Solid-phase Extraction Disks Research Articles

Simple determination of 99Tc in radioactive waste using Tc extraction disk and imaging plates

A simple method was developed for determination of 99Tc in low-level radioactive waste: Technetium-99 retained by a solid phase extraction disk was directly measured with imaging plates system. It was found that more than 97% of Tc were retained by the disk from a solution of pH 2 to 12, whereas depth profile of Tc in the disk, which greatly influences the counting efficiency, depended on solution pH. The present method was successfully applied to actual radioactive liquid waste samples arising from nuclear research facilities.

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p, p′-DDE, and p, p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL −1 for PCBs and from 0.12 to 0.36 ng mL −1 for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.

Comparing the passive sampler and biomonitoring of organic pollutants in water: A laboratory study

Passive sampling could provide the solution to problems associated with costly and time consuming sampling programmes and biomonitoring. Mussels (Mytilus edulis) and Chemcatcher passive sampler were simultaneously analyzed for sequestered pesticides and polychlorinated biphenyls (PCBs) by gas chromatography with mass spectrometry (GC/MSD). The Chemcatcher passive sampler based on a solid phase extraction disc with two types of diffusion-limiting membranes (polyethelene and polysulphone), were also compared. Diuron, atrazine, irgarol and lindane were accumulated in the polysulphone passive sampler in greater concentration than in the mussels or in the other passive samplers with polyethelene limiting-membrane. Mussels can accumulate in their tissue high concentration of non polar compounds such as PCB 52, dieldren and PCB 153; more than the passive sampler with polysulphone membrane. The device with polyethelene limiting membrane has high affinity capacity to concentrate high amount of phenenthrene, dieldrin, PCB 153 and PCB 52, so it acts as a sampler for non-polar compounds. The highest uptake rate of hydrophobic compounds by Chemcatcher was observed for analytes with log octanol-water partition coefficient (KOW) between 4.5 and 7.5. Laboratory-based studies using passive samplers to assess the potential for bioaccumulation could provide robust and reliable information at relatively low cost compared to biomonitoring data. Laboratory data obtained using passive samplers could be related to accumulation under field conditions where field assessments are required.

Simultaneous determination of 15 steroidal oral contraceptives in water using solid-phase disk extraction followed by high performance liquid chromatography–tandem mass spectrometry

A rapid, accurate and sensitive method for simultaneous determination of 15 steroidal hormones including four estrogens (estrone, 17β-estradiol, 17α-ethynylestradiol, estriol) and eleven progestogens (17β-estradiol-3-benzoate, 19-norethindrone, gestodene, levonorgestrel, medroxyprogesterone, cyproterone acetate, megestrol-17-acetate, progesterone, norethindrone acetate, chlormadinone-17-acetate, and hydroxy progesterone caproate) in environmental waters was developed by coupling solid-phase disk extraction (SPDE) to ultra performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) with electrospray ionization. Among three types of extraction tested (C 8 SPDE, C 18 SPDE and C 18 SPE), the most satisfactory result was achieved using C 18 SPDE for its satisfactory recovery (75.6 to 101.4%) and short extraction time (15 min for 1 L deionised water). The validity of this method was investigated and good analytical performance for all the analytes was obtained, including low limits of method detection (0.5–3.4 ng/L) and excellent linear dynamic range (1.0–50.0 ng/L). The method was applied to determine the steroidal hormones in 10 environmental waters including tap water, river water, lake water and waste water in Beijing. No progestogen was detected in all samples and estrone, estriol, 17α-ethynylestradiol were found in most samples at levels between 1.8 and 127.9 ng/L.

Use and Reuse of SPE Disks for the Determination of Pyrethroids in Water by GC-ECD

Seven pyrethroids (bifenthrin, fenpropathrin, λ-cyhalothrin, permethrin, α-cypermethrin, fenvalerate, and deltamethrin) were extracted from water using C18 solid-phase extraction disks, followed by gas chromatography with an electron capture detector (GC-ECD) analysis. The limits of detection in water samples ranged from 0.5 ng L−1 (fenpropathrin) to 110 ng L−1 (permethrin), applying the calibration graph. The effects of different numbers of (re)utilizations of the same disks (up to four times with several concentrations) on the recoveries of the pyrethroids were considered. The recoveries were all between 70 and 120% after four utilizations of the same disk. There was no difference between these recoveries at a confidence level of 95%.

Total concentration analysis of polycylic aromatic hydrocarbons in aqueous samples with high suspended particulate matter content

The European water framework directive (WFD) requires priority pollutants to be measured in the whole water sample and not only in the dissolved phase. However, it does not give clear definitions on how to achieve this. To overcome this limitation, a new methodology of sample preparation procedure for the analysis of polycyclic aromatic hydrocarbons on the basis of extraction disks is introduced here. The automatable procedure includes a “one-step” extraction of the analytes both dissolved in the liquid phase of the sample and sorbed to suspended particulate matter. The latter is extracted concurrently with the solid-phase extraction (SPE) material within the elution step of the procedure. Separation, identification, and quantification of the analytes is performed by GC–MS. Results from surface water samples spiked with certified sediment up to 1000 mg/l are presented in this work and compared with results derived from liquid–liquid extraction (LLE). Most measured values are within or at least near certified uncertainty limits of the sediment. The SPE disk method shows much higher recoveries and better precision (relative standard deviations between 2% and 11%) than the standard LLE method. For all substances under investigation, the limits of quantification achieved range between 0.001 and 0.005 μg/l.

脱離エレクトロスプレーイオン化質量分析用イオン源の試作と迅速分析への応用

High-performance liquid chromatography/mass spectrometry (LC/MS) is the most useful tool for qualitative and quantitative chemical analysis in the life sciences. However, sample preparation and LC separation demand an extraordinary amount of time and effort. Desorption electrospray ionization (DESI) and direct analysis in real time (DART) techniques that obtain mass spectra of samples without difficulty have been developed in recent years. We connected a home-built DESI ion source to an existing mass spectrometer and examined its performance. In this paper, we report the application of DESI to thin-layer chromatography (TLC)/DESI-MS in rapid analysis of medicines in serum and concentrated analysis with a solid-phase extraction disk.

Determination of dissolved domoic acid in seawater with reversed-phase extraction disks and rapid resolution liquid chromatography tandem mass spectrometry with head-column trapping

Domoic acid (DA) is the principal neurotoxin responsible for amnesic shellfish poisoning (ASP) and is produced, among other species, by marine diatoms of the genus Pseudo-nitzschia. In this work, a method for the determination of dissolved DA and its isomers present in seawater has been developed, based on a solid-phase extraction (SPE) disks followed by rapid resolution liquid chromatography coupled with tandem mass spectrometry. SPE provided sample desalting and 20-fold concentration of dissolved DA, while complete resolution between DA and its isomers was achieved in less than 3 min with rapid resolution chromatography thus providing high sample throughput. Additionally, a simple on-column chromatographic procedure allowed head-column trapping of DA providing 15-fold higher sensitivity. The conditions developed in this work have shown appropriate quality parameters in a within-laboratory validation. The detection limit was 0.02 ng mL −1 for the whole method, while trueness ranged between 92.1% and 110.6% recovery and precision between 8.4% and 19.0% relative standard deviation. Expanded uncertainty measured was 1.92, 0.23 and 0.03 for 10.0, 1.0 and 0.1 ng mL −1 DA concentrations, respectively, which demonstrated the accuracy of this method for confirmation and quantification of DA present at very low concentration levels in seawater.

A new solid-phase extraction disk based on a sheet of single-walled carbon nanotubes

A new kind of solid-phase extraction disk based on a sheet of single-walled carbon nanotubes (SWCNTs) is developed in this study. The properties of such disks are tested, and different disks showed satisfactory reproducibility. One liter of aqueous solution can pass through the disk within 10-100 min while still allowing good recoveries. Two disks (DD-disk) can be stacked to enrich phthalate esters, bisphenol A (BPA), 4-n-nonylphenol (4-NP), 4-tert-octylphenol (4-OP) and chlorophenols from various volumes of solution. The results show that SWCNT disks have high extraction ability for all analytes. The SWCNT disk can extract polar chlorophenols more efficiently than a C(18) disk from water solution. Unlike the activated carbon disk, analytes adsorbed by the new disks can be eluted completely with 8-15 mL of methanol or acetonitrile. Finally, the DD-disk system is used to pretreat 1000-mL real-world water samples spiked with BPA, 4-OP and 4-NP. Detection limits of 7, 25, and 38 ng L(-1) for BPA, 4-OP, and 4-NP, respectively, were achieved under optimized conditions. The advantages of this new disk include its strong adsorption ability, its high flow rate and its easy preparation.

A new approach to the application of solid phase extraction disks with LC–MS/MS for the analysis of drugs on a 96-well plate format

A new 96-well disk solid phase extraction sample preparation technique which does not involve vacuum pumps integrated with liquid chromatographic tandem mass spectrometric (LC–MS/MS) was developed for high throughput determination of benzodiazepines (nordiazepam, diazepam, lorazepam and oxazepam). In addition, the method completely allows the re-use of the SPE disk membranes for subsequent analyses after re-conditioning. The method utilizes a robotic autosampler for parallel extractions in a 96-well plate format. Results have been presented for independent extractions from three matrices; phosphate buffer solution, urine, and plasma. Factors affecting data reproducibility, extraction kinetics, sample throughput, and reliability of the system were investigated and optimized. A total time required per sample was 0.94 min using 96-well format. Method reproducibility was ≤9% relative standard deviation for all three matrices. Limits of detection and quantitation recorded were respectively in the range 0.02–0.15 and 0.2–2.0 ng/mL with linearity ranging from 0.2 to 500 ng/mL for all matrices.

Solid-phase extraction of sulfonylurea herbicides from water samples with single-walled carbon nanotubes disk

This study presents a new, easily made and practical solid-phase extraction disk, a single-walled carbon nanotubes (SWCNTs) disk. The properties of the disk were evaluated by extracting large volumes of aqueous solution (500–3,000 mL) spiked with trace levels of sulfonylurea herbicides, metsulfuron-methyl, chlorsulfuron, bensulfuron-methyl, pyrazosulfuron-ethyl, and chlorimuron-ethyl. The adsorption of analytes on the SWCNTs disk was more favorable at pH 3.0, and the adsorbed sulfonylurea herbicides could be eluted completely with acetonitrile (1% acetic acid) solvent. The disks were stacked to enhance their extraction ability to analytes. The triple layered SWCNTs disks system showed excellent extraction efficiency when the sample volume was up to 3,000 mL. A comparative study was conducted with a commercial C18 disk and an activated carbon disk. The SWCNTs disks showed an adsorption capacity comparable to sulfonylurea herbicides to the C18 disk and activated carbon disk, but the analytes retained on the activated carbon disk were hardly desorbed. Finally, the triple layered SWCNTs disks system was used to pretreat 1,000 mL of several environmental water samples spiked with the analytes, and satisfactory recoveries (79–102%) were obtained. Detection limits of 1.1–7.2 ng L−1 for analytes were achieved under the optimized conditions.

Utility of disk solid-phase extraction for whole blood samples: analysis of some tetracyclic antidepressants by gas chromatography with nitrogen-phosphorus detection

Four tetracyclic antidepressants, maprotiline, mianserin, mirtazapine, and setiptiline, were extracted from human whole blood and plasma samples by disk solid-phase extraction with Empore C18 cartridges. They were determined by gas chromatography (GC) with nitrogen-phosphorus detection. Recoveries of maprotiline, mianserin, mirtazapine, and setiptiline spiked into whole blood or plasma were more than 83%. Regression equations for the four drugs showed excellent linearity in the range of 25–1000 ng in 0.2 ml whole blood and in 0.5 ml plasma. The limits of detection for the drugs were 4.1–18.2 ng per 0.2 ml for whole blood and 3.4–13.5 ng per 0.5 ml for plasma. The limits of quantification for the four drugs were 25 ng in 0.2 ml whole blood and in 0.5 ml plasma. Intraday and interday coefficients of variation for the antidepressants in both human specimens were below 15%. The above data show that relatively hydrophobic and basic drugs in crude biological samples such as whole blood can be extracted by disk solid-phase extraction very efficiently and with good reproducibility, and suggest that the extraction method is also useful as pretreatments before more sophisticated detection methods such as GC-mass spectrometry (MS) and liquid chromatography-MS(-MS).

Monolithic solid-phase extraction for the rapid on-line monitoring of microcystins in surface waters

We describe the development and optimization of a sensitive and selective screening method for the measurement of trace levels of microcystins in surface waters. Several sample preparation techniques were compared, including solid-phase microextraction (SPME), particle-based solid-phase extraction (SPE), and monolith-based SPE. A flow-injection (FI) based approach employing a reversed-phase monolithic SPE column was found to be optimal. Quantification was performed by directly interfacing the FI-based SPE system to an electrospray ionization-mass spectrometer (ESI-MS). To more safely simulate peptidyl toxins such as the microcystins, a model peptide (i.e., angiotensin II) was used for method optimization. Sample loading flow rate and volume, eluent composition, and elution flow rate were optimized. Sample throughput was six samples per hour, a detection limit of 1.31 ng angiotensin II was demonstrated for a linear dynamic range from 1–1,000 ng and 3.4% relative standard deviation (n = 4, 100 ng sample). Sample volumes up to 1,000 ml of surface water could be loaded onto the monolithic SPE disk without exceeding the sorbent’s capacity. Unlike conventional particle-based SPE methods, the monolithic SPE disk does not need to be replaced between samples and could be used indefinitely. The FI-based SPE-ESI-MS method was successfully applied to the determination of microcystin-LR, the most common of the microcystins, in environmental samples and was demonstrated for the direct monitoring of chlorinated drinking water, with trends tracked over a period of eight months.

Analysis of polybrominated diphenyl ethers in atmospheric deposition and snow samples by solid-phase disk extraction

An extraction method for the quantitative analysis of polybrominated diphenyl ethers (PBDEs) in aqueous samples has been evaluated. The analytical methodology includes the sample filtration through glass fiber filter and subsequent extraction of dissolved phase compounds by C18 solid-phase disk extraction. Dependence of extraction efficiency on factors such as pollutant concentrations, sample volume, and stability during storage has been investigated. Mean extraction efficiencies of 97% for total PBDEs (13 tri- to heptabrominated congeners at spiking levels in the range of 15–90 pg) with a RSD between 9 and 20% were achieved. Higher recoveries were observed for the more volatile PBDEs (112%) in relation to more brominated congeners (88%). The developed methodology was successfully applied to the analysis of these compounds in atmospheric deposition and snow samples from remote sites in Europe with method detection and quantitation limits in the range of 2.1–10 pg L −1 for almost all congeners, which allow the determination of PBDEs in remote areas with levels in the range of low to medium pg L −1 for ΣPBDEs.

Isolation and Recovery of Selected Polybrominated Diphenyl Ethers from Human Serum and Sheep Serum: Coupling Reversed-Phase Solid-Phase Disk Extraction and Liquid-Liquid Extraction Techniques with a Capillary Gas Chromatographic Electron Capture Negative Ion Mass Spectrometric Determinative Technique

Polybrominated diphenyl ethers (PBDEs) are isolated and recovered with acceptable percent recoveries from human serum via liquid-liquid extraction and column chromatographic cleanup and fractionation with quantitation using capillary gas chromatography-mass spectrometry with electron capture negative ion and selected ion monitoring. PBDEs are found in unspiked serum. An alternative sample preparation approach is developed using sheep serum that utilizes a formic acid pre-treatment followed by reversed-phase solid-phase disk extraction and normal-phase solid-phase cleanup using acidified silica gel that yields>50% recoveries. When these percent recoveries are combined with a minimized phase ratio for human serum and very low instrument detection limits, method detection limits below 500 parts-per-trillion are realized.

Determination of Endocrine Disrupting Compounds and Acidic Drugs in Water by Coupling of Derivatization, Gas Chromatography and Negative‐Chemical Ionization Mass Spectrometry

AbstractThe determination of acidic pharmaceutical and endocrine disrupting compounds at low ng/L levels in surface and wastewater requires highly selective and sensitive analytical procedures. Therefore, the water samples under study were prepared by means of solid phase extraction (SPE) for analyte enrichment and clean up. Prior to GC‐NCI‐MS, the polar analytes were derivatized using pentafluorobenzyl bromide. The performance of this analytical method has been revealed in fortification experiments by limits of detection ranging from 0.01 to 0.2 ng/L for, e. g., ibuprofen and 17α‐ethinylestradiol, respectively. SPE may be the most rate determining step of the analytical procedure. Therefore, the performance of SPE disks and cartridges was additionally compared. Method evaluation demonstrated that even complex sample matrices, such as model wastewater or even synthetic humic acids, did not interfere with the quantification and identification of target analytes. The performance of the analytical method developed for water monitoring was further emphasized by the investigation of surface water of the River Saale and effluents of the wastewater treatment plant (WWTP) at Halle, Saxony‐Anhalt, Germany. In those samples, acidic pharmaceuticals and corresponding metabolites occurred at 0.1 ng/L for clofibric acid up to 498 ng/L for bezafibrate. Technical nonylphenol and bisphenol A were found in every water sample. Meanwhile, 17α‐ethinylestradiol was determined only in one WWTP effluent sample at 1 ng/L.

Determination of trimethylamine in fish by capillary electrophoresis with electrogenerated tris(2,2′‐bipyridyl)ruthenium(II) chemiluminescence detection

A capillary electrophoresis with electrogenerated chemiluminescence (CE-ECL) method for the determination of trimethylamine (TMA) in fish was studied. In the presence of TMA, ECL from the reaction of analyte and in situ generated tris(2,2'-bipyridyl)ruthenium(III) [Ru(bpy)(3) (3+)] at electrode surface could be produced. The ECL detection was performed using a Pt working electrode biased at 1.23 V (vs. Ag/AgCl) potential in a 10 mmol/L sodium borate buffer solution, pH 9.2, containing 3 mmol/L Ru(bpy)(3) (2+). A linear calibration curve (correlation coefficient = 0.9996) was obtained in the range 8 x 10(-5)-4 x 10(-8) mol/L for TMA concentration. Recoveries obtained were in the range 98.78-101.46%. The method was successfully applied for the assay of TMA in fish, in combination with solid phase extraction (SPE) disks for sample clean-up and enrichment.

Development and validation of a disk solid phase extraction and gas chromatography–mass spectrometry method for MDMA, MDA, HMMA, HMA, MDEA, methamphetamine and amphetamine in sweat

We describe the development and validation of a method for the simultaneous quantification of 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA), 3-hydroxy-4-methoxymethamphetamine (HMMA), 3-hydroxy-4-methoxyamphetamine (HMA), 3,4-methylenedioxyethylamphetamine (MDEA), methamphetamine (MAMP) and amphetamine (AMP) in sweat. Drugs were eluted from PharmChek™ sweat patches with sodium acetate buffer, extracted with disk solid phase extraction and analyzed using GC/MS-EI with selected ion monitoring. Limits of quantification (LOQ) for MDMA, MDEA, MAMP and AMP were 2.5 ng/patch, and 5 ng/patch for MDA, HMA and HMMA. This fully validated procedure was more sensitive than previously published analytical methods and permitted the simultaneous analysis of multiple amphetamine analogs in human sweat.

A Comparison of the Performance of Two Chromatographic and Three Extraction Techniques for the Analysis of PAHs in Sources of Drinking Water

The aim of this work is to establish a sensitive and reliable method for the analysis of the 16 priority Environmental Protection Agency-defined polycyclic aromatic hydrocarbons (PAHs) found in water samples. Gas chromatography (GC)-mass spectrometry (MS) and high-performance liquid chromatography (HPLC)-fluorescence detection (FLD)-UV techniques are optimized to obtain an adequate resolution of all compounds. Validation of the methods is carried out, and a good performance is observed for both techniques. The HPLC-FLD-UV technique is somewhat more sensitive than the GC-MS technique for the determination of PAHs; thus, the HPLC-FLD-UV method is used to follow up both the solid-phase extraction (SPE) analysis using cartridges and discs and the liquid-liquid extraction (LLE), which are also evaluated for the extraction of the PAHs. Low recoveries between 43% and 79% are obtained using SPE cartridges, and higher values are obtained using SPE discs (56-96%) and LLE (60-105%). Better results are obtained using the LLE technique, and, thus, analysis of real water samples is carried out using this technique. LODs between 0.6 and 21 ng/L and relative standard deviations less than 15% are obtained using a spiked water sample analyzed using the full LLE HPLC-FLD-UV method.

High throughput method for the determination of organochlorine pesticides and polychlorinated biphenyls in human serum

An improved method for the determination of selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in human serum was developed. The method requires low volume of serum (500 μl) and 48–96 samples per day can be prepared by one analyst without special automatic equipment. Initial extraction was performed using 96-well solid-phase extraction disk plates and was followed by a clean-up with silica gel/sulfuric acid. Different denaturation, elution and clean-up conditions were tested. Quantification was carried out by gas chromatography equipped with electron capture detector (GC-ECD) or mass spectrometer (GC–MS). Recoveries of PCB congeners 28, 52, 101, 118, 138, 153 and 180 and OCPs HCB, β-HCH, p, p′-DDE and p, p′-DDT at two spiking levels ( n = 8) varied from 57 to 120%, and intra-day relative standard deviation from 1 to 11%, both depending on spiking level and compound. Inter-day relative standard deviation was <15% in all cases. Limit of quantification (LOQ) for these PCBs ranged from 0.08 to 0.13 ng/ml and for these OCPs from 0.16 to 0.40 ng/ml. The optimized method was applied to the analysis of 1000 serum samples from different places of Spain.