A platinized stainless steel fiber with in-situ coated polyaniline/polypyrrole/graphene oxide nanocomposite sorbent for headspace solid-phase microextraction of aliphatic aldehydes in rice samples.

PubMed

Ghiasvand, Alireza; Nasirian, Afagh; Koonani, Samira; Nouriasl, Kolsoum

2017-12-01

The surface of a stainless steel fiber was made larger, porous and cohesive by platinizing for tight attachment of its coating. Then it was coated by a polyaniline/polypyrrole/graphene oxide (PANI/PP/GO) nanocomposite film using electrochemical polymerization. The prepared PANI/PP/GO fiber was used for headspace solid-phase microextraction (HS-SPME) of linear aliphatic aldehydes in rice samples followed by GC-FID determination. To achieve the highest extraction efficiency, various experimental parameters including extraction time and temperature, matrix modifier and desorption condition were studied. The linear calibration curves were obtained over the range of 0.05-20 μg g -1 (R 2  > 0.99) for C 4 -C 11 aldehydes. The limits of detection were found to be in the range of 0.01-0.04 μg g -1 . RSD values were calculated to be <7.4 and 10.7% for intra- and inter-day, respectively. The superiority of the prepared nanocomposite SPME fiber was established by comparison of its results with those obtained by polydimethylsiloxane, carbowax-divinylbenzene, divinylbenzene-carboxen-polydimethylsiloxane and polyacrylate commercial ones. Finally, the nanocomposite fiber was used to extract and determine linear aliphatic aldehydes in 18 rice samples. Copyright © 2017 John Wiley & Sons, Ltd.

Novel combined stir bar sorptive extraction coupled with ultrasonic assisted extraction for the determination of brominated flame retardants in environmental samples using high performance liquid chromatography.

PubMed

Yu, Chunhe; Hu, Bin

2007-08-10

A combined stir bar coated with poly (dimethysiloxane)-beta-cyclodextrin (PDMS-beta-CD) on single side has been prepared for the first time by sol-gel method and was coupled with ultrasonic assisted extraction (UAE) for the determination of some brominated flame-retardant compounds (BFRs) in soil and dust samples by high performance liquid chromatography (HPLC). Four different kinds of coatings including PDMS-beta-CD, PDMS, carbowax (CW)-PDMS-poly (vinyl alcohol) (PVA) and PDMS-PVA were evaluated for stir bar sorptive extraction of BFRs by orthogonal experiment design. The experimental results reveal that the PDMS-beta-CD combined stir bar exhibited the best extraction efficiency for the target analytes. The reproducibility for the preparation of PDMS-beta-CD combined stir bar ranged from 1.3% to 15.7% in one batch, and 7.2% to 15.1% among batches. Extraction time, desorption solvent, concentration of methanol and NaCl in the matrix, pH, temperature and stirring speed were optimized. The combined stir bar can avoid direct friction of the coating with the bottom of the vessel, and could be used for more than 100 times. Linearity (>0.993), repeatability (<10.5%), reproducibility (<16.5%), recovery (56-118%) and detection limits (2.9-4.2 microg L(-1)) were proper to determine the seven BFRs. The developed method was applied to the determination of BFRs in soil and dust with satisfactory results.

Volatile methacrylates in dental practices.

PubMed

Marquardt, Wolfgang; Seiss, Mario; Hickel, Reinhard; Reichl, Franz X

2009-04-01

In recent years, an increase of occupational respiratory diseases, such as asthma caused by methacrylates, has been observed in dental personnel. In this study, the exposure of dental personnel to various volatile methacrylates was investigated. The air levels of methacrylates were measured during filling treatment while bonding agents were used in 4 dental practices in Munich, Germany. Short-term air sampling (15 min) was performed using solid phase microextraction (SPME). The SPME fibers were coated with carbowax/divinyl benzene to enrich the analytes. For analysis, the analytes were thermically desorbed from the fiber and subsequently analyzed directly by gas chromatography/mass spectrometry. The methacrylates methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA), and triethylene glycol dimethacrylate (TEG-DMA) were identified in the air of dental practices. The exposure levels of the four methacrylates varied during the filling treatments. The maximum concentrations found were 0.4 mg/m3 for MMA, 45 microg/m3 for HEMA, 13 microg/m3 for EGDMA, and 45 microg/m3 for TEG-DMA. The detection of TEG-DMA correlated with the application of bonding agents during performance of dental fillings. Exposure levels of different methacrylates were observed at all investigated dental practices. The maximum levels of MMA measured in this study were at least 200 times lower than the toxicologically relevant maximum allowable concentrations defined in various countries. Nevertheless, the exposure levels of methacrylates should be kept as low as possible due to the allergenic potential of some methacrylates.

On-line solid-phase microextraction of triclosan, bisphenol A, chlorophenols, and selected pharmaceuticals in environmental water samples by high-performance liquid chromatography-ultraviolet detection.

PubMed

Kim, Dalho; Han, Jungho; Choi, Yongwook

2013-01-01

A method using on-line solid-phase microextraction (SPME) on a carbowax-templated fiber followed by liquid chromatography (LC) with ultraviolet (UV) detection was developed for the determination of triclosan in environmental water samples. Along with triclosan, other selected phenolic compounds, bisphenol A, and acidic pharmaceuticals were studied. Previous SPME/LC or stir-bar sorptive extraction/LC-UV for polar analytes showed lack of sensitivity. In this study, the calculated octanol-water distribution coefficient (log D) values of the target analytes at different pH values were used to estimate polarity of the analytes. The lack of sensitivity observed in earlier studies is identified as a lack of desorption by strong polar-polar interactions between analyte and solid-phase. Calculated log D values were useful to understand or predict the interaction between analyte and solid phase. Under the optimized conditions, the method detection limit of selected analytes by using on-line SPME-LC-UV method ranged from 5 to 33 ng L(-1), except for very polar 3-chlorophenol and 2,4-dichlorophenol which was obscured in wastewater samples by an interfering substance. This level of detection represented a remarkable improvement over the conventional existing methods. The on-line SPME-LC-UV method, which did not require derivatization of analytes, was applied to the determination of TCS including phenolic compounds and acidic pharmaceuticals in tap water and river water and municipal wastewater samples.

Development of a sensitive methodology for the analysis of chlorobenzenes in air by combination of solid-phase extraction and headspace solid-phase microextraction.

PubMed

Barro, Ruth; Ares, Sergio; Garcia-Jares, Carmen; Llompart, Maria; Cela, Rafael

2004-08-06

In this study, a combination of solid-phase extraction (SPE) and solid-phase microextraction (SPME) has been used to determine chlorobenzenes in air. Analytes were sampled by pumping a known volume of air through a porous polymer (Tenax TA). Then, the adsorbent was transferred into a glass vial and SPME was performed. The quantification was carried out using gas chromatography (GC)-electron-capture detection or GC-MS. Several SPME coatings (100 microm poly(dimethylsiloxane) (PDMS), 75 microm Carboxen (CAR)-PDMS, 65 microm PDMS-divinylbenzene (DVB), 65 microm PDMS-DVB and 85 microm polyacrylate (PA) were evaluated, obtaining the highest responses with Carbowax (CW)- PDMS for the most volatile chlorobenzenes, and with PDMS-DVB or CW-DVB fibers for the semivolatile compounds. To optimize some other factors that could affect the SPME step, a factorial design was used. Kinetic studies of the SPME process were also performed. Concerning the SPE step, breakthrough was studied, showing that 2.5 m3 of air could be processed without losses of the most volatile compounds. The performance of the method was evaluated. External calibration, which does not require the complete sampling process, demonstrated to be suitable, obtaining good linearity (R2 > 0.99) for all chlorobenzenes. Recovery studies were performed at two concentration levels (4 and 40 ng/m3), obtaining quantitative recoveries (>80%). Limits of detection at the sub ng/m3 were achieved for all the target compounds.

Determination of paraldehyde by gas chromatography in whole blood from children.

PubMed

Githiga, Isaiah M; Muchohi, Simon N; Ogutu, Bernhards R; Newton, Charles R J C; Otieno, Godfrey O; Gitau, Evelyn N; Kokwaro, Gilbert O

2004-06-15

A rapid, sensitive and selective gas chromatographic method with flame ionization detection was developed for the determination of paraldehyde in small blood samples taken from children. Whole blood samples (300 microl) collected in a 3 ml Wheaton glass sample vial were spiked with acetone (internal standard: 15 ng) followed by addition of concentrated hydrochloric acid. The mixture was heated in the sealed airtight sample vial in a water bath (96 Celsius; 5 min) to depolymerize paraldehyde to acetaldehyde. A 2 ml aliquot of the headspace was analyzed by gas chromatography with flame ionization detector using a stainless steel column (3 m x 4 mm i.d.) packed with 10% Carbowax 20 M/ 2% KOH on 80/100 Chromosorb WAW. Calibration curves were linear from 1.0-20 microg (r2>0.99). The limit of detection was 1.5 microg/ml, while relative mean recoveries at 2 and 18 microg were 105.6 +/- 8.4 and 101.2 +/- 5.9%, respectively (n = 10 for each level). Intra- and inter-assay relative standard deviations at 2, 10 and 18 microg were <15%. There was no interference from other drugs concurrently used in children with severe malaria, such as anticonvulsants (diazepam, phenytoin, phenobarbitone), antipyretics/analgesics (paracetamol and salicylate), antibiotics (gentamicin, chloramphenicol, benzyl penicillin) and antimalarials (chloroquine, quinine, proguanil, cycloguanil, pyrimethamine and sulfadoxine). The method was successfully applied for pharmacokinetic studies of paraldehyde in children with convulsions associated with severe malaria.

Novel capsule phase microextraction in combination with liquid chromatography-tandem mass spectrometry for determining personal care products in environmental water.

PubMed

Lakade, Sameer S; Borrull, Francesc; Furton, Kenneth G; Kabir, Abuzar; Marcé, Rosa Maria; Fontanals, Núria

2018-05-01

A novel sample preparation technique named capsule phase microextraction (CPME) is presented here. The technique utilizes a miniaturized microextraction capsule (MEC) as the extraction medium. The MEC consists of two conjoined porous tubular polypropylene membranes, one of which encapsulates the sorbent through sol-gel technology, while the other encapsulates a magnetic metal rod. As such, MEC integrates both the extraction and stirring mechanisms into a single device. The aim of this article is to demonstrate the application potential of CPME as sample preparation technique for the extraction of a group of personal care products (PCPs) from water matrices. Among the different sol-gel sorbent materials (UCON ® , poly(caprolactone-dimethylsiloxane-caprolactone) (PCAP-DMS-CAP) and Carbowax 20M (CW-20M)) evaluated, CW-20M MEC demonstrated the best extraction performance for the selected PCPs. The extraction conditions for sol-gel CW-20M MEC were optimized, including sample pH, stirring speed, addition of salt, extraction time, sample volume, liquid desorption solvent, and time. Under the optimal conditions, sol-gel CW-20M MEC provided recoveries, ranging between 47 and 90% for all analytes, except for ethylparaben, which showed a recovery of 26%. The method based on CPME with sol-gel CW-20M followed by liquid chromatography-tandem mass spectrometry was developed and validated for the extraction of PCPs from river water and effluent wastewater samples. When analyzing different environmental samples, some analytes such as 2,4-dihydroxybenzophenone, 2,2-dihydroxy-4-4 methoxybenzophenone and 3-benzophenone were found at low ng L -1 .

Emission pattern of semi-volatile organic compounds from recycled styrenic polymers using headspace solid-phase microextraction gas chromatography-mass spectrometry.

PubMed

Vilaplana, Francisco; Martínez-Sanz, Marta; Ribes-Greus, Amparo; Karlsson, Sigbritt

2010-01-15

The emission of low molecular weight compounds from recycled high-impact polystyrene (HIPS) has been investigated using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS). Four released target analytes (styrene, benzaldehyde, acetophenone, and 2-phenylpropanal) were selected for the optimisation of the HS-SPME sampling procedure, by analysing operating parameters such as type of SPME fibre (polarity and operating mechanism), particle size, extraction temperature and time. 26 different compounds were identified to be released at different temperatures from recycled HIPS, including residues of polymerisation, oxidated derivates of styrene, and additives. The type of SPME fibre employed in the sampling procedure affected the detection of emitted components. An adsorptive fibre such as carbowax/polydimethylsiloxane (CAR/PDMS fibre) offered good selectivity for both non-polar and polar volatile compounds at lower temperatures; higher temperatures result in interferences from less-volatile released compounds. An absorptive fibre as polydimethylsiloxane (PDMS) fibre is suitable for the detection of less-volatile non-polar molecules at higher temperatures. The nature and relative amount of the emitted compounds increased with higher exposure temperature and smaller polymeric particle size. HS-SPME proves to be a suitable technique for screening the emission of semi-volatile organic compounds (SVOCs) from polymeric materials; reliable quantification of the content of target analytes in recycled HIPS is however difficult due to the complex mass-transfer processes involved, matrix effects, and the difficulties in equilibrating the analytical system. 2009 Elsevier B.V. All rights reserved.

A comparison of solid-phase microextraction and stir bar sorptive extraction coupled to liquid chromatography for the rapid analysis of resveratrol isomers in wines, musts and fruit juices.

PubMed

Viñas, Pilar; Campillo, Natalia; Hernández-Pérez, Mónica; Hernández-Córdoba, Manuel

2008-03-17

A comparison of direct immersion solid-phase microextraction (DI-SPME) and stir bar sorptive extraction (SBSE) coupled to liquid chromatography (HPLC) with fluorimetric detection for the rapid analysis of resveratrol isomers is described. For DI-SPME, a polar Carbowax-template resin (CW/TPR) 50mum fiber was the most efficient and optimum extraction conditions were 40 degrees C and an extraction time of 30min, stirring in the presence of 5% (m/v) sodium chloride and 0.07M acetate/acetic acid buffer (pH 6). Desorption was carried out using the static mode for 10min. Linearity was obtained in the 5-150 and 2-150ngmL(-1) ranges for trans- and cis-resveratrol, with detection limits of 2 and 0.5ngmL(-1), respectively. When using SBSE, a polydimethylsiloxane (PDMS) twister provided best extraction by means of a derivatization reaction in the presence of acetic anhydride and potassium carbonate. The same time and temperature were used for the extraction step in the presence of 2.5% (m/v) sodium chloride, and liquid desorption was performed with 150microL of a 50/50 (v/v) acetonitrile/1% (v/v) acetic acid solution in a desorption time of 15min. Linearity was now between 0.5 and 50ngmL(-1) for trans-resveratrol with a detection limit of 0.1ngmL(-1), while cis-resveratrol could not be extracted. The proposed methods were successfully applied to determining the resveratrol isomer content of wine, must and fruit juices.

Comparison of three different poly(dimethylsiloxane)-divinylbenzene fibres for the analysis of pesticide multiresidues in water samples: structure and efficiency.

PubMed

Gonçalves, C; Alpendurada, M F

2002-07-19

Despite the continuing development of SPME (solid-phase microextraction) fibre coatings, their selection presents some difficulties for analysts in choosing the appropriate fibre for a certain application. There are two distinct types of SPME coatings available commercially. The most widely used are poly(dimethylsiloxane) (PDMS) and poly(acrylate) (PA). Supelco has developed new mixed phases consisting of porous polymer particles, either poly(divinylbenzene) (DVB) or Carboxen suspended in a matrix of PDMS or Carbowax for extracting analytes via adsorption. In addition to the nature of the extracting phase, the thickness of the polymeric film must be taken into account and, surprisingly, the construction of the fibres when apparently they bear the same coating, as it is the case of the three PDMS-DVB fibres available. Other fibre structure properties not well explored were identified and must be taken into consideration. To elucidate their extraction efficiency, three PDMS-DVB fibres, namely 60 microm for HPLC use, 65 microm for GC use and 65 microm StableFlex for GC use, were compared with regard to the extraction of 36 compounds included in four pesticide groups. The first was particularly suited for the extraction of organophosphorus pesticides and triazines whereas the StableFlex exhibited advantages in the analysis of organochlorine pesticides and pyrethroids. An explanation for the extraction differences is suggested based on the different structure of the fibres. Detection limits in the range of 1-10 ng/l for organochlorine pesticides, 1-30 ng/l for organophosphorus pesticides, 8-50 ng/l for triazines and 10-20 ng/l for pyrethroids were attained in a method using the 60 microm PDMS-DVB fibre. The fibre maintains its performance at well above 100 extractions with between-day precision below 10%.

Partitioning behavior of aromatic components in jet fuel into diverse membrane-coated fibers.

PubMed

Baynes, Ronald E; Xia, Xin-Rui; Barlow, Beth M; Riviere, Jim E

2007-11-01

Jet fuel components are known to partition into skin and produce occupational irritant contact dermatitis (OICD) and potentially adverse systemic effects. The purpose of this study was to determine how jet fuel components partition (1) from solvent mixtures into diverse membrane-coated fibers (MCFs) and (2) from biological media into MCFs to predict tissue distribution. Three diverse MCFs, polydimethylsiloxane (PDMS, lipophilic), polyacrylate (PA, polarizable), and carbowax (CAR, polar), were selected to simulate the physicochemical properties of skin in vivo. Following an appropriate equilibrium time between the MCF and dosing solutions, the MCF was injected directly into a gas chromatograph/mass spectrometer (GC-MS) to quantify the amount that partitioned into the membrane. Three vehicles (water, 50% ethanol-water, and albumin-containing media solution) were studied for selected jet fuel components. The more hydrophobic the component, the greater was the partitioning into the membranes across all MCF types, especially from water. The presence of ethanol as a surrogate solvent resulted in significantly reduced partitioning into the MCFs with discernible differences across the three fibers based on their chemistries. The presence of a plasma substitute (media) also reduced partitioning into the MCF, with the CAR MCF system being better correlated to the predicted partitioning of aromatic components into skin. This study demonstrated that a single or multiple set of MCF fibers may be used as a surrogate for octanol/water systems and skin to assess partitioning behavior of nine aromatic components frequently formulated with jet fuels. These diverse inert fibers were able to assess solute partitioning from a blood substitute such as media into a membrane possessing physicochemical properties similar to human skin. This information may be incorporated into physiologically based pharmacokinetic (PBPK) models to provide a more accurate assessment of tissue dosimetry of related toxicants.

Determination of phenoxy acid herbicides in water by electron-capture and microcoulometric gas chromatography

USGS Publications Warehouse

Goerlitz, D.F.; Lamar, William L.

1967-01-01

A sensitive gas chromatographic method using microcoulometric titration and electron-capture detection for the analysis of 2,4-D, silvex, 2,4,5-T, and other phenoxy acid herbicides in water is described. The herbicides are extracted from unfiltered water samples (800-1,000 ml) by use of ethyl ether ; then the herbicides are concentrated and esterilied. To allow the analyst a choice, two esterilication procedures--using either boron trifluoride-methanol or diazomethane--are evaluated. Microcoulometric gas chromatography is specific for the detection of halogenated compounds such as the phenoxy acid herbicides whereas it does not respond to nonhalogenated components. Microcoulometric gas chromatography requires care and patience. It is not convenient for rapid screening of l-liter samples that contain less than 1 microgram of the herbicide. Although electroncapture gas chromatography is less selective and more critically affected by interfering substances, it is, nevertheless, convenient and more sensitive than microcoulometric gas chromatography. Two different liquid phases are used in the gas chromatographic columns--DC-200 silicone in one column and QF-1 silicone in the other. The performance of both columns is improved by the addition of Carbowax 20M. The Gas Chrom Q support is coated with the liquid phases by the 'frontal-analysis' technique. The practical lower limits for measurement of the phenoxy acid herbicides in water primarily depend upon the sample size, interferences present, anal instrumentation used. With l-liter samples of water, the practical lower limits of measurement are 10 ppt (parts per trillion) for 2,4-D and 2 ppt for silvex and 2,4,5-T when electron-capture detection is used, and approximately 20 ppt for each herbicide when analyzed by microcoulometric-titration gas chromatography. Recoveries of the herbicides immediately after addition to unfiltered water samples averaged 92 percent for 2,4-D, 90 percent for silvex, and 98 percent for 2,4,5-T. Studies on the stability of herbicides added to water samples showed that 2,4-D may be rapidly degraded, especially if the samples are obtained from areas which have been repeatedly sprayed with 2,4-D. When degradation was observed, added 2,4-D rapidly decomposed within 10 days. At concentrations of about 200 ppt, however, the degradation rate was diminished. In 20 days the concentration of 2,4-D was reduced to 160-180 ppt.