acetonitrile:20 m M phosphate buffer pH 3.1 (50:50, v/v) followed by UV detection at 360 nm. The validation of the methods demonstrated good recoveries (over 90%), sensitivity (limits of quantification of 0.05 μg/ml with on-line SPE and 0.1 μg/ml with off-line SPE, based on a 100 μl and 200 μl sample volume, respectively), accuracy and precision (better than 9.5%). Both methodologies have been used for bioequivalence studies.

Fully automated analytical method for codeine quantification in human plasma using on-line solid-phase extraction and high-performance liquid chromatography with ultraviolet detection

A simple, sensitive and fully automated analytical method for the analysis of codeine in human plasma is presented. Samples are added with oxycodone, used as internal standard (I.S.), and directly loaded in the autosampler tray. An on-line sample clean-up system based on solid-phase extraction (SPE) cartridges (Bond-Elut C 2, 20 mg) and valve switching (Prospekt) is used. Isocratic elution improved reproducibility and allowed the recirculation of the mobile phase. A Hypersil BDS C 18, 3 μm, 10×0.46 cm column was used and detection was done by UV monitoring at 212 nm. Retention times of norcodeine (codeine metabolite), codeine and oxycodone (I.S.) were 5.5, 6.4 and 9.1 min, respectively. Morphine was left to elute in the chromatographic front. Detection limit for codeine was 0.5 μg l −1 and inter-assay precision (expressed as relative standard deviation) and accuracy (expressed as relative error) measured at 2 μg l −1 were 5.03% and 1.82%. Calibration range was 2–140 μg l −1.

On-line solid-phase extraction liquid chromatography-continuous flow frit fast atom bombardment mass spectrometric and tandem mass spectrometric determination of hydrolysis products of nerve agents alkyl methylphosphonic acids by p-bromophenacyl derivatization

For proof of the presence of chemical warfare agents sarin, soman and VX, a rapid, accurate and sensitive method which allows us to determine their hydrolysis products ethyl methylphosphonic acid, isopropyl methylphosphonic acid and pinacolyl methyl phosphonic acid was explored by using continuous flow frit fast atom bombardment (FAB) LC–MS and LC–MS–MS. After derivatization of analytes with p-bromophenacyl bromide, LC–MS–MS analyses for screening were performed by a flow injection method. The three alkyl methylphosphonic acids (AMPAs) were eluted within 5 min, and the detection limits for the three AMPAs ranged from 1 to 5 ng/ml. For confirmation of the screening results, LC–MS–MS analysis with chromatographic separation was conducted by using a narrow bore column. The three AMPAs were all eluted with excellent separation within 25 min, and the detection limits ranged from 1 to 20 ng/ml. Quantitative measurement was performed by LC–MS in selected ion monitoring (SIM) mode with chromatographic separation. Linear calibration curves were obtained for the three AMPAs and the detection limits ranged from 0.5 to 3 ng/ml. The relative standard deviation for peak area ranged from 3.4 to 6.0% at 50 ng/ml for the three AMPAs.

Accurate mass determinations for the confirmation and identification of organic microcontaminants in surface water using on-line solid-phase extraction liquid chromatography electrospray orthogonal-acceleration time-of-flight mass spectrometry.

The identification of polar microcontaminants in surface water is an important issue in environmental analysis. Liquid chromatography/mass spectrometry (LC/MS) is frequently applied for this purpose. However, even in combination with tandem mass spectrometry (MS/MS), unambiguous identification of the compounds detected is often difficult. The potential of an alternative strategy, based on the ability of an orthogonal-acceleration time-of-flight mass spectrometer to routinely perform accurate mass determination at 10 ppm in on-line LC/MS, is explored. On-line solid-phase extraction LC electrospray orthogonal-acceleration time-of-flight mass spectrometry is shown to enable the determination of pesticides from various compound classes in surface water in the concentration range of 0.1 to 10 micrograms/L. In addition, the ability to discriminate and unambiguously identify pesticides in mixtures of isobaric and/or isomeric compounds is investigated.

Chemical removal of humic substances interfering with the on-line solid-phase extraction—Liquid chromatographic determination of polar water pollutants

Different methods for removing interference by humic substances in the analysis of polar pollutants have been compared in the analysis of environmental water by solid-phase extraction (SPE) with a chemically modified polymeric resin coupled on-line to liquid chromatography with UV detection.

Identification of Carbofuran And Methiocarb and their Transformation Products in Estuarine Waters by On-line Solid Phase Extraction Liquid Chromatography—Mass Spectrometry

Abstract The degradation of the carbamate insecticides carbofuran and methiocarb in distilled and natural waters was determined. Degradation studies were carried out both under a xenon arc irradiation and natural sunlight at pesticide concentrations of 50–100 μg/L. 50–100 mL water sample were preconcentrated using automated online solid phase extraction (SPE) followed by liquid chromatography (LC), UV detection or post column fluorescence detection (EPA method 531.1 for carbamate insecticides). Structure identification was carried out by on-line SPE-LC-MS either with thermospray and/or high flow pneumatically assisted electrospray interfaces. Half-lives varying between 4–12.5 days for carbofuran and methiocarb were determined under natural sunlight exposure, being chemical hydrolysis the major degradation pathway. When using xenon arc lamp irradiation both pesticides degraded very rapidly with half-lives varying from 0.3–1.7 hours. The various degradation products identified were: methiocarb sulfoxide, 4-methylthio-3, 5-dimethylphenol, 3-hydroxy-7-carbofuranphenol and 2-hydroxy-3-(2-methylprop-1-enyl)-phenyl-N-methylcarbamate.

On-line solid-phase extraction–liquid chromatography–particle beam mass spectrometry and gas chromatography–mass spectrometry of carbamate pesticides

On-line solid-phase extraction–liquid chromatography–particle beam mass spectrometry (SPE–LC–PB-MS) was used to study 32 carbamates and 11 of their transformation products in environmental water samples. The analytes were enriched from 100 ml samples on Bondesil-C18/OH, packed in a 10 mm × 3.0 mm id precolumn, eluted on-line with a gradient of methanol–0.1 mol l–1 ammonium acetate to a C18 analytical column and detected by PB-MS. Detection limits of 12 carbamates and five degradation products were 0.1–8 µg l–1 in surface water, using full-scan electron impact mode detection. The RSDs of the retention times were 0.05–0.2% and those of peak areas 5–35%. Twenty-eight analytes proved to be amenable to GC with detection limits of 0.05–3 ng injected on-column. When using the same mass spectrometer, the spectra obtained by LC–PB-MS and GC–MS were identical.

Rapid and highly automated determination of morphine and morphine glucuronides in plasma by on-line solid-phase extraction and column liquid chromatography

A high-performance liquid chromatography (HPLC) method has been developed for the determination of morphine and its main metabolites, morphine-6-glucuronide (M-6-G) and morphine-3-glucuronide (M-3-G), in plasma or cerebrospinal fluid. Samples were extracted using on-line solid-phase extraction followed by reversed-phase HPLC with fluorescence detection. Recoveries of 20 ng morphine and morphine glucuronides in plasma were over 95%. The limit of detection using 400 μl of a biological matrix was 0.85, 3.4 and 1.0 ng/ml of M-3-G, M-6-G and morphine, respectively. Inter- and intra-day assay precision was better than 10%. The main advantages of the present described method are increased recoveries (>95%) and a high degree of automation allowing a high speed in routine analysis. The time required for the fully automated analysis of one sample was less than 26 min.

Behavioral states and the central nervous system

Used frequently in food contact materials, bisphenol A (BPA) has been studied extensively in recent years, and ubiquitous exposure in the general population has been demonstrated worldwide. Characterizing within- and between-individual variability of BPA concentrations is important for characterizing exposure in biomonitoring studies, and this has been investigated previously in adults, but not in children. The aim of this study was to characterize the short-term variability of BPA in spot urine samples in young children. Children aged ≥ 2–< 4 years (n = 25) were recruited from an existing cohort in Queensland, Australia, and donated four spot urine samples each over a two day period. Samples were analysed for total BPA using isotope dilution online solid phase extraction–liquid chromatography–tandem mass spectrometry, and concentrations ranged from 0.53 to 74.5 ng/ml, with geometric mean and standard deviation of 2.70 ng/ml and 2.94 ng/ml, respectively. Sex and time of sample collection were not significant predictors of BPA concentration. The between-individual variability was approximately equal to the within-individual variability (ICC = 0.51), and this ICC is somewhat higher than previously reported literature values. This may be the result of physiological or behavioural differences between children and adults or of the relatively short exposure window assessed. Using a bootstrapping methodology, a single sample resulted in correct tertile classification approximately 70% of the time. This study suggests that single spot samples obtained from young children provide a reliable characterization of absolute and relative exposure over the short time window studied, but this may not hold true over longer timeframes.