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Sample records for solid-phase microextraction fiber

  1. Cold fiber solid-phase microextraction device based on thermoelectric cooling of metal fiber.

    Science.gov (United States)

    Haddadi, Shokouh Hosseinzadeh; Pawliszyn, Janusz

    2009-04-03

    A new cold fiber solid-phase microextraction device was designed and constructed based on thermoelectric cooling. A three-stage thermoelectric cooler (TEC) was used for cooling a copper rod coated with a poly(dimethylsiloxane) (PDMS) hollow fiber, which served as the solid-phase microextraction (SPME) fiber. The copper rod was mounted on a commercial SPME plunger and exposed to the cold surface of the TEC, which was enclosed in a small aluminum box. A heat sink and a fan were used to dissipate the generated heat at the hot side of the TEC. By applying an appropriate dc voltage to the TEC, the upper part of the copper rod, which was in contact to the cold side of the TEC, was cooled and the hollow fiber reached a lower temperature through heat transfer. A thermocouple was embedded in the cold side of the TEC for indirect measurement of the fiber temperature. The device was applied in quantitative analysis of off-flavors in a rice sample. Hexanal, nonanal, and undecanal were chosen as three off-flavors in rice. They were identified according to their retention times and analyzed by GC-flame ionization detection instrument. Headspace extraction conditions (i.e., temperature and time) were optimized. Standard addition calibration graphs were obtained at the optimized conditions and the concentrations of the three analytes were calculated. The concentration of hexanal was also measured using a conventional solvent extraction method (697+/-143ng/g) which was comparable to that obtained from the cold fiber SPME method (644+/-8). Moreover, the cold fiber SPME resulted in better reproducibility and shorter analysis time. Cold fiber SPME with TEC device can also be used as a portable device for field sampling.

  2. ZnO nanorod array solid phase micro-extraction fiber coating: fabrication and extraction capability

    International Nuclear Information System (INIS)

    Wang Dan; Zhang Zhuomin; Li Tiemei; Zhang Lan; Chen Guonan; Luo Lin

    2009-01-01

    In this paper, a ZnO nanorod array has been introduced as a coating to the headspace solid phase micro-extraction (HSSPME) field. The coating shows good extraction capability for volatile organic compounds (VOCs) by use of BTEX as a standard and can be considered suitable for sampling trace and small molecular VOC targets. In comparison with the randomly oriented ZnO nanorod HSSPME coating, ZnO nanorod array HSSPME fiber coating shows better extraction capability, which is attributed to the nanorod array structure of the coating. Also, this novel nanorod array coating shows good extraction selectivity to 1-propanethiol.

  3. Improvement of solid-phase microextraction efficiency by the application of a carbon-nanotubes-based ternary microextraction fiber composite.

    Science.gov (United States)

    Mohammadiazar, Sirwan; Fallahpour, Nastaran; Roostaie, Ali; Ebrahimi, Bahram

    2017-09-01

    In this study, a novel technique is proposed for preparation of an efficient and unbreakable metal-wire-supported solid-phase microextraction fiber. A sol-gel film was deposited on electrophoretically deposited carbon nanotubes on a stainless-steel wire. The applicability of the fiber was evaluated through the extraction of some aromatic pollutants as model compounds from the headspace of aqueous samples in combination with gas chromatography and mass spectrometry. The parameters affecting the structure and extraction efficiency of the fiber (including the type of solvent, time, and potential for electrophoretic deposition) and the parameters affecting the extraction efficiency (such as coating type, salt content, extraction temperature, and time) were investigated. The results showed that the film thickness will be increased by increasing the potential and time duration. Finally, the characterization of the deposited film was accomplished by scanning electron microscopy and thermogravimetric analysis. After the optimization of the extraction parameters, the limit of detection of less than 20 pg/mL was achieved, and the calibration curves were all linear (r 2  ≥ 0.9737), in the range from 50 to 500 pg/mL. The solid-phase microextraction fiber has a high mechanical strength; good stability and long service life, making it potentially applicable in the extraction of trace polycyclic aromatic hydrocarbons from aqueous samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Solid phase microextraction.

    Science.gov (United States)

    Pawliszyn, J

    2001-01-01

    Solid Phase Microextraction (SPME) uses a small volume of sorbent dispersed typically on the surface of small fibres, to isolate and concentrate analytes from sample matrix. After contact with sample, analytes are absorbed or adsorbed by the fibre phase (depending on the nature of the coating) until an equilibrium is reached in the system. The amount of an analyte extracted by the coating at equilibrium is determined by the magnitude of the partition coefficient of the analyte between the sample matrix and the coating material. After the extraction step, the fibres are transferred, with the help of a syringe-like handling device, to analytical instrument, for separation and quantitation of target analytes. This technique integrates sampling, extraction and sample introduction and is a simple way of facilitating on-site monitoring. Applications of this technique include environmental monitoring, industrial hygiene, process monitoring, clinical, forensic, food, flavour, fragrance and drug analyses, in laboratory and on-site analysis.

  5. Critical micelle concentration values for different surfactants measured with solid-phase microextraction fibers.

    Science.gov (United States)

    Haftka, Joris J-H; Scherpenisse, Peter; Oetter, Günter; Hodges, Geoff; Eadsforth, Charles V; Kotthoff, Matthias; Hermens, Joop L M

    2016-09-01

    The amphiphilic nature of surfactants drives the formation of micelles at the critical micelle concentration (CMC). Solid-phase microextraction (SPME) fibers were used in the present study to measure CMC values of 12 nonionic, anionic, cationic, and zwitterionic surfactants. The SPME-derived CMC values were compared to values determined using a traditional surface tension method. At the CMC of a surfactant, a break in the relationship between the concentration in SPME fibers and the concentration in water is observed. The CMC values determined with SPME fibers deviated by less than a factor of 3 from values determined with a surface tension method for 7 out of 12 compounds. In addition, the fiber-water sorption isotherms gave information about the sorption mechanism to polyacrylate-coated SPME fibers. A limitation of the SPME method is that CMCs for very hydrophobic cationic surfactants cannot be determined when the cation exchange capacity of the SPME fibers is lower than the CMC value. The advantage of the SPME method over other methods is that CMC values of individual compounds in a mixture can be determined with this method. However, CMC values may be affected by the presence of compounds with other chain lengths in the mixture because of possible mixed micelle formation. Environ Toxicol Chem 2016;35:2173-2181. © 2016 SETAC. © 2016 SETAC.

  6. Passive sampling of ambient ozone by solid phase microextraction with on-fiber derivatization.

    Science.gov (United States)

    Lee, I-Su; Tsai, Shih-Wei

    2008-03-10

    The solid phase microextraction (SPME) device with the polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used as a passive sampler for ambient ozone. Both O-2,3,4,5,6-(pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) and 1,2-di-(4-pyridyl)ethylene (DPE) were loaded onto the fiber before sampling. The SPME fiber assembly was then inserted into a PTFE tubing as a passive sampler. Known concentrations of ozone around the ambient ground level were generated by a calibrated ozone generator. Laboratory validations of the SPME passive sampler with the direct-reading ozone monitor were performed side-by-side in an exposure chamber at 25 degrees C. After exposures, pyriden-4-aldehyde was formed due to the reaction between DPE and ozone. Further on-fiber derivatizations between pyriden-4-aldehyde and PFBHA were followed and the derivatives, oximes, were then determined by portable gas chromatography with electron capture detector. The experimental sampling rate of the SPME ozone passive sampler was found to be 1.10 x 10(-4) cm(3) s(-1) with detection limit of 58.8 microg m(-3) h(-1). Field validations with both SPME device and the direct-reading ozone monitor were also performed. The correlations between the results from both methods were found to be consistent with r=0.9837. Compared with other methods, the current designed sampler provides a convenient and sensitive tool for the exposure assessments of ozone.

  7. Preparation and evaluation of graphene-coated solid-phase microextraction fiber

    Energy Technology Data Exchange (ETDEWEB)

    Chen Jinmei; Zou Jing; Zeng Jingbin; Song Xinhong; Ji Jiaojiao; Wang Yiru [Department of Chemistry and the Key Laboratory of Analytical Sciences of the Ministry of Education, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Ha, Jaeho [Food Analysis Center, Korea Food Research Institute, San 46-1, Baekhyun, Bundang, Seongnam, Gyonggi Province 463-746 (Korea, Republic of); Chen Xi, E-mail: xichen@xmu.edu.cn [Department of Chemistry and the Key Laboratory of Analytical Sciences of the Ministry of Education, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); State Key Laboratory of Marine Environmental Science, Xiamen University, Xiamen 361005 (China)

    2010-09-23

    In this paper, a novel graphene (G) based solid-phase microextraction (SPME) fiber was firstly prepared by immobilizing the synthesized G on stainless steel wire as coating. The new fiber possessed a homogeneous, porous and wrinkled surface and showed excellent thermal (over 330 {sup o}C), chemical and mechanical stability, and long lifespan (over 250 extractions). The SPME performance of the G-coated fiber was evaluated in detail through extraction of six pyrethroid pesticides. Although the thickness of G-coated fiber was only 6-8 {mu}m, its extraction efficiencies were higher than those of two commercial fibers (PDMS, 100 {mu}m; PDMS/DVB, 65 {mu}m). This high extraction efficiency may be mainly attributed to huge delocalized {pi}-electron system of G, which shows strong {pi}-stacking interaction with pyrethroid pesticide. The G-coated fiber was applied in the gas chromatographic determination of six pyrethroids, and their limits of detection were found to be ranged from 3.69 to 69.4 ng L{sup -1}. The reproducibility for each single fiber was evaluated and the relative standard deviations (RSDs) were calculated to be in the range from 1.9% to 6.5%. The repeatability of fiber-to-fiber and batch-to-batch was 4.3-9.2% and 4.1-9.9%. The method developed was successfully applied to three pond water samples, and the recoveries were 83-110% at a spiking of 1 {mu}g L{sup -1}.

  8. Chemically bonded carbon nanotubes on modified gold substrate as novel unbreakable solid phase microextraction fiber

    International Nuclear Information System (INIS)

    Bagheri, H.; Ayazi, Z.; Sistani, H.

    2011-01-01

    A new technique is introduced for preparation of an unbreakable fiber using gold wire as a substrate for solid phase microextraction (SPME). A gold wire is used as a solid support, onto which a first film is deposited that consists of a two-dimensional polymer obtained by hydrolysis of a self-assembled monolayer of 3-(trimethoxysilyl)-1-propanthiol. This first film is covered with a layer of 3-(triethoxysilyl)-propylamine. Next, a stationary phase of oxidized multi-walled carbon nanotubes was chemically bound to the surface. The synthetic strategy was verified by Fourier transform infrared spectroscopy and scanning electron microscopy. Thermal stability of new fiber was examined by thermogravimetric analysis. The applicability of the novel coating was verified by its employment as a SPME fiber for isolation of diazinon and fenthion, as model compounds. Parameters influencing the extraction process were optimized to result in limits of detection as low as 0.2 ng mL -1 for diazinon, and 0.3 ng mL -1 for fenthion using the time-scheduled selected ion monitoring mode. The method was successfully applied to real water, and the recoveries for spiked samples were 104% for diazinon and 97% for fenthion. (author)

  9. Critical micelle concentration values for different surfactants measured with solid-phase microextraction fibers

    NARCIS (Netherlands)

    Haftka, Joris J H; Scherpenisse, Peter; Oetter, G??nter; Hodges, Geoff; Eadsforth, Charles V.; Kotthoff, Matthias; Hermens, Joop L M

    The amphiphilic nature of surfactants drives the formation of micelles at the critical micelle concentration (CMC). Solid-phase microextraction (SPME) fibres were used in the present study to measure CMC values of twelve nonionic, anionic, cationic and zwitterionic surfactants. The SPME derived CMC

  10. Electrophoretic deposition of graphene oxide onto carbon fibers for in-tube solid-phase microextraction.

    Science.gov (United States)

    Feng, Juanjuan; Wang, Xiuqin; Tian, Yu; Bu, Yanan; Luo, Chuannan; Sun, Min

    2017-09-29

    Carbon fibers (CFs) were functionalized with graphene oxide (GO) by an electrophoretic deposition (EPD) method for in-tube solid-phase microextraction (SPME). GO-CFs were filled into a poly(ether ether ketone) (PEEK) tube to obtain a fibers-in-tube SPME device, which was connected with high performance liquid chromatography (HPLC) equipment to build online SPME-HPLC system. Compared with CFs, GO-CFs presented obviously better extraction performance, due to excellent adsorption property and large surface area of GO. Using ten polycyclic aromatic hydrocarbons (PAHs) as model analytes, the important extraction conditions were optimized, such as sample flow rate, extraction time, organic solvent content and desorption time. An online analysis method was established with wide linear range (0.01-50μgL -1 ) and low detection limits (0.001-0.004μgL -1 ). Good sensitivity resulted from high enrichment factors (1133-3840) of GO-CFs in-tube device towards PAHs. The analysis method was used to online determination of PAHs in wastewater samples. Some target analytes were detected and relative recoveries were in the range of 90.2-112%. It is obvious that the proposed GO-CFs in-tube device was an efficient extraction device, and EPD could be used to develop nanomaterials functionalized sorbents for sample preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Introduction of a coiled solid-phase microextraction fiber based on a coating of animal bone waste for chromatographic analysis.

    Science.gov (United States)

    Razmi, Habib; Farrokhzadeh, Samaneh

    2017-04-01

    We attempt to introduce animal bone waste as a coating material with an organic-inorganic structure for the fabrication of a coiled solid-phase microextraction fiber for the first time. The coiled fiber was simply prepared with the use of copper wire and coated with bone waste suspension through the dip-coating method. The bone waste coating was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction analysis. It was applied as new type of solid-phase microextraction fiber for preconcentration of polycyclic aromatic hydrocarbons before determination by high-performance liquid chromatography with UV detection. A wide linear range 0.01-99.0 μg/L and limits of detection in the range 3.0-11.1 ng/L were obtained at optimized conditions. The bone waste coated coiled solid-phase microextraction fiber has promise in sample preparation techniques because it is cost effective, available, stable in aqueous and organic solutions, environmentally friendly, and easy to fabricate and operate. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Coating of optical fiber with a smart thermosensitive polymer for the separation of phthalate esters by solid-phase microextraction.

    Science.gov (United States)

    Hashemi-Moghaddam, Hamid; Maddah, Setayesh

    2018-02-01

    A solid-phase microextraction fiber was prepared by coating an optical fiber with a temperature-sensitive polymer to determine phthalate esters. N-Isopropylacrylamide and N,N'-methylenebisacrylamide were used as the monomer and the cross linker, respectively. The fabricated fiber was characterized by FTIR spectroscopy, thermogravimetric analysis, and scanning electron microscopy. During extraction, important factors such as extraction time, pH, temperature, and ionic strength were optimized. The fabricated fiber, which is firm, inexpensive, stable, and efficient, is a vital material used in solid-phase microextraction. Under optimum conditions, the calibration curve was linear and in the range of 1-20 μg/L (r 2  = 0.9747). The high extraction efficiency was obtained for phthalates with a detection limit of 0.12 μg/L. The fabricated fiber was successfully applied to the solid-phase micro extraction of phthalates from water samples after its extraction, followed by gas chromatography with flame ionization detection. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Graphene oxide decorated with silver nanoparticles as a coating on a stainless-steel fiber for solid-phase microextraction.

    Science.gov (United States)

    Wang, Licheng; Hou, Xiudan; Li, Jubai; Liu, Shujuan; Guo, Yong

    2015-07-01

    A novel graphene oxide decorated with silver nanoparticles coating on a stainless-steel fiber for solid-phase microextraction was prepared. Scanning electron microscopy and X-ray photoelectron spectroscopy were used to characterize the coating surface and showed that silver nanoparticles were dispersed on the wrinkled graphene oxide surface. Coupled to gas chromatography with flame ionization detection, the extraction abilities of the fiber for polycyclic aromatic hydrocarbons were examined in the headspace solid-phase microextraction mode. The extraction parameters including adsorption time, adsorption temperature, salt concentration, desorption time and desorption temperature were investigated. Under the optimized condition, wide linearity with low limits of detection from 2 to 10 ng/L was obtained. The relative standard deviations for single-fiber repeatability and fiber-to-fiber reproducibility were less than 10.6 and 17.5%, respectively. The enrichment factors were from 1712.5 to 4503.7, showing the fiber has good extraction abilities. Moreover, the fiber exhibited a good stability and could be reused for more than 120 times. The established method was also applied for determination of polycyclic aromatic hydrocarbons in two real water samples and the recoveries of analytes ranged from 84.4-116.3% with relative standard deviations less than 16.2%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ultrasensitive determination of highly polar trimethyl phosphate in environmental water by molecularly imprinted polymeric fiber headspace solid-phase microextraction.

    Science.gov (United States)

    Cai, Cuicui; Zhang, Pengcheng; Deng, Jiali; Zhou, Hongbin; Cheng, Jing

    2018-03-01

    A sensitive, accurate, and cost effective method for the quantification of trimethyl phosphate, which is highly polar and volatile, in environmental water is presented. Trimethyl phosphate was headspace solid-phase microextracted on a molecularly imprinted polymeric fiber, and then the fiber was thermally desorbed in the gas chromatograph injector, and the compound was determined. The trimethyl phosphate imprinted polymeric fiber was prepared by copolymerization in a fused silica capillary tube and obtained by removal of the wall of fused silica capillary tube. The monolithic fiber displayed good selectivity toward trimethyl phosphate among its structural analogues. It was thermally stable up to 320°C so that it can withstand the high temperature of the gas chromatograph injector for desorption. The factors influencing the performance of its headspace solid-phase microextraction were studied. Under the optimal conditions, the method for quantification of trimethyl phosphate in environmental water was well developed. It exhibited significant linearity, the lowest limit of quantification to date, and good recoveries. Using this method, trimethyl phosphate was detected in five out of seven environmental water samples at concentration levels from 0.28 to 1.22 μg/L, illustrating the heavy pollution of trimethyl phosphate in environmental water. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Automated headspace solid-phase microextraction and on-fiber derivatization for the determination of clenbuterol in meat products by gas chromatography coupled to mass spectrometry.

    Science.gov (United States)

    Jiang, Yong; Ni, Yongnian

    2015-02-01

    A method was developed for the determination of clenbuterol in meat using stable-isotope-dilution gas chromatography with mass spectrometry coupled with solid-phase microextraction and on-fiber derivatization. The samples were first homogenized with hydrochloric acid followed by protein deposition. After headspace solid-phase microextraction and on-fiber derivatization, the content of clenbuterol was measured with the aid of stable-isotope dilution. The condition of solid-phase microextraction was optimized by central composite design. The relative standard deviations, limit of detection, and recoveries for clenbuterol were 4.2-9.2%, 0.48 μg/kg, and 96-104%, respectively. The proposed method was satisfactory for analysis of real samples as compared with the Chinese standard method. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Preparation by low-temperature nonthermal plasma of graphite fiber and its characteristics for solid-phase microextraction.

    Science.gov (United States)

    Luo, Fan; Wu, Zucheng; Tao, Ping; Cong, Yanqing

    2009-01-05

    Low-temperature nonthermal plasma has been used to prepare solid-phase microextraction (SPME) fibers with high adsorbability, long-term serviceability, and high reproducibility. Graphite rods serving as fiber precursors were treated by an air plasma discharged at 15.2-15.5 kV for a duration of 8 min. Sampling results revealed that the adsorptive capacity of the homemade fiber was 2.5-34.6 times that of a polyacrylate (PA) fiber for alcohols (methanol, ethanol, isopropyl alcohol, n-butyl alcohol), and about 1.4-1.6 times and 2.5-5.1 times that of an activated carbon fiber (ACF) for alcohols and BTEX (benzene, toluene, ethylbenzene, and xylenes), respectively. It is confirmed from FTIR (Fourier transform infrared spectrophotometer) and SEM (scanning electron microscope) analyses that the improvement in the adsorptive performance attributed to increased surface energy and roughness of the graphite fiber. Using gas chromatography (GC)-flame-ionization detector (FID), the limits of detection (LODs) of the alcohols and BTEX ranged between 0.19 and 3.75 microg L(-1), the linear ranges were between 0.6 and 35,619 microg L(-1) with good linearity (R(2)=0.9964-0.9997). It was demonstrated that nonthermal plasma offers a fast and simple method for preparing an efficient graphite SPME fiber, and that SPME using the homemade fiber represents a sensitive and selective extraction method for the analysis of a wide range of organic compounds.

  17. Preparation by low-temperature nonthermal plasma of graphite fiber and its characteristics for solid-phase microextraction

    International Nuclear Information System (INIS)

    Luo Fan; Wu Zucheng; Tao Ping; Cong Yanqing

    2009-01-01

    Low-temperature nonthermal plasma has been used to prepare solid-phase microextraction (SPME) fibers with high adsorbability, long-term serviceability, and high reproducibility. Graphite rods serving as fiber precursors were treated by an air plasma discharged at 15.2-15.5 kV for a duration of 8 min. Sampling results revealed that the adsorptive capacity of the homemade fiber was 2.5-34.6 times that of a polyacrylate (PA) fiber for alcohols (methanol, ethanol, isopropyl alcohol, n-butyl alcohol), and about 1.4-1.6 times and 2.5-5.1 times that of an activated carbon fiber (ACF) for alcohols and BTEX (benzene, toluene, ethylbenzene, and xylenes), respectively. It is confirmed from FTIR (Fourier transform infrared spectrophotometer) and SEM (scanning electron microscope) analyses that the improvement in the adsorptive performance attributed to increased surface energy and roughness of the graphite fiber. Using gas chromatography (GC)-flame-ionization detector (FID), the limits of detection (LODs) of the alcohols and BTEX ranged between 0.19 and 3.75 μg L -1 , the linear ranges were between 0.6 and 35619 μg L -1 with good linearity (R 2 = 0.9964-0.9997). It was demonstrated that nonthermal plasma offers a fast and simple method for preparing an efficient graphite SPME fiber, and that SPME using the homemade fiber represents a sensitive and selective extraction method for the analysis of a wide range of organic compounds

  18. In situ growth of IRMOF-3 combined with ionic liquids to prepare solid-phase microextraction fibers.

    Science.gov (United States)

    Zheng, Juan; Li, Siyan; Wang, Ying; Li, Lei; Su, Chengyong; Liu, Hong; Zhu, Fang; Jiang, Ruifen; Ouyang, Gangfeng

    2014-06-04

    A superior solid-phase microextraction (SPME) fiber-coating material, IRMOF-3@ILs/PDMS, was prepared by the in situ growth of IRMOF-3 onto stainless-steel wires and protection with ionic liquids (ILs) and polydimethylsiloxane (PDMS). The ILs can efficiently prevent the substantial cracking of IRMOF-3 caused by moisture, and a thin PDMS film can protect the IRMOF-3@ILs material to achieve a much better extraction efficiency as well as excellent resistance to high temperature and high humidity. This IRMOF-3@ILs/PDMS coating possessed a porous structure, a rough surface and an increased lifespan (by at least 100 times) compared with that of IRMOF-3. The coating was evaluated by analyzing four polycyclic aromatic hydrocarbons (PAHs) in water, and good precision (analysis of PAHs in rainwater by coupling it with gas chromatography-mass spectrometry (GC-MS). Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Preparation and characterization of metal-organic framework MIL-101(Cr)-coated solid-phase microextraction fiber.

    Science.gov (United States)

    Xie, Lijun; Liu, Shuqin; Han, Zhubing; Jiang, Ruifen; Liu, Hong; Zhu, Fang; Zeng, Feng; Su, Chengyong; Ouyang, Gangfeng

    2015-01-01

    Metal-organic frameworks (MOFs) have received great attention as novel sorbents due to their fascinating structures and intriguing potential applications in various fields. In this work, a MIL-101(Cr)-coated solid-phase microextraction (SPME) fiber was fabricated by a simple direct coating method and applied to the determination of volatile compounds (BTEX, benzene, toluene, ethylbenzene, m-xylene and o-xylene) and semi-volatile compounds (PAHs, polycyclic aromatic hydrocarbons) from water samples. The extraction and desorption conditions of headspace SPME (HS-SPME) were optimized. Under the optimized conditions, the established methods exhibited excellent extraction performance. Good precision (<7.7%) and low detection limits (0.32-1.7 ng L(-1) and 0.12-2.1 ng L(-1) for BTEX and PAHs, respectively) were achieved. In addition, the MIL-101(Cr)-coated fiber possessed good thermal stability, and the fiber can be reused over 150 times. The fiber was successfully applied to the analysis of BTEX and PAHs in river water by coupling with gas chromatography-mass spectrometry (GC-MS). The analytes at low concentrations (1.7 and 10 ng L(-1)) were detected, and the recoveries obtained with the spiked river water samples were in the range of 80.0-113% and 84.8-106% for BTEX and PAHs, respectively, which demonstrated the applicability of the self-made fiber. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. C12-Ag wire as solid-phase microextraction fiber for determination of benzophenone ultraviolet filters in river water.

    Science.gov (United States)

    Li, Jian; Ma, Liyun; Tang, Minqiong; Xu, Li

    2013-07-12

    In the present study, a novel approach for fabrication of solid-phase microextraction (SPME) fiber based on silver wire was proposed. 3-(Mercaptopropyl) trimethoxysilane (MPTS) was self-assembled on the silver wire by the special interaction between Ag and S, producing MPTS-Ag wire. The MPTS-Ag wire was then functionalized with dodecyltrimethoxysilane via sol-gel approach, giving C12-Ag wire. The preparation conditions were systematically optimized. The prepared fiber was then used as the SPME fiber to extract three benzophenone UV filters from the river water. The developed method showed good linearity between 0.005 and 0.200 μg mL(-1) with regression determination coefficients in the range of 0.9929-0.9988 and detection limits ranging from 0.58 to 1.86 ng mL(-1). The C12-Ag fiber exhibited good stability and long lifetime, and could be an alternative to the traditional fused silica fiber. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Application of β-cyclodextrin-modified, carbon nanotube-reinforced hollow fiber to solid-phase microextraction of plant hormones.

    Science.gov (United States)

    Song, Xin-Yue; Ha, Wei; Chen, Juan; Shi, Yan-Ping

    2014-12-29

    A new, efficient, and environmental friendly solid-phase microextraction (SPME) medium based on β-cyclodextrin (β-CD)-modified carbon nanotubes (CNTs) and a hollow fiber (HF) was prepared. Functionalized β-CD was covalently linked to the surface of the carboxylic CNTs and then the obtained nanocomposite was immobilized into the wall pores of HFs under ultrasonic-assisted effect. The scanning electron microscope was used to inspect surface characteristics of fibers, demonstrating the presence of nanocomposites in their wall pores. The reinforced HF was employed in SPME, and its extraction performance was evaluated by analyzing 1-naphthaleneacetic acid (NAA) and 2-naphthoxyacetic acid (2-NOA) in vegetables. Without any tedious clean-up procedure, analytes were extracted from the sample to the adsorbent and organic solvent immobilized in HFs and then desorbed in acetonitrile prior to chromatographic analysis. Under the optimized extraction conditions, the method provided 275- and 283-fold enrichment factors of NAA and 2-NOA, low limits of detection and quantification (at an ngg(-1) level), satisfactory spiked recoveries, good inter-fiber repeatability, and batch-to-batch reproducibility. The selectivity of the developed fiber was investigated to three structurally similar compounds and two reference compounds with recognition coefficients up to 3.18. The obtained results indicate that the newly developed fiber is a feasible, selective, green, and cost-effective microextraction medium and could be successfully applied for extraction and determination of naphthalene-derived plant hormones in complex matrices. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Electropolymerized multiwalled carbon nanotubes/polypyrrole fiber for solid-phase microextraction and its applications in the determination of pyrethroids.

    Science.gov (United States)

    Chen, Liangbi; Chen, Wenfeng; Ma, Chunhua; Du, Dan; Chen, Xi

    2011-03-15

    A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes/polypyrrole (MWCNTs/Ppy) was prepared with an electrochemical method and used for the extraction of pyrethroids in natural water samples. The results showed that the MWCNTs/Ppy coated fiber had high organic stability, and remarkable acid and alkali resistance. In addition, the MWCNTs/Ppy coated fiber was more effective and superior to commercial PDMS and PDMS/DVD fibers in extracting pyrethroids in natural water samples. Under optimized conditions, the calibration curves were found to be linear from 0.001 to 10 μg mL(-1) for five of the six pyrethroids studied, the exception being fenvalerate (which was from 0.005 to 10 μg mL(-1)), and detection limits were within the range 0.12-0.43 ng mL(-1). The recoveries of the pyrethroids spiked in water samples at 10 ng mL(-1) ranged from 83 to 112%. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. Analysis of ammonium nitrate headspace by on-fiber solid phase microextraction derivatization with gas chromatography mass spectrometry.

    Science.gov (United States)

    Lubrano, Adam L; Andrews, Benjamin; Hammond, Mark; Collins, Greg E; Rose-Pehrsson, Susan

    2016-01-15

    A novel analytical method has been developed for the quantitation of trace levels of ammonia in the headspace of ammonium nitrate (AN) using derivatized solid phase microextraction (SPME) fibers with gas chromatography mass spectrometry (GC-MS). Ammonia is difficult to detect via direct injection into a GC-MS because of its low molecular weight and extreme polarity. To circumvent this issue, ammonia was derivatized directly onto a SPME fiber by the reaction of butyl chloroformate coated fibers with the ammonia to form butyl carbamate. A derivatized externally sampled internal standard (dESIS) method based upon the reactivity of diethylamine with unreacted butyl chloroformate on the SPME fiber to form butyl diethylcarbamate was established for the reproducible quantification of ammonia concentration. Both of these compounds are easily detectable and separable via GC-MS. The optimized method was then used to quantitate the vapor concentration of ammonia in the headspace of two commonly used improvised explosive device (IED) materials, ammonium nitrate fuel oil (ANFO) and ammonium nitrate aluminum powder (Ammonal), as well as identify the presence of additional fuel components within the headspace. Published by Elsevier B.V.

  4. Preparation by low-temperature nonthermal plasma of graphite fiber and its characteristics for solid-phase microextraction

    Energy Technology Data Exchange (ETDEWEB)

    Luo Fan [Department of Environmental Engineering, State Key Laboratory of Clean Energy Utilization, Key Laboratory of Polluted Environment Remediation and Ecological Health, MOE, Zhejiang University, Hangzhou 310027 (China); Wu Zucheng [Department of Environmental Engineering, State Key Laboratory of Clean Energy Utilization, Key Laboratory of Polluted Environment Remediation and Ecological Health, MOE, Zhejiang University, Hangzhou 310027 (China)], E-mail: wuzc@zju.edu.cn; Tao Ping [Institute of Structural Mechanics, China Academy of Engineering Physics, Mianyang 621900 (China); Cong Yanqing [College of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310012 (China)

    2009-01-05

    Low-temperature nonthermal plasma has been used to prepare solid-phase microextraction (SPME) fibers with high adsorbability, long-term serviceability, and high reproducibility. Graphite rods serving as fiber precursors were treated by an air plasma discharged at 15.2-15.5 kV for a duration of 8 min. Sampling results revealed that the adsorptive capacity of the homemade fiber was 2.5-34.6 times that of a polyacrylate (PA) fiber for alcohols (methanol, ethanol, isopropyl alcohol, n-butyl alcohol), and about 1.4-1.6 times and 2.5-5.1 times that of an activated carbon fiber (ACF) for alcohols and BTEX (benzene, toluene, ethylbenzene, and xylenes), respectively. It is confirmed from FTIR (Fourier transform infrared spectrophotometer) and SEM (scanning electron microscope) analyses that the improvement in the adsorptive performance attributed to increased surface energy and roughness of the graphite fiber. Using gas chromatography (GC)-flame-ionization detector (FID), the limits of detection (LODs) of the alcohols and BTEX ranged between 0.19 and 3.75 {mu}g L{sup -1}, the linear ranges were between 0.6 and 35619 {mu}g L{sup -1} with good linearity (R{sup 2} = 0.9964-0.9997). It was demonstrated that nonthermal plasma offers a fast and simple method for preparing an efficient graphite SPME fiber, and that SPME using the homemade fiber represents a sensitive and selective extraction method for the analysis of a wide range of organic compounds.

  5. Polyoxotungstate nanoclusters supported on silica as an efficient solid-phase microextraction fiber of polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Abolghasemi, Mir Mahdi; Yousefi, Vahid; Rafiee, Ezzat

    2014-01-01

    A highly porous silica-supported tungstophosphoric acid (PW) nanocluster was prepared for use in solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs). The PWs represent a class of discrete transition metal-oxide nanoclusters and their structures resemble discrete fragments of metal-oxide structures of definite size and shape. Transition metal-oxide nanoclusters display large structural diversity, and their monodisperse sizes can be tuned from several Ångstroms up to 10 nm. The highly porous silica-supported tungstophosphoric acid nanocluster material is found to be capable of efficiently extracting PAHs from aqueous sample solutions. The nanomaterial was immobilized on a stainless steel wire for fabrication of the SPME fiber. Following thermal desorption, the PAHs were quantified by GC-MS. Analytical merits include limits of detection that range from 0.02 to 0.1 pg mL −1 and a dynamic range as wide as from 0.001 to 100 ng mL −1 . Under optimum conditions, the repeatability for one fiber (n = 3), expressed as the relative standard deviation, is between 4.3 % and 8.6 %. The method is simple, rapid, and inexpensive. The thermal stability of the fiber and the high relative recovery make this method superior to conventional methods of extraction. (author)

  6. Introduction of coiled solid phase microextraction fiber coated by mesoporous silica/cetyltrimethylammonium bromide for ultra-trace environmental analysis.

    Science.gov (United States)

    Razmi, Habib; Khosrowshahi, Elnaz Marzi; Farrokhzadeh, Samaneh

    2017-07-14

    In this study, a tiny coiled cupper wire as a novel solid phase microextraction (SPME) fiber was coated with mesoporous silica/cetyltrimethylammonium bromide (MCM-41/CTAB) as an adsorbent by electrochemically assisted self-assembly method and used for the preconcentration of polycyclic aromatic hydrocarbons (PAHs) as model analytes prior to chromatographic determination. Deposition of MCM-41/CTAB on the coiled SPME (C-SPME) fiber resulted in easily controlled and reproducible SPME coatings. Non-calcined MCM-41/CTAB on C-SPME plays a key role in the adsorption of PAHs. Under the optimized experimental conditions, low detection limits (36-1220pgL -1 ), and wide linear dynamic ranges (R 2 >0.98) were achieved in the range of 0.25-25,000, 0.12-15,000, 0.56-32,000, 4.1-100,000ngL -1 for phenanthrene, anthracene, fluoranthene and pyrene respectively. The reusability of proposed fiber as well as relative standard deviations for repetitive determination of the target analytes was evaluated. The proposed method was successfully applied for determination of PAHs in several real samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Rapid determination of 54 pharmaceutical and personal care products in fish samples using microwave-assisted extraction-Hollow fiber-Liquid/solid phase microextraction.

    Science.gov (United States)

    Zhang, Yi; Guo, Wen; Yue, Zhenfeng; Lin, Li; Zhao, Fengjuan; Chen, Peijin; Wu, Weidong; Zhu, Hong; Yang, Bo; Kuang, Yanyun; Wang, Jiong

    2017-04-15

    In this paper, a simple, rapid, solvent-less and environmental friendliness microextraction method, microwave-assisted extraction-hollow fiber-liquid/solid phase microextraction (MAE-HF-L/SME), was developed for simultaneous extraction and enrichment of 54 trace hydrophilic/lipophilic pharmaceutical and personal care products (PPCPs) from fish samples. A solid-phase extraction material, solid-phase microextraction (SPME) fiber, was synthesized. The SPME fiber had a homogeneous, loose structure and good mechanical properties, and they exhibited a good adsorption capacity for most PPCPs selected. The material formed the basis for the method of MAE-HF-L/SME. A method of liquid chromatography-high resolution mass spectroscopy (LC-HRMS) for analysis of 54 PPCPs. Under optimal synthesis and extraction conditions, the limits of detection (LODs, n=3) and the limits of quantitation (LOQs, n=10) for the 54 PPCPs were between 0.01-0.50μg·kg -1 and 0.052.00μg·kg -1 , respectively. Percent recoveries and the relative standard deviations (RSDs) in spiked fish samples (n=6) were between 56.3%-119.9% and 0.3%-17.1%, respectively. The microextraction process of 54 PPCPs in MAE-HF-L/SME took approximately 12min. The method has a low matrix interference and high enrichment factor and may be applicable for determination of 54 different PPCPs in fish samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. A novel polythiophene – ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis

    International Nuclear Information System (INIS)

    Pelit, Füsun Okçu; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E.E.; Türkmen, Hayati; Ertaş, F.N.

    2015-01-01

    Highlights: • A novel polythiophene – ionic liquid modified clay surface has been prepared. • Polymerization was performed electrochemically on a stainless steel wire. • This material was used as a SPME fiber in head space mode. • This new SPME fiber was applied for analysis of pesticides in juice samples. • Fiber adsorption properties were improved by modification of ionic liquids. - Abstract: This report comprises the novel usage of polythiophene – ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett–Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box–Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002–0.667 ng mL −1 . Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues

  9. A novel polythiophene – ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis

    Energy Technology Data Exchange (ETDEWEB)

    Pelit, Füsun Okçu, E-mail: fusun.okcu@ege.edu.tr; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E.E.; Türkmen, Hayati; Ertaş, F.N.

    2015-02-15

    Highlights: • A novel polythiophene – ionic liquid modified clay surface has been prepared. • Polymerization was performed electrochemically on a stainless steel wire. • This material was used as a SPME fiber in head space mode. • This new SPME fiber was applied for analysis of pesticides in juice samples. • Fiber adsorption properties were improved by modification of ionic liquids. - Abstract: This report comprises the novel usage of polythiophene – ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett–Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box–Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002–0.667 ng mL{sup −1}. Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues.

  10. Carbon nanotubes reinforced hollow fiber solid phase microextraction for the determination of strychnine and brucine in urine.

    Science.gov (United States)

    Song, Xin-Yue; Shi, Yan-Ping; Chen, Juan

    2013-11-15

    A mixed matrix membrane (MMM), based on carbon nanotubes (CNTs) and hollow fiber (HF), was prepared and combined with solid phase microextraction (SPME) mode to determine strychnine and brucine in urine. This MMM was prepared by dispersing CNTs in water via surfactant assistance, and then immobilizing CNTs into the pores of HF by capillary forces and sonification. The prepared carbon nanotubes reinforced hollow fiber (CNTs-HF) was subsequently wetted by a few microliters of organic solvent (1-octanol), and then applied to extract the target analytes in direct immersion sampling mode. After extraction, analytes were desorbed via ultrasonic-assisted effect, and then detected via high-performance liquid chromatography (HPLC). To achieve the highest extraction efficiency, main extraction parameters such as the type and amount of surfactant, the diameter and doping level of CNTs, extraction time, desorption condition, pH value, stirring rate and volume of the donor phase were optimized. Under the optimum extraction conditions, the method showed good linearity ranges with correlation coefficients higher than 0.9990, good repeatability and batch-to-batch reproducibility with relative standard deviations (RSDs) less than 6% and 5% for strychnine and brucine, respectively, and low limits of detection (0.7 and 0.9 µg L(-1) for strychnine and brucine, respectively). The recoveries were in the range of 83.81-116.14% at three spiked levels. The developed method was successfully applied to real urine sample with mean relative recoveries of 94.28% and 91.30% for strychnine and brucine, respectively. The developed method shows comparable results against reference methods and is a simple, green, and cost-effective microextraction technique. © 2013 Elsevier B.V. All rights reserved.

  11. Solid-phase microextraction of methadone in urine samples by electrochemically co-deposited sol-gel/Cu nanocomposite fiber.

    Science.gov (United States)

    Mohammadiazar, Sirwan; Hasanli, Fateme; Maham, Mehdi; Payami Samarin, Somayeh

    2017-08-01

    Electrochemically co-deposited sol-gel/Cu nanocomposites have been introduced as a novel, simple and single-step technique for preparation of solid-phase microextraction (SPME) coating to extract methadone (MDN) (a synthetic opioid) in urine samples. The porous surface structure of the sol-gel/Cu nanocomposite coating was revealed by scanning electron microscopy. Direct immersion SPME followed by HPLC-UV determination was employed. The factors influencing the SPME procedure, such as the salt content, desorption solvent type, pH and equilibration time, were optimized. The best conditions were obtained with no salt content, acetonitrile as desorption solvent type, pH 9 and 10 min equilibration time. The calibration graphs for urine samples showed good linearity. The detection limit was about 0.2 ng mL -1 . Also, the novel method for preparation of nanocomposite fiber was compared with previously reported techniques for MDN determination. The results show that the novel nanocomposite fiber has relatively high extraction efficiency. Copyright © 2016 John Wiley & Sons, Ltd.

  12. Comparison between solid phase microextraction (SPME) and hollow fiber liquid phase microextraction (HFLPME) for determination of extractables from post-consumer recycled PET into food simulants.

    Science.gov (United States)

    Oliveira, Éder Costa; Echegoyen, Yolanda; Cruz, Sandra Andrea; Nerin, Cristina

    2014-09-01

    Hollow fiber liquid phase microextraction (HFLPME) and solid phase microextraction (SPME) methods for pre-concentration of contaminants (toluene, benzophenone, tetracosane and chloroform) in food simulants were investigated. For HFLPME 1-heptanol, 2-octanone and dibutyl-ether were studied as extracting solvents. Analysis by gas chromatography coupled to mass spectrometry (GC-MS), flame ionization (GC-FID) and electron capture detectors (GC-ECD) were carried out. In addition, the methods were employed to evaluate the safety in use of a PET material after the recycling process (comprising washing, extrusion and solid state polymerization (SSP)) through extractability studies of the contaminants using 10% (v/v) ethanol in deionized water and 3% (w/v) acetic acid in deionized water as food simulants in different conditions: 10 days at 40°C and 2h at 70°C. The HFLPME preconcentration method provided increased sensitivity when compared to the SPME method and allowed to analyze concentration levels below 10 µg surrogate per kg food simulant. The results of the extractability studies showed considerable reductions after the extrusion and SSP processes and indicated the compliance with regulations for using recycled PET in contact with food. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Development of headspace solid-phase microextraction method for ...

    African Journals Online (AJOL)

    ... analysis of 14 multiclass pesticide residues in fruits and vegetable samples. The gas chromatography mass spectrometry parameters (desorption temperature and time, column flow rate, interface temperature) and solid phase microextraction parameters (fiber coating type, extraction temperature and time, pH, salt addition ...

  14. Improvement of solid phase microextraction fiber assembly and interface for liquid chromatography.

    Science.gov (United States)

    Chen, Yong; Sidisky, Leonard M

    2012-09-19

    Modifications were made on commercial SPME fiber assembly and SPME-LC interface to improve the applicability of SPME for LC. Polyacrylonitrile (PAN)/C18 bonded fuse silica was used as the fiber coating for LC applications because the fiber coating was not swollen in common LC solvents at room temperature. The inner tubing of SPME fiber assembly was replaced with a 457 μm outside diameter (o.d.) solid nitinol rod. And the coated fiber (o.d. 290 μm) was installed onto the nitinol rod. The inner diameter (i.d.) of the through hole of the ferrule in the SPME-LC interface was enlarged to 508 μm to accommodate the nitinol rod. The much larger inner rod protected the fiber coating from being stripped when the fiber was withdrawn from the SPME-LC interface. The system was evaluated in term of pressure test, desorption optimization, peak shape, carryovers, linear range, precision, and limit of detection (LOD) with polycyclic aromatic hydrocarbons (PAHs) as the test analytes. The results demonstrated that the improved system was robust and reliable. It overcame the drawbacks, such as leak of solvents and damage of fiber coatings, associated with current SPME fibers and SPME-LC interface. Another sealing mechanism was proposed by sealing the nitinol rod with a specially designed poly(ether ether ketone) (PEEK) fitting. The device was fabricated and tested for manual use. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Critical evaluation of fiber coatings for organotin determination by using solid phase microextraction in headspace mode.

    Science.gov (United States)

    Bravo, Manuel M; Valenzuela, Aníbal S; Fuentes, Edwar P; Quiroz, Waldo V

    2012-02-03

    In the present work three different SPME fibers have been investigated for simultaneous determination of methyl-, butyl- and phenyltins by using gas chromatography-pulsed flame photometer detection (GC-PFPD). The optimal experimental conditions for each fiber were determined and the respective figures of merit were evaluated. All fiber evaluated presented similar limit of detection (sub ng L⁻¹) and requires two internal standards to reach an acceptable repeatability. However, the CAR-PDMS fiber offers the best compromise between selectivity and sensibility for determination of organotins selected. The developed method was validated for analysis of certified reference material and spiked samples, obtaining satisfactory results. Finally, some contaminated samples were analyzed demonstrating the applicability of developed method for determination of organotin compounds in the environment and for monitoring their biochemical cycle. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. Comparison of solid phase microextraction and hollow fiber liquid phase microextraction for the determination of pesticides in aqueous samples by gas chromatography triple quadrupole tandem mass spectrometry.

    Science.gov (United States)

    Garrido Frenich, Antonia; Romero-González, R; Martínez Vidal, José Luis; Martínez Ocaña, R; Baquero Feria, P

    2011-02-01

    This work compares two miniaturised sample preparation methods, solid phase microextraction (SPME) and hollow fiber liquid phase microextraction (HF-LPME), in combination with gas chromatography coupled to tandem mass spectrometry with a triple quadrupole analyzer for the determination of 77 pesticides in drinking water. In the case of SPME, extraction temperature and time were optimized by experimental design, although other parameters, as desorption time, pH, and ionic strength, were also evaluated. The extraction and desorption solvents [octanol/dihexyl ether (75:25, v/v) and cyclohexane, respectively], as well as the extraction and desorption time, ionic strength, and pH, were studied for the HF-LPME procedure. Under the optimal conditions, recoveries (70.2-113.5% for SPME and 70.0-119.5% for HF-LPME), intra-day precision (2.1-19.4% for SPME and 4.3-22.5% for HF-LPME), inter-day precision (5.2-21.5% for SPME and 8.4-27.3% for HF-LPME), and limits of detection, between 0.1 and 28.8 ng/L for SPME and 0.2 and 47.1 ng/L for HF-LPME and overall uncertainty (9.6-25.2% for SPME and 13.3-27.5% for HF-LPME) were established for both extraction procedures. Finally, the proposed methods were successfully applied to the analysis of 41 drinking water samples, and similar results were obtained with both extraction approaches.

  17. Magnetic in-tube solid phase microextraction.

    Science.gov (United States)

    Moliner-Martínez, Y; Prima-Garcia, Helena; Ribera, Antonio; Coronado, Eugenio; Campíns-Falcó, P

    2012-08-21

    We report a new in-tube solid phase microextraction approach named magnetic in-tube solid phase microextraction, magnetic-IT-SPME. Magnetic-IT-SPME has been developed, taking advantage of magnetic microfluidic principles with the aim to improve extraction efficiency of IT-SPME systems. First, a magnetic hybrid material formed by Fe(3)O(4) nanoparticles supported on SiO(2) was synthesized and immobilized in the surface of a bared fused silica capillary column to obtain a magnetic adsorbent extraction phase. The capillary column was placed inside a magnetic coil that allowed the application of a variable magnetic field. Acetylsalicylic acid, acetaminophen, atenolol, diclofenac, and ibuprofen were tested as target analytes. The application of a controlled magnetic field resulted in quantitative extraction efficiencies of the target analytes between 70 and 100%. These results demonstrated that magnetic forces solve the low extraction efficiency (10-30%) of IT-SPME systems, which is one of their main drawbacks.

  18. Air sampling with solid phase microextraction

    Science.gov (United States)

    Martos, Perry Anthony

    There is an increasing need for simple yet accurate air sampling methods. The acceptance of new air sampling methods requires compatibility with conventional chromatographic equipment, and the new methods have to be environmentally friendly, simple to use, yet with equal, or better, detection limits, accuracy and precision than standard methods. Solid phase microextraction (SPME) satisfies the conditions for new air sampling methods. Analyte detection limits, accuracy and precision of analysis with SPME are typically better than with any conventional air sampling methods. Yet, air sampling with SPME requires no pumps, solvents, is re-usable, extremely simple to use, is completely compatible with current chromatographic equipment, and requires a small capital investment. The first SPME fiber coating used in this study was poly(dimethylsiloxane) (PDMS), a hydrophobic liquid film, to sample a large range of airborne hydrocarbons such as benzene and octane. Quantification without an external calibration procedure is possible with this coating. Well understood are the physical and chemical properties of this coating, which are quite similar to those of the siloxane stationary phase used in capillary columns. The log of analyte distribution coefficients for PDMS are linearly related to chromatographic retention indices and to the inverse of temperature. Therefore, the actual chromatogram from the analysis of the PDMS air sampler will yield the calibration parameters which are used to quantify unknown airborne analyte concentrations (ppb v to ppm v range). The second fiber coating used in this study was PDMS/divinyl benzene (PDMS/DVB) onto which o-(2,3,4,5,6- pentafluorobenzyl) hydroxylamine (PFBHA) was adsorbed for the on-fiber derivatization of gaseous formaldehyde (ppb v range), with and without external calibration. The oxime formed from the reaction can be detected with conventional gas chromatographic detectors. Typical grab sampling times were as small as 5 seconds

  19. Solid phase microextraction of diclofenac using molecularly imprinted polymer sorbent in hollow fiber combined with fiber optic-linear array spectrophotometry

    Science.gov (United States)

    Pebdani, Arezou Amiri; Shabani, Ali Mohammad Haji; Dadfarnia, Shayessteh; Khodadoust, Saeid

    2015-08-01

    A simple solid phase microextraction method based on molecularly imprinted polymer sorbent in the hollow fiber (MIP-HF-SPME) combined with fiber optic-linear array spectrophotometer has been applied for the extraction and determination of diclofenac in environmental and biological samples. The effects of different parameters such as pH, times of extraction, type and volume of the organic solvent, stirring rate and donor phase volume on the extraction efficiency of the diclofenac were investigated and optimized. Under the optimal conditions, the calibration graph was linear (r2 = 0.998) in the range of 3.0-85.0 μg L-1 with a detection limit of 0.7 μg L-1 for preconcentration of 25.0 mL of the sample and the relative standard deviation (n = 6) less than 5%. This method was applied successfully for the extraction and determination of diclofenac in different matrices (water, urine and plasma) and accuracy was examined through the recovery experiments.

  20. Solid phase microextraction of diclofenac using molecularly imprinted polymer sorbent in hollow fiber combined with fiber optic-linear array spectrophotometry.

    Science.gov (United States)

    Pebdani, Arezou Amiri; Shabani, Ali Mohammad Haji; Dadfarnia, Shayessteh; Khodadoust, Saeid

    2015-08-05

    A simple solid phase microextraction method based on molecularly imprinted polymer sorbent in the hollow fiber (MIP-HF-SPME) combined with fiber optic-linear array spectrophotometer has been applied for the extraction and determination of diclofenac in environmental and biological samples. The effects of different parameters such as pH, times of extraction, type and volume of the organic solvent, stirring rate and donor phase volume on the extraction efficiency of the diclofenac were investigated and optimized. Under the optimal conditions, the calibration graph was linear (r(2)=0.998) in the range of 3.0-85.0 μg L(-1) with a detection limit of 0.7 μg L(-1) for preconcentration of 25.0 mL of the sample and the relative standard deviation (n=6) less than 5%. This method was applied successfully for the extraction and determination of diclofenac in different matrices (water, urine and plasma) and accuracy was examined through the recovery experiments. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Cobalt oxide nanoparticles as a novel high-efficiency fiber coating for solid phase microextraction of benzene, toluene, ethylbenzene and xylene from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Gholivand, Mohammad Bagher, E-mail: MB.Gholivand@yahoo.com [Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of); Shamsipur, Mojtaba; Shamizadeh, Mohammad [Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah (Iran, Islamic Republic of); Moradian, Rostam; Astinchap, Bandar [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of); Nano Technology Research Laboratory, Razi University, Kermanshah (Iran, Islamic Republic of)

    2014-04-01

    Highlights: • Co{sub 3}O{sub 4} nanoparticles were introduced as a novel SPME fiber coating. • The fiber was evaluated for the extraction of BTEX in combination with GC–MS. • The fiber showed extraction efficiencies better than a PDMS fiber toward BTEX. • The fiber was successfully applied to the determination of BTEX in real samples. - Abstract: In this work cobalt oxide nanoparticles were introduced for preparation of a novel solid phase microextraction (SPME) fiber coating. Chemical bath deposition (CBD) technique was used in order for synthesis and immobilization of the Co{sub 3}O{sub 4} nanomaterials on a Pt wire for fabrication of SPME fiber. The prepared cobalt oxide coating was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The fiber was evaluated for the extraction of benzene, toluene, ethylbenzene and xylene (BTEX) in combination with GC–MS. A simplex optimization method was used to optimize the factors affecting the extraction efficiency. Under optimized conditions, the proposed fiber showed extraction efficiencies comparable to those of a commercial polydimethylsiloxane (PDMS) fiber toward the BTEX compounds. The repeatability of the fiber and its reproducibility, expressed as relative standard deviation (RSD), were lower than about 11%. No significant change was observed in the extraction efficiency of the new SPME fiber after over 50 extractions. The fiber was successfully applied to the determination of BTEX compounds in real samples. The proposed nanostructure cobalt oxide fiber is a promising alternative to the commercial fibers as it is robust, inexpensive and easily prepared.

  2. Preparation of C18 composite solid-phase microextraction fiber and its application to the determination of organochlorine pesticides in water samples.

    Science.gov (United States)

    Li, Siyan; Lu, Chengwei; Zhu, Fang; Jiang, Ruifen; Ouyang, Gangfeng

    2015-05-11

    In this work, a C18 composite solid-phase microextraction (SPME) fiber was prepared with a new method and applied to the analysis of organochlorine pesticides (OCPs) in water sample. A stainless steel wire (o.d. 127 μm) was used as the substrate, and a mixture of the C18 particle (3.5 μm) and the 184 silicone was used as the coating material. During the process of fiber preparation, a section of capillary column was used to fix the mixture onto the stainless steel wire and to ensure the constant of coating thickness. The prepared fiber showed excellent thermal stability and solvent resistance. By coupling with gas chromatography-mass spectrometry (GC-MS), the fiber exhibited wide linearity (2-500 ng L(-1)) and good sensitivity for the determination of six OCPs in water samples, the OCPs tested included hexachlorobezene, trans-chlordane, cis-chlordane, o,p-DDT, p,p-DDT and mirex. Not only the extraction performance of the newly prepared fiber was more than seven times higher than those of commercial fibers, the limits of detections (LODs) (0.059-0.151 ng L(-1)) for OCPs achieved under optimized conditions were also lower than those of reported SPME methods. The fiber was successfully applied to the determination of OCPs in real water samples by using developed SPME-GC-MS method. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Bioinspired Polyelectrolyte-Assembled Graphene-Oxide-Coated C18 Composite Solid-Phase Microextraction Fibers for In Vivo Monitoring of Acidic Pharmaceuticals in Fish.

    Science.gov (United States)

    Qiu, Junlang; Chen, Guosheng; Liu, Shuqin; Zhang, Tianlang; Wu, Jiayi; Wang, Fuxin; Xu, Jianqiao; Liu, Yan; Zhu, Fang; Ouyang, Gangfeng

    2016-06-07

    A novel solid-phase microextraction (SPME) fiber was prepared by gluing poly(diallyldimethylammonium chloride) (PDDA) assembled graphene oxide (GO)-coated C18 composite particles (C18@GO@PDDA) onto a quartz fiber with polyaniline (PANI). The fiber surface coating was sequentially modified with bioinspired polynorepinephrine, which provided a smooth biointerface and makes the coating suitable for in vivo sampling. The novel custom-made coating was used to extract acidic pharmaceuticals, and high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was employed for analysis. The custom-made coating exhibited a much higher extraction efficiency than the previously used commercial polydimethylsiloxane (PDMS) and polyacrylate (PA) coatings. The custom-made coating also possessed satisfactory stability (the relative standard deviations (RSDs) ranged from 1.60% to 10.3% for six sampling-desorption cycles), interfiber reproducibility (the RSDs ranged from 2.61% to 11.5%), and resistance to matrix effects. The custom-made fibers were used to monitor the presence of acid pharmaceuticals in dorsal-epaxial muscle of living fish, and satisfactory sensitivities (limits of detection ranged from 0.13 ng/g to 7.56 ng/g) were achieved. The accuracies were verified by the comparison with liquid extraction. Moreover, the novel fibers were successfully used to monitor the presence of acidic pharmaceuticals in living fish, which demonstrated that the custom-made fibers were feasible for possible long-term in vivo continuous pharmaceutical monitoring.

  4. A two-component mass balance model for calibration of solid-phase microextraction fibers for pyrethroids in seawater.

    Science.gov (United States)

    Lao, Wenjian; Maruya, Keith A; Tsukada, David

    2012-11-06

    Determination of the analyte-specific distribution coefficient between the aqueous and sorbing phases is required for estimation of the aqueous-phase concentration of the analyte of interest using polymeric materials. Poly(dimethylsiloxane)-coated solid-phase microextration (PDMS-SPME) fiber-water partition coefficient (K(f)) values for eight common-use pyrethroids were determined using a two-compartment mass balance model and parameters determined in experimental seawater microcosms. Mass balance, epimerization, and aqueous-phase degradation (i.e., hydrolysis) were characterized using gas chromatography-negative chemical ionization mass spectrometry to facilitate K(f) estimation. Of the eight pyrethroids, only bifenthrin exhibited increasing sorption on the SPME fiber over the entire time-series exposure, indicating that its K(f) value could be estimated through a stable-compound model. The remaining pyrethroids were found to be unstable (half-life of 0.98) and the remaining unstable pyrethroids (R(2) > 0.7), leading to estimated values of log K(f) between 5.7 and 6.4, after correcting for residual dissolved organic carbon (DOC) in the experimental seawater. These K(f) values can be used to determine freely dissolved pyrethroid concentrations in the pg/L range using PDMS-SPME in fresh or seawater matrices under equilibrium conditions in laboratory or field applications.

  5. Polypyrrole nanowire as an excellent solid phase microextraction fiber for bisphenol A analysis in food samples followed by ion mobility spectrometry.

    Science.gov (United States)

    Kamalabadi, Mahdie; Mohammadi, Abdorreza; Alizadeh, Naader

    2016-08-15

    A polypyrrole nanowire coated fiber was prepared and used in head-space solid phase microextraction coupled with ion mobility spectrometry (HS-SPME-IMS) to the analysis of bisphenol A (BPA) in canned food samples, for the first time. This fiber was synthesized by electrochemical oxidation of the monomer in aqueous solution. The fiber characterization by scanning electron microscopy (SEM) revealed that the new fiber exhibited two-dimensional structures with a nanowire morphology. The effects of important extraction parameters on the efficiency of HS-SPME were investigated and optimized. Under the optimum conditions, the linearity of 10-150ngg(-1) and limit of detection (based on S/N=3) of 1ngg(-1) were obtained in BPA analysis. The repeatability (n=5) expressed as the relative standard deviation (RSD%) was 5.8%. At the end, the proposed method was successfully applied to determine BPA in various canned food samples (peas, corns, beans). Relative recoveries were obtained 93-96%. Method validation was conducted by comparing our results with those obtained through HPLC with fluorescence detection (FLD). Compatible results indicate that the proposed method can be successfully used in BPA analysis. This method is simple and cheaper than chromatographic methods, with no need of extra organic solvent consumption and derivatization prior to sample introduction. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Membrane solid phase microextraction with alumina hollow fiber on line coupled with ICP-OES for the determination of trace copper, manganese and nickel in environmental water samples.

    Science.gov (United States)

    Cui, Chao; He, Man; Hu, Bin

    2011-03-15

    A novel alumina hollow fiber was synthesized by sol-gel template method and was characterized by scanning electron microscopy, N(2) adsorption technique and X-ray diffraction. With the use of prepared alumina hollow fiber as extraction membrane, a new method of flow injection (FI)-membrane solid phase microextraction (MSPME) on-line coupled to inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for simultaneous determination of trace metals (Cu, Mn and Ni) in environmental water samples. The adsorption capacities of the alumina hollow fiber for Cu, Mn and Ni were found to be 6.6, 8.7 and 13.3 mg g(-1), respectively. With a preconcentration factor of 10, the limits of detection (LODs) for Cu, Mn and Ni were found to be 0.88, 0.61 and 0.38 ng mL(-1), respectively, and the relative standard deviations (RSDs) were ranging from 6.2 to 7.9% (n = 7, c = 10 ng mL(-1)). To validate the accuracy, the proposed method was applied to the analysis of certified reference material GSBZ50009-88 environmental water and the determined values are in good agreement with the certified values. The developed method was also employed for the analysis of Yangtze River water and East Lake water, and the recoveries for the spiked samples were in the range of 87.4-110.2%. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Fabrication of novel nanoporous array anodic alumina solid-phase microextraction fiber coating and its potential application for headspace sampling of biological volatile organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Zhuomin [School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Wang Qingtang [Key Laboratory of Analysis and Detection for Food Safety of Ministry of Education, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350002 (China); Li Gongke, E-mail: cesgkl@mail.sysu.edu.cn [School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275 (China)

    2012-05-21

    Highlights: Black-Right-Pointing-Pointer Nanoporous array anodic alumina (NAAA) SPME coating was originally prepared. Black-Right-Pointing-Pointer NAAA SPME coating achieved excellent enrichment capability and selectivity for VOCs. Black-Right-Pointing-Pointer NAAA SPME coating can be applied for the headspace sampling of biological VOCs. - Abstract: In the study, nanoporous array anodic alumina (NAAA) prepared by a simple, rapid and stable two-step anodic oxidization method was introduced as a novel solid-phase microextraction (SPME) fiber coating. The regular nanoporous array structure and chemical composition of NAAA SPME fiber coating was characterized and validated by scanning electron microscopy and energy dispersive spectroscopy, respectively. Compared with the commercial polydimethylsiloxane (PDMS) SPME fiber coating, NAAA SPME fiber coating achieved the higher enrichment capability (1.7-4.7 folds) for the mixed standards of volatile organic compounds (VOCs). The selectivity for volatile alcohols by NAAA SPME fiber coating demonstrated an increasing trend with the increasing polarity of alcohols caused by the gradually shortening carbon chains from 1-undecanol to 1-heptanol or the isomerization of carbon chains of some typical volatile alcohols including 2-ethyl hexanol, 1-octanol, 2-phenylethanol, 1-phenylethanol, 5-undecanol, 2-undecanol and 1-undecanol. Finally, NAAA SPME fiber coating was originally applied for the analysis of biological VOCs of Bailan flower, stinkbug and orange peel samples coupled with gas chromatography-mass spectrometry (GC-MS) detection. Thirty, twenty-seven and forty-four VOCs of Bailan flower, stinkbug and orange peel samples were sampled and identified, respectively. Moreover, the contents of trace 1-octanol and nonanal of real orange peel samples were quantified for the further method validation with satisfactory recoveries of 106.5 and 120.5%, respectively. This work proposed a sensitive, rapid, reliable and convenient

  8. Fabrication of novel nanoporous array anodic alumina solid-phase microextraction fiber coating and its potential application for headspace sampling of biological volatile organic compounds

    International Nuclear Information System (INIS)

    Zhang Zhuomin; Wang Qingtang; Li Gongke

    2012-01-01

    Highlights: ► Nanoporous array anodic alumina (NAAA) SPME coating was originally prepared. ► NAAA SPME coating achieved excellent enrichment capability and selectivity for VOCs. ► NAAA SPME coating can be applied for the headspace sampling of biological VOCs. - Abstract: In the study, nanoporous array anodic alumina (NAAA) prepared by a simple, rapid and stable two-step anodic oxidization method was introduced as a novel solid-phase microextraction (SPME) fiber coating. The regular nanoporous array structure and chemical composition of NAAA SPME fiber coating was characterized and validated by scanning electron microscopy and energy dispersive spectroscopy, respectively. Compared with the commercial polydimethylsiloxane (PDMS) SPME fiber coating, NAAA SPME fiber coating achieved the higher enrichment capability (1.7–4.7 folds) for the mixed standards of volatile organic compounds (VOCs). The selectivity for volatile alcohols by NAAA SPME fiber coating demonstrated an increasing trend with the increasing polarity of alcohols caused by the gradually shortening carbon chains from 1-undecanol to 1-heptanol or the isomerization of carbon chains of some typical volatile alcohols including 2-ethyl hexanol, 1-octanol, 2-phenylethanol, 1-phenylethanol, 5-undecanol, 2-undecanol and 1-undecanol. Finally, NAAA SPME fiber coating was originally applied for the analysis of biological VOCs of Bailan flower, stinkbug and orange peel samples coupled with gas chromatography–mass spectrometry (GC–MS) detection. Thirty, twenty-seven and forty-four VOCs of Bailan flower, stinkbug and orange peel samples were sampled and identified, respectively. Moreover, the contents of trace 1-octanol and nonanal of real orange peel samples were quantified for the further method validation with satisfactory recoveries of 106.5 and 120.5%, respectively. This work proposed a sensitive, rapid, reliable and convenient analytical method for the potential study of trace and small molecular

  9. Headspace Solid-Phase Microextraction Coupled with Gas ...

    African Journals Online (AJOL)

    contact temperature measurement system (ONTMS). Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used to analyze the volatile composition of raw FCP and its various ...

  10. Novel metal-ion-mediated, complex-imprinted solid-phase microextraction fiber for the selective recognition of thiabendazole in citrus and soil samples.

    Science.gov (United States)

    Lian, Haixian; Hu, Yuling; Li, Gongke

    2014-01-01

    A novel metal-ion-mediated complex-imprinted-polymer-coated solid-phase microextraction (SPME) fiber used to specifically recognize thiabendazole (TBZ) in citrus and soil samples was developed. The complex-imprinted polymer was introduced as a novel SPME coating using a "complex template" constructed with Cu(II) ions and TBZ. The recognition and enrichment properties of the coating in water were significantly improved based on the metal ion coordination interaction rather than relying on hydrogen bonding interactions that are commonly applied for the molecularly imprinting technique. Several parameters controlling the extraction performance of the complex-imprinted-polymer-coated fiber were investigated including extraction solvent, pH value, extraction time, metal ion species, etc. Furthermore, SPME coupled with HPLC was developed for detection of TBZ, and the methods resulted in good linearity in the range of 10.0-150.0 ng/mL with a detection limit of 2.4 ng/mL. The proposed method was applied to the analysis of TBZ in spiked soil, orange, and lemon with recoveries of 80.0-86.9% and RSDs of 2.0-8.1%. This research provides an example to prepare a desirable water-compatible and specifically selective SPME coating to extract target molecules from aqueous samples by introducing metal ions as the mediator. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Preliminary construction of integral analysis for characteristic components in complex matrices by in-house fabricated solid-phase microextraction fibers combined with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Tang, Zhentao; Hou, Wenqian; Liu, Xiuming; Wang, Mingfeng; Duan, Yixiang

    2016-08-26

    Integral analysis plays an important role in study and quality control of substances with complex matrices in our daily life. As the preliminary construction of integral analysis of substances with complex matrices, developing a relatively comprehensive and sensitive methodology might offer more informative and reliable characteristic components. Flavoring mixtures belonging to the representatives of substances with complex matrices have now been widely used in various fields. To better study and control the quality of flavoring mixtures as additives in food industry, an in-house fabricated solid-phase microextraction (SPME) fiber was prepared based on sol-gel technology in this work. The active organic component of the fiber coating was multi-walled carbon nanotubes (MWCNTs) functionalized with hydroxyl-terminated polydimethyldiphenylsiloxane, which integrate the non-polar and polar chains of both materials. In this way, more sensitive extraction capability for a wider range of compounds can be obtained in comparison with commercial SPME fibers. Preliminarily integral analysis of three similar types of samples were realized by the optimized SPME-GC-MS method. With the obtained GC-MS data, a valid and well-fit model was established by partial least square discriminant analysis (PLS-DA) for classification of these samples (R2X=0.661, R2Y=0.996, Q2=0.986). The validity of the model (R2=0.266, Q2=-0.465) has also approved the potential to predict the "belongingness" of new samples. With the PLS-DA and SPSS method, further screening out the markers among three similar batches of samples may be helpful for monitoring and controlling the quality of the flavoring mixtures as additives in food industry. Conversely, the reliability and effectiveness of the GC-MS data has verified the comprehensive and efficient extraction performance of the in-house fabricated fiber. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Preparation of molecularly imprinted solid-phase microextraction fiber for the selective removal and extraction of the antiviral drug abacavir in environmental and biological matrices

    International Nuclear Information System (INIS)

    Terzopoulou, Zoi; Papageorgiou, Myrsini; Kyzas, George Z.; Bikiaris, Dimitrios N.; Lambropoulou, Dimitra A.

    2016-01-01

    In the present study, a molecularly imprinted solid-phase microextraction fiber (MIP-SPME f ) was synthesized and applied for the selective removal and extraction of the antiviral drug, abacavir (ABA). Morphology and structure characterization of fibers were performed by scanning electron microscopy and Fourier transform infrared spectra, respectively. The effects on the adsorption behavior of the process parameters were studied and the equilibrium data were fitted by the Langmuir, Freundlich and Langmuir-Freundlich models. The maximum adsorption capability (Q max ) was determined by Langmuir- Freundlich model and was 149 mg/g for MIP-SPME f . In the next step, SPME methodology followed by liquid desorption and liquid chromatography with mass spectrometry (LC/MS) has been developed and evaluated for the determination of the target compound in environmental and biological matrices (surface waters, wastewaters and urine). Parameters that could influence SPME efficiency were investigated. Then, optimization of stirring speed, extraction time and salt content was carried out by using a central composite design (CCD) and response surface methodology (RSM). A quadratic model between dependent and independent variables was built. Under the optimum conditions (extraction time 40 min, stirring rate 650 rpm and salt content 0.3% NaCl w/v) the validated method presented a high sensitivity and selectivity with LODs and LOQs in the range of 10.1–13.6 and 33.3–43.9 ng/L, respectively. The developed method was successfully applied to the analysis of ABA in real samples. The percentage extraction efficiency ranged from 88 to 99% revealing good accuracy and absence of matrix effects. - Highlights: • Preparation of a novel SPME MIP fiber with remarkable recognition properties. • Selective removal and extraction of abacavir from environmental & biological media. • Detailed adsorbent characterization and adsorption studies. • Successful application of synthesized MIPs

  13. Solid-phase microextraction and the human fecal VOC metabolome.

    Directory of Open Access Journals (Sweden)

    Emma Dixon

    2011-04-01

    Full Text Available The diagnostic potential and health implications of volatile organic compounds (VOCs present in human feces has begun to receive considerable attention. Headspace solid-phase microextraction (SPME has greatly facilitated the isolation and analysis of VOCs from human feces. Pioneering human fecal VOC metabolomic investigations have utilized a single SPME fiber type for analyte extraction and analysis. However, we hypothesized that the multifarious nature of metabolites present in human feces dictates the use of several diverse SPME fiber coatings for more comprehensive metabolomic coverage. We report here an evaluation of eight different commercially available SPME fibers, in combination with both GC-MS and GC-FID, and identify the 50/30 µm CAR-DVB-PDMS, 85 µm CAR-PDMS, 65 µm DVB-PDMS, 7 µm PDMS, and 60 µm PEG SPME fibers as a minimal set of fibers appropriate for human fecal VOC metabolomics, collectively isolating approximately 90% of the total metabolites obtained when using all eight fibers. We also evaluate the effect of extraction duration on metabolite isolation and illustrate that ex vivo enteric microbial fermentation has no effect on metabolite composition during prolonged extractions if the SPME is performed as described herein.

  14. Graphitic carbon nitrides modified hollow fiber solid phase microextraction for extraction and determination of uric acid in urine and serum coupled with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Sun, Ying-pei; Chen, Juan; Qi, Huan-yang; Shi, Yan-ping

    2015-11-01

    An elevated uric acid (UA) in urine or serum can affect renal function and blood pressure, which is an indicator of gout, cardiovascular and renal diseases, hypertension, etc. In this work, a new type of mixed matrix membrane (MMM), based on graphitic carbon nitrides (g-CNs) and hollow fiber (HF), was prepared and combined with solid phase microextraction (SPME) mode to determine UA in urine and serum followed by gas chromatography-mass spectrometry (GC/MS). The porous g-CNs were dispersed in ammonia, and then the exfoliated g-CNs nanosheets were held in the pores of HF by capillary forces and sonification. The prepared g-CNs modified HF (g-CNs-HF) was immersed in biofluid directly to extract UA with SPME mode and the solvent-free mode is convenient for further derivatization and analysis. To achieve the highest extraction efficiency (EF), main extraction and derivatization parameters, such as g-CNs-HF immobilizing time, sonification power and time of extraction, derivatization and desorption time, were optimized. Under the optimum extraction conditions, a favorable linearity of UA was obtained in the range 0.1-200μgmL(-1) with correlation coefficients higher than 0.9990, and the average recoveries at three spiked levels of UA in urine and serum ranged from 80.7% to 121.6%, from 84.7% to 101.1%, respectively. The obtained results demonstrated the developed g-CNs-HF-SPME is a simple, rapid, cost-effective, solvent-free method for the analysis of UA in biofluid. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. A porous carbon derived from amino-functionalized material of Institut Lavoisier as a solid-phase microextraction fiber coating for the extraction of phthalate esters from tea.

    Science.gov (United States)

    Liang, Weiqian; Wang, Juntao; Zang, Xiaohuan; Wang, Chun; Wang, Zhi

    2016-04-01

    In this work, a porous carbon derived from amino-functionalized material of Institut Lavoisier (C-NH2 -MIL-125) was prepared and coated onto a stainless-steel wire through sol-gel technique. The coated fiber was used for the solid-phase microextraction of trace levels of phthalate esters (diallyl phthalate, di-iso-butyl ortho-phthalate, di-n-butyl ortho-phthalate, benzyl-n-butyl ortho-phthalate, and bis(2-ethylhexy) ortho-phthalate) from tea beverage samples before gas chromatography with mass spectrometric analysis. Several experimental parameters that could influence the extraction efficiency such as extraction time, extraction temperature, sample pH, sample salinity, stirring rate, desorption temperature and desorption time, were investigated. Under the optimal conditions, the linearity existed in the range of 0.05-30.00 μg/L for green jasmine tea beverage samples, and 0.10-30.00 μg/L for honey jasmine tea beverage samples, with the correlation coefficients (r) ranging from 0.9939 to 0.9981. The limits of detection of the analytes for the method were 2.0-3.0 ng/L for green jasmine tea beverage sample, and 4.0-5.0 ng/L for honey jasmine tea beverage sample, depending on the compounds. The recoveries of the analytes for the spiked samples were in the range of 82.0-106.0%, and the precision, expressed as the relative standard deviations, was less than 11.1%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Preparation of molecularly imprinted solid-phase microextraction fiber for the selective removal and extraction of the antiviral drug abacavir in environmental and biological matrices

    Energy Technology Data Exchange (ETDEWEB)

    Terzopoulou, Zoi [Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24, Thessaloniki (Greece); Papageorgiou, Myrsini [Laboratory of Environmental Pollution Control, Department of Chemistry, Aristotle University of Thessaloniki, GR–541 24, Thessaloniki (Greece); Kyzas, George Z.; Bikiaris, Dimitrios N. [Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24, Thessaloniki (Greece); Lambropoulou, Dimitra A., E-mail: dlambro@chem.auth.gr [Laboratory of Environmental Pollution Control, Department of Chemistry, Aristotle University of Thessaloniki, GR–541 24, Thessaloniki (Greece)

    2016-03-24

    In the present study, a molecularly imprinted solid-phase microextraction fiber (MIP-SPME{sub f}) was synthesized and applied for the selective removal and extraction of the antiviral drug, abacavir (ABA). Morphology and structure characterization of fibers were performed by scanning electron microscopy and Fourier transform infrared spectra, respectively. The effects on the adsorption behavior of the process parameters were studied and the equilibrium data were fitted by the Langmuir, Freundlich and Langmuir-Freundlich models. The maximum adsorption capability (Q{sub max}) was determined by Langmuir- Freundlich model and was 149 mg/g for MIP-SPME{sub f}. In the next step, SPME methodology followed by liquid desorption and liquid chromatography with mass spectrometry (LC/MS) has been developed and evaluated for the determination of the target compound in environmental and biological matrices (surface waters, wastewaters and urine). Parameters that could influence SPME efficiency were investigated. Then, optimization of stirring speed, extraction time and salt content was carried out by using a central composite design (CCD) and response surface methodology (RSM). A quadratic model between dependent and independent variables was built. Under the optimum conditions (extraction time 40 min, stirring rate 650 rpm and salt content 0.3% NaCl w/v) the validated method presented a high sensitivity and selectivity with LODs and LOQs in the range of 10.1–13.6 and 33.3–43.9 ng/L, respectively. The developed method was successfully applied to the analysis of ABA in real samples. The percentage extraction efficiency ranged from 88 to 99% revealing good accuracy and absence of matrix effects. - Highlights: • Preparation of a novel SPME MIP fiber with remarkable recognition properties. • Selective removal and extraction of abacavir from environmental & biological media. • Detailed adsorbent characterization and adsorption studies. • Successful application of

  17. Headspace solid-phase microextraction and gas chromatography ...

    African Journals Online (AJOL)

    Purpose: To extract and analyze the volatile components of Chrysanthemum morifolium Ramat. 'huaiju' by headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry. (GC–MS). Methods: Volatile components were extracted by HS-SPME and identified by GC–MS. The relative contents ...

  18. Solid-phase microextraction for the analysis of biological samples

    NARCIS (Netherlands)

    Theodoridis, G; Koster, EHM; de Jong, GJ

    2000-01-01

    Solid-phase microextraction (SPME) has been introduced for the extraction of organic compounds from environmental samples. This relatively new extraction technique has now also gained a lot of interest in a broad field of analysis including food, biological and pharmaceutical samples. SPME has a

  19. Headspace solid-phase microextraction and gas chromatography ...

    African Journals Online (AJOL)

    Purpose: To extract and analyze the volatile components of Chrysanthemum morifolium Ramat. 'huaiju' by headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry (GC–MS). Methods: Volatile components were extracted by HS-SPME and identified by GC–MS. The relative contents ...

  20. Full automation of solid-phase microextraction/on-fiber derivatization for simultaneous determination of endocrine-disrupting chemicals and steroid hormones by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Yang, Lihua; Lan, Chongyu; Liu, Hongtao; Dong, Jun; Luan, Tiangang

    2006-09-01

    A fully automated method using direct immersion solid-phase microextraction (DI-SPME) and headspace on-fiber silylation for simultaneous determinations of exogenous endocrine-disrupting chemicals (EDCs) and endogenous steroid hormones in environmental aqueous and biological samples by gas chromatography-mass spectrometry (GC-MS) was developed and compared to a previously reported manual method. Three EDCs and five endocrine steroid hormones were selected to evaluate this method. The extraction and derivatization time, ion strength, pH, incubation temperature, sample volume, and extraction solvent were optimized. Satisfactory results in pure water were obtained in terms of linearity of calibration curve (R2=0.9932-1.0000), dynamic range (3 orders of magnitude), precision (4-9% RSD), as well as LOD (0.001-0.124 microg L(-1)) and LOQ (0.004-0.413 microg L(-1)), respectively. These results were similar to those obtained using a manual method, and moreover, the precision was improved. This new automated method has been applied to the determinations of target compounds in real samples used in our previous study on a manual SPME method. Exogenous octylphenol (OP), technical grade nonylphenol (t-NP), and diethylstilbestrol (DES) were at 0.13, 5.03, and 0.02 microg L(-1) in river water and 3.76, 13.25, and 0.10 microg L(-1) in fish serum, respectively. Natural steroid hormones estrone (E1), 17beta-estradiol (E2), and testosterone (T) were at 0.19, 0.11, and 6.22 microg L(-1) in river water; and in female fish serum E1, E2, and pregnenolone (PREG) were at 1.37, 1.95, and 6.25 microg L(-1), respectively. These results were confirmed by the manual method. The developed fully automated SPME and on-fiber silylation procedures showed satisfactory applications in environmental analysis and the performances show improved precision and a reduced analysis time compared to the manual method.

  1. Application of solid-phase microextraction in analytical toxicology.

    Science.gov (United States)

    Pragst, Fritz

    2007-08-01

    Solid-phase microextraction (SPME) is a miniaturized and solvent-free sample preparation technique for chromatographic-spectrometric analysis by which the analytes are extracted from a gaseous or liquid sample by absorption in, or adsorption on, a thin polymer coating fixed to the solid surface of a fiber, inside an injection needle or inside a capillary. In this paper, the present state of practical performance and of applications of SPME to the analysis of blood, urine, oral fluid and hair in clinical and forensic toxicology is reviewed. The commercial coatings for fibers or needles have not essentially changed for many years, but there are interesting laboratory developments, such as conductive polypyrrole coatings for electrochemically controlled SPME of anions or cations and coatings with restricted-access properties for direct extraction from whole blood or immunoaffinity SPME. In-tube SPME uses segments of commercial gas chromatography (GC) capillaries for highly efficient extraction by repeated aspiration-ejection cycles of the liquid sample. It can be easily automated in combination with liquid chromatography but, as it is very sensitive to capillary plugging, it requires completely homogeneous liquid samples. In contrast, fiber-based SPME has not yet been performed automatically in combination with high-performance liquid chromatography. The headspace extractions on fibers or needles (solid-phase dynamic extraction) combined with GC methods are the most advantageous versions of SPME because of very pure extracts and the availability of automatic samplers. Surprisingly, substances with quite high boiling points, such as tricyclic antidepressants or phenothiazines, can be measured by headspace SPME from aqueous samples. The applicability and sensitivity of SPME was essentially extended by in-sample or on-fiber derivatization. The different modes of SPME were applied to analysis of solvents and inhalation narcotics, amphetamines, cocaine and metabolites

  2. Preparation, characterization, and applications of a novel solid-phase microextraction fiber by sol-gel technology on the surface of stainless steel wire for determination of poly cyclic aromatic hydrocarbons in aquatic environmental samples.

    Science.gov (United States)

    Es-haghi, Ali; Hosseininasab, Valiallah; Bagheri, Habib

    2014-02-27

    A novel solid-phase microextraction(SPME) fiber was prepared using sol-gel technology with ethoxylated nonylphenol as a fiber coating material. The fiber was employed to develop a headspace SPME-GC-MS method suitable for quantification of 13 polycyclic aromatic hydrocarbons (PAHs) in water samples. Surface characteristics of the fibers were inspected by energy dispersive X-ray (EDX) spectroscopy as well as by scanning electron microscopy (SEM). The SEM measurements showed the presence of highly porous nano-sized particles in the coating. Important parameters affecting the extraction efficiency such as extraction temperature and time, desorption conditions as well as ionic strength have been evaluated and optimized. In the next step, the validation of the new method have been performed, finding it to be specific in the trace analysis of PAHs, with the limit of detection (LOD) ranging from 0.01 to 0.5 μg L(-1) and the linear range from the respective LOD to 200 μg L(-1) with RSD amounting to less than 8%. The thermal stability of the fibers was investigated as well and they were found to be durable at 280°C for 345 min. Furthermore, the proposed method was successfully applied for quantification of PAHs in real water samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Covalent Bonding of Metal-Organic Framework-5/Graphene Oxide Hybrid Composite to Stainless Steel Fiber for Solid-Phase Microextraction of Triazole Fungicides from Fruit and Vegetable Samples.

    Science.gov (United States)

    Zhang, Shuaihua; Yang, Qian; Wang, Wenchang; Wang, Chun; Wang, Zhi

    2016-04-06

    A hybrid material of the zinc-based metal-organic framework-5 and graphene oxide (metal-organic framework-5/graphene oxide) was prepared as a novel fiber coating material for solid-phase microextraction (SPME). The SPME fibers were fabricated by covalent bonding via chemical cross-linking between the coating material metal-organic framework-5/graphene oxide and stainless steel wire. The prepared fiber was used for the extraction of five triazole fungicides from fruit and vegetable samples. Gas chromatography coupled with microelectron capture detector (GC-μECD) was used for quantification. The developed method gave a low limit of detection (0.05-1.58 ng g(-1)) and good linearity (0.17-100 ng g(-1)) for the determination of the triazole fungicides in fruit and vegetable samples. The relative standard deviations (RSDs) for five replicate extractions of the triazole fungicides ranged from 3.7 to 8.9%. The method recoveries for spiked fungicides (5, 20, and 50 ng g(-1)) in grape, apple, cucumber, celery cabbage, pear, cabbage, and tomato samples were in the range of 85.6-105.8% with the RSDs ranging from 3.6 to 11.4%, respectively, depending on both the analytes and samples. The metal-organic framework-5/graphene oxide coated fiber was stable enough for 120 extraction cycles without a significant loss of extraction efficiency. The method was suitable for the determination of triazole fungicides in fruit and vegetable samples.

  4. 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.

    Science.gov (United States)

    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.

  5. A star-shaped polythiophene dendrimer coating for solid-phase microextraction of triazole agrochemicals.

    Science.gov (United States)

    Abolghasemi, Mir Mahdi; Habibiyan, Rahim; Jaymand, Mehdi; Piryaei, Marzieh

    2018-02-14

    A nanostructured star-shaped polythiophene dendrimer was prepared and used as a fiber coating for headspace solid phase microextraction of selected triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole) from water samples. The dendrimer with its large surface area was characterized by thermogravimetric analysis, UV-Vis spectroscopy and field emission scanning electron microscopy. It was placed on a stainless steel wire for use in SPME. The experimental conditions for fiber coating, extraction, stirring rate, ionic strength, pH value, desorption temperature and time were optimized. Following thermal desorption, the pesticides were quantified by GC-MS. Under optimum conditions, the repeatability (RSD) for one fiber (for n = 3) ranges from 4.3 to 5.6%. The detection limits are between 8 and 12 pg mL -1 . The method is fast, inexpensive (in terms of equipment), and the fiber has high thermal stability. Graphical abstract Schematic presentation of a nanostructured star-shaped polythiophene dendrimer for use in headspace solid phase microextraction of the triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole). They were then quantified by gas chromatography-mass spectrometry.

  6. Optimization of a novel method for determination of benzene, toluene, ethylbenzene, and xylenes in hair and waste water samples by carbon nanotubes reinforced sol-gel based hollow fiber solid phase microextraction and gas chromatography using factorial experimental design.

    Science.gov (United States)

    Es'haghi, Zarrin; Ebrahimi, Mahmoud; Hosseini, Mohammad-Saeid

    2011-05-27

    A novel design of solid phase microextraction fiber containing carbon nanotube reinforced sol-gel which was protected by polypropylene hollow fiber (HF-SPME) was developed for pre-concentration and determination of BTEX in environmental waste water and human hair samples. The method validation was included and satisfying results with high pre-concentration factors were obtained. In the present study orthogonal array experimental design (OAD) procedure with OA(16) (4(4)) matrix was applied to study the effect of four factors influencing the HF-SPME method efficiency: stirring speed, volume of adsorption organic solvent, extraction and desorption time of the sample solution, by which the effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance (ANOVA) was employed for estimating the main significant factors and their percentage contributions in extraction. Calibration curves were plotted using ten spiking levels of BTEX in the concentration ranges of 0.02-30,000ng/mL with correlation coefficients (r) 0.989-0.9991 for analytes. Under the optimized extraction conditions, the method showed good linearity (0.3-20,000ng/L), repeatability, low limits of detections (0.49-0.7ng/L) and excellent pre-concentration factors (185-1872). The best conditions which were estimated then applied for the analysis of BTEX compounds in the real samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Polypyrrole/montmorillonite nanocomposite as a new solid phase microextraction fiber combined with gas chromatography–corona discharge ion mobility spectrometry for the simultaneous determination of diazinon and fenthion organophosphorus pesticides

    International Nuclear Information System (INIS)

    Jafari, Mohammad T.; Saraji, Mohammad; Sherafatmand, Hossein

    2014-01-01

    Graphical abstract: - Highlights: • A novel SPME fiber based on polypyrrole/montmorillonite nanocomposites with highly porous and thermal stability was prepared. • The two-dimensional separation technique, GC–IMS, was used for analysis of complex matrices extracted by SPME. • Direct and simultaneous analysis of diazinon and fenthion in various real samples was successfully accomplished. - Abstract: A novel solid phase microextraction (SPME) fiber was prepared and coupled with gas chromatography corona discharge ion mobility spectrometry (GC–CD–IMS) based on polypyrrole/montmorillonite nanocomposites for the simultaneous determination of diazinon and fenthion. The nanocomposite polymer was coated using a three-electrode electrochemical system and directly deposited on a Ni–Cr wire by applying a constant potential. The scanning electron microscopy images revealed that the new fiber exhibited a rather porous and homogenous surface. The thermal stability of the fabricated fiber was investigated by thermogravimetric analysis. The effects of different parameters influencing the extraction efficiency such as extraction temperature and time, salt addition, stirring rate, the amount of nanoclay, and desorption temperature were investigated and optimized. The method was exhaustively evaluated in terms of sensitivity, recovery, and reproducibility. The linearity ranges of 0.05–10 and 0.08–10 μg L −1 , and the detection limits of 0.020 and 0.035 μg L −1 were obtained for diazinon and fenthion, respectively. The relative standard deviation values were calculated to be lower than 5% and 8% for intra-day and inter-day, respectively. Finally, the developed method was applied to determine the diazinon and fenthion (as model compounds) in cucumber, lettuce, apple, tap and river water samples. The satisfactory recoveries revealed the capability of the two-dimensional separation technique (retention time in GC and drift time in IMS) for the analysis of complex

  8. Use of solid phase microextraction (SPME) for profiling the volatile metabolites produced by Glomerella cingulata.

    Science.gov (United States)

    Miyazawa, Mitsuo; Kimura, Minako; Yabe, Yoshito; Tsukamoto, Daisuke; Sakamoto, Masaya; Horibe, Isao; Okuno, Yoshiharu

    2008-01-01

    The profile of volatile organic compounds (VOCs) released from Glomerella cingulata using solid phase microextraction (SPME) with different fibers, Polydimethylsiloxane (PDMS), Polydimethylsiloxane/Divinylbenzene (PDMS/DVB), Carboxen/Polydimethylsiloxane (CAR/PDMS) and Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), was investigated. C4-C6 aliphatic alcohols were the predominant fraction of VOCs isolated by CAR/PDMS fiber. Sesquiterpene hydrocarbons represented 20.3% of VOCs isolated by PDMS fiber. During the growth phase, Ochracin was produced in the large majority of VOCs. 3-Methylbutanol and phenylethyl alcohol were found in the log phase of it. Alcohols were found in cultures of higher age, while sesquiterpenes were found to be characteristic of initial growth stage of G. cingulata.

  9. Headspace solid-phase microextraction for wine volatile analysis.

    Science.gov (United States)

    Azzi-Achkouty, Samar; Estephan, Nathalie; Ouaini, Naïm; Rutledge, Douglas N

    2017-07-03

    The most commonly used technique to prepare samples for the analysis of wine volatile is the headspace solid-phase microextraction (HS-SPME). This method has gained popularity in last few years, as it is a unique solventless preparation technique. In this paper, a summary of recently published studies using HS-SPME for the analysis of wine aromas, with special emphasis on the method developed, has been compiled. Several papers are discussed in detail, mainly with respect to the SPME conditions used. A brief summary of the reviews related to HS-SPME analysis is given and discussed. Several parameters affecting the HS-SPME, such as the salt concentration and the agitation conditions, are used in the same way as used in several papers. The HS-SPME extraction proved to be sufficiently sensitive to satisfy legislative requirements related to low detection and quantification limits as well as method accuracy and precision requirements. However, in order to achieve the best performance and precision, the protocol needs to be optimized for each case. The effect of different parameters must be well characterized to ensure correct extraction and desorption to ensure the transfer of extracted compounds into the analytical system. The operating parameters, such as time, temperature, and agitation, must then be kept constant for all the samples.

  10. Determination of Δ9-tetrahydrocannabinol and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol in water samples by solid-phase microextraction with on-fiber derivatization and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Racamonde, Inés; Villaverde-de-Sáa, Eugenia; Rodil, Rosario; Quintana, José Benito; Cela, Rafael

    2012-07-06

    A new method for the determination of two cannabinoids, Δ9-tetrahydrocannabinol (THC) and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THCCOOH), in wastewater samples is proposed using solid-phase microextraction (SPME) as extraction technique and gas chromatography coupled to mass spectrometry (GC-MS) as determination technique. Several parameters involved in SPME extraction were studied and optimized (time, temperature, volume, pH and ionic strength of sample, and type of fiber). Moreover two derivatization reagents, N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), were studied in depth, providing MSTFA the best results. The use of internal standard calibration (with their corresponding deuterated analogs) allows avoiding standard addition calibration for the quantification of samples. Under optimal conditions, limits of detection at low nanograms per liter were achieved (1.0 and 2.5 ng L⁻¹ for THC and THCCOOH respectively). Precision (RSDTHC and 50-153 ng L⁻¹ for THCCOOH) and an incomplete removal, which translates into their detection in the receiving river. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Determination of arsenic and selenium by hydride generation and headspace solid phase microextraction coupled with optical emission spectrometry

    Science.gov (United States)

    Tyburska, Anna; Jankowski, Krzysztof; Rodzik, Agnieszka

    2011-07-01

    A hydride generation headspace solid phase microextraction technique has been developed in combination with optical emission spectrometry for determination of total arsenic and selenium. Hydrides were generated in a 10 mL volume septum-sealed vial and subsequently collected onto a polydimethylsiloxane/Carboxen solid phase microextraction fiber from the headspace of sample solution. After completion of the sorption, the fiber was transferred into a thermal desorption unit and the analytes were vaporized and directly introduced into argon inductively coupled plasma or helium microwave induced plasma radiation source. Experimental conditions of hydride formation reaction as well as sorption and desorption of analytes have been optimized showing the significant effect of the type of the solid phase microextraction fiber coating, the sorption time and hydrochloric acid concentration of the sample solution on analytical characteristics of the method developed. The limits of detection of arsenic and selenium were 0.1 and 0.8 ng mL - 1 , respectively. The limit of detection of selenium could be improved further using biosorption with baker's yeast Saccharomyces cerevisiae for analyte preconcentration. The technique was applied for the determination of total As and Se in real samples.

  12. Preparation and application of solid-phase microextraction fiber based on molecularly imprinted polymer for determination of anabolic steroids in complicated samples.

    Science.gov (United States)

    Qiu, Lijun; Liu, Wei; Huang, Min; Zhang, Lan

    2010-11-26

    A relatively selective, chemically and physically robust SPME fiber was developed in a simple way with testosterone-imprinted polymer, and then directly coupled with gas chromatography-mass spectrometry (GC-MS) for selective extraction and analysis of anabolic steroids. The factors influencing polymerization (i.e., cross-linker, polymerization solvent, polymerization time) were optimized in detail and the polymer was characterized by scanning electron microscope, infrared spectrometer and thermogravimetric analyzer. Furthermore, the extraction performance of the MIP-coated SPME fibers such as extraction ability and selectivity was evaluated. Moreover, the interaction mode between target analytes and fiber coating was deducted. Finally, the method for extraction and determination of androsterone, stanolone, androstenedione and methyltestosterone by the homemade MIP-coated SPME fibers with GC-MS was obtained. It was applied to the simultaneous analysis of four anabolic steroids in the spiked human urine with the satisfactory recoveries. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. Fast detection of triacetone triperoxide (TATP) from headspace using planar solid-phase microextraction (PSPME) coupled to an IMS detector.

    Science.gov (United States)

    Fan, Wen; Young, Mimy; Canino, Jon; Smith, James; Oxley, Jimmie; Almirall, Jose R

    2012-04-01

    Triacetone triperoxide (TATP) is a high explosive synthesized from easily available reactants making it accessible for illicit uses. In this study, fast detection of TATP is achieved using a novel planar solid-phase microextraction (PSPME) as a preconcentration and sampling device for headspace analysis offering improved sensitivity and reduced sampling time over the conventional fiber-based solid-phase microextraction (SPME) when followed by ion mobility spectrometer (IMS) detection. Quantitation and comparison of the retention capabilities of PSPME as compared to the commercially available SPME were determined using TATP standards and analyzed using gas chromatography-mass spectrometry for SPME analysis and a commercial IMS with no instrumental modification for PSPME. Static and dynamic headspace extractions were used and compared for PSPME extractions, in which low milligram quantities of TATP were detected within 30 s of static mode sampling and less than 5 s in the dynamic mode sampling for PSPME-IMS.

  14. Preparation and application of a poly (ionic liquid)-based molecularly imprinted polymer for multiple monolithic fiber solid-phase microextraction of phenolic acids in fruit juice and beer samples.

    Science.gov (United States)

    Chen, Lei; Huang, Xiaojia

    2017-10-23

    In this work, a new molecularly imprinted polymer (MIP) using a poly (ionic liquid) (PIL) as a functional monomer was prepared and utilized as the extraction medium of multiple monolithic fiber solid-phase microextraction (MMF-SPME). A PIL, 1-ally-3-vinylimidazolium chloride, was used as a functional monomer, and 3,4-dihydroxybenzenepropanoic acid (DBA) and ethylene dimethacrylate were chosen as the template molecule and cross-linker, respectively, to synthesize the PIL/MIP. Under the optimized preparation conditions, the recognition coefficient of PIL-MIP for DBA was as high as 11.6. The combination of PIL/MIP-MMF-SPME and high-performance liquid chromatography with diode array detection (HPLC/DAD) was developed for the sensitive determination of phenolic acids (PAs) in fruit juice and beer samples. Under the optimal conditions which were investigated in detail, the limits of detection (LODs, S/N = 3) for PAs in fruit juice were 0.024-0.24 μg L -1 , and the related values were 0.011-0.052 μg L -1 for the beer sample. The intra-day and inter-day precision (relative standard deviations, n = 4, %) at 1.0 and 100.0 μg L -1 spiking concentration were both less than 10%. In the analysis of PAs in fruit juice and beer samples, satisfactory recoveries and repeatability were achieved. In comparison with reported approaches, the proposed method exhibited some advantages including high selectivity, convenience, satisfactory sensitivity and environmental friendliness.

  15. Headspace Solid-Phase Microextraction Analysis of Volatile Components in Phalaenopsis Nobby’s Pacific Sunset

    Directory of Open Access Journals (Sweden)

    Chih-Hsin Yeh

    2014-09-01

    Full Text Available Phalaenopsis is the most important economic crop in the Orchidaceae family. There are currently numerous beautiful and colorful Phalaenopsis flowers, but only a few species of Phalaenopsis have an aroma. This study reports the analysis volatile components present in P. Nobby’s Pacific Sunset by solid-phase microextraction (SPME coupled with gas chromatography (GC and gas chromatography/mass spectrometry (GC-MS. The results show that the optimal extraction conditions were obtained by using a DVB/CAR/PDMS fiber. A total of 31 compounds were identified, with the major compounds being geraniol, linalool and α-farnesene. P. Nobby’s Pacific Sunset had the highest odor concentration from 09:00 to 13:00 on the eighth day of storage. It was also found that in P. Nobby’s Pacific Sunset orchids the dorsal sepals and petals had the highest odor concentrations, whereas the column had the lowest.

  16. Determination of diphenylether herbicides in water samples by solid-phase microextraction coupled to liquid chromatography.

    Science.gov (United States)

    Sheu, Hong-Li; Sung, Yu-Hsiang; Melwanki, Mahaveer B; Huang, Shang-Da

    2006-11-01

    Solid-phase microextraction (SPME) coupled to LC for the analysis of five diphenylether herbicides (aclonifen, bifenox, fluoroglycofen-ethyl, oxyfluorfen, and lactofen) is described. Various parameters of extraction of analytes onto the fiber (such as type of fiber, extraction time and temperature, pH, impact of salt and organic solute) and desorption from the fiber in the desorption chamber prior to separation (such as type and composition of desorption solvent, desorption mode, soaking time, and flush-out time) were studied and optimized. Four commercially available SPME fibers were studied. PDMS/divinylbenzene (PDMS/DVB, 60 microm) and carbowax/ templated resin (CW/TPR, 50 microm) fibers were selected due to better extraction efficiencies. Repeatability (RSD, 0.994), and detection limit (0.33-1.74 and 0.22-1.94 ng/mL, respectively, for PDMS/DVB and CW/TPR) were investigated. Relative recovery (81-104% for PDMS/DVB and 83-100% for CW/TPR fiber) values have also been calculated. The developed method was successfully applied to the analysis of river water and water collected from a vegetable garden.

  17. Modified headspace solid-phase microextraction for the determination of quantitative relationships between components of mixtures consisting of alcohols, esters, and ethers - impact of the vapor pressure difference of the compounds.

    Science.gov (United States)

    Dawidowicz, Andrzej Lech; Szewczyk, Joanna; Dybowski, Michal P

    2017-07-01

    The quantitative relationship between analytes established by the headspace solid-phase microextraction procedure for multicomponent mixtures depends not only on the character and strength of interactions of individual components with solid-phase microextraction fiber but also on their vapor pressure in the applied headspace solid-phase microextraction system. This study proves that vapor pressure is of minor importance when the sample is dissolved/suspended in a low-volatility liquid of the same physicochemical character as that of the used solid phase microextraction fiber coating. It is demonstrated for mixtures of alcohols, esters, ethers and their selected representatives by applying a headspace solid-phase microextraction system composed of Carbowax fiber and sample solutions in polyethyleneglycol. The observed differences in quantitative relations between components of the examined mixtures established by their direct analysis and by modified headspace solid-phase microextraction are insignificant (F exp  difference between individual components of the examined mixture in the applied headspace solid phase microextraction system due to low components concentration in polyethyleneglycol suspensions (Raoult's law) and due to strong specific interactions of analyte molecules with polyethyleneglycol molecules. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Metal-organic aerogel as a coating for solid-phase microextraction

    Energy Technology Data Exchange (ETDEWEB)

    Saraji, Mohammad, E-mail: saraji@cc.iut.ac.ir; Shahvar, Ali

    2017-06-22

    An iron-based metal-organic aerogel was synthesized using metal-organic framework nanoparticles and applied as a fiber coating for solid-phase microextraction (SPME). Chemical, thermal and morphological characteristics of the material were investigated. Headspace SPME followed by gas chromatography-electron capture detection was used for the determination of chlorobenzenes in the environmental samples. The key experimental factors affecting the extraction efficiency of the analytes, such as ionic strength, extraction and desorption temperature, and extraction time were investigated and optimized. The applicability of the coating for the extraction of chlorobenzenes from the environmental samples including river and tap water, sludge, and coastal soil was evaluated. The detection limits were in the range of 0.1–60 ng L{sup −1}. The relative standard deviations were between 2.0 and 5.0%. The extraction recovery of the analytes was in the range of 88–100%. Compared to the commercial PDMS fiber, the present fiber showed better extraction efficiency. - Highlights: • Metal-organic aerogel was synthesized and used as a novel fiber coating for SPME. • The new coating material showed high surface area and good thermal stability. • GC-ECD was used for determination of chlorobenzenes in environmental samples. • The method showed fast extraction and better efficiency than PDMS commercial fiber.

  19. Determination of Trichloroethylene in Water by Liquid–Liquid Microextraction Assisted Solid Phase Microextraction

    Directory of Open Access Journals (Sweden)

    Mengliang Zhang

    2015-02-01

    Full Text Available A method for the determination of trichloroethylene (TCE in water using portable gas chromatography/mass spectrometry (GC/MS was developed. A novel sample preparation method, liquid–liquid microextraction assisted solid phase microextraction (LLME–SPME, is introduced. In this method, 20 µL of hexane was added to 10 mL of TCE contaminated aqueous samples to assist headspace SPME. The extraction efficiency of SPME was significantly improved with the addition of minute amounts of organic solvents (i.e., 20 µL hexane. The absolute recoveries of TCE at different concentrations were increased from 11%–17% for the samples extracted by SPME to 29%–41% for the samples extracted by LLME–SPME. The method was demonstrated to be linear from 10 to 1000 ng mL−1 for TCE in water. The improvements on extraction efficiencies were also observed for toluene and 1, 2, 4-trichlorobenzene in water by using LLME–SPME method. The LLME–SPME method was optimized by using response surface modeling (RSM.

  20. Solid-phase microextraction may catalize hydrogenation when using hydrogen as carrier in gas chromatography.

    Science.gov (United States)

    Fiorini, D; Boarelli, M C

    2016-07-01

    When hydrogen is used as carrier gas, carbon-carbon double bonds may be hydrogenated in the hot gas chromatograph (GC) injector if introduced by solid-phase microextraction (SPME). SPME fibers coated with polydimethylsiloxane (PDMS)/carboxen/divinylbenzene (DVB), PDMS/carboxen, polyacrylate, PDMS/DVB and PDMS on fused silica, stableflex or metal alloy core have been tested with fatty acid methyl esters (FAMEs) from olive oil. Using coatings containing DVB, hydrogenation took place with high conversion rates (82.0-92.9%) independently of the core material. With all fibers having a metal core, hydrogenation was observed to a certain extent (27.4-85.3%). PDMS, PDMS/carboxen and polyacrylate coated fibers with a fused silica or stableflex core resulted in negligible hydrogenation (0.2-2.5%). The occurrence of hydrogenation was confirmed also with other substances containing carbon-carbon double bonds (n-alkenes, alkenoic acids, mono- and polyunsaturated fatty acid methyl and ethyl esters). Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Speciation analysis of aqueous nanoparticulate diclofenac complexes by solid-phase microextraction

    NARCIS (Netherlands)

    Zielinska, K.; Leeuwen, van H.P.; Thibault, S.; Town, R.M.

    2012-01-01

    The dynamic sorption of an organic compound by nanoparticles (NPs) is analyzed by solid-phase microextraction (SPME) for the example case of the pharmaceutical diclofenac in dispersions of impermeable (silica, SiO(2)) and permeable (bovine serum albumin, BSA) NPs. It is shown that only the

  2. Solid phase microextraction speciation analysis of triclosan in aqueous mediacontaining sorbing nanoparticles

    NARCIS (Netherlands)

    Zielinska, K.

    2014-01-01

    Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid

  3. Determination of Plant Volatiles Using Solid Phase Microextraction GC-MS

    Science.gov (United States)

    Van Bramer, Scott; Goodrich, Katherine R.

    2015-01-01

    This experiment combines analytical techniques of solid phase microextraction and gas chromatography-mass spectrometry with easily relatable and accessible plant volatile chemistry (floral and vegetative scents of local/available plants). The biosynthesis and structure of these chemicals are of interest in the areas of organic chemistry,…

  4. Determination of lidocaine in plasma by direct solid-phase microextraction combined with gas chromatography

    NARCIS (Netherlands)

    Koster, EHM; Wemes, C; Morsink, JB; de Jong, GJ

    2000-01-01

    Direct-immersion solid-phase microextraction (SPME) has been used to extract the local anesthetic lidocaine from human plasma. A simplified model shows the relationship between the total amount of drug in plasma and the amount of drug extracted. The model takes into account that the drug

  5. Fast and robust direct immersion solid phase microextraction coupled with gas chromatography-time-of-flight mass spectrometry method employing a matrix compatible fiber for determination of triazole fungicides in fruits.

    Science.gov (United States)

    Silva, Érica A Souza; Lopez-Avila, Viorica; Pawliszyn, Janusz

    2013-10-25

    A fast and robust method was developed for the determination of ten triazole fungicides in fruit samples using direct immersion solid-phase microextraction coupled to gas chromatography with time-of-flight mass spectrometry detection (DI-SPME-GC-ToFMS). In this work, a newly developed concept of solid-phase microextraction (SPME) sorbent, which allows for direct immersion extraction in complex food matrices, has been applied in the analysis of 10 triazole fungicides in grapes and strawberries pulps. Potential factors affecting the extraction efficiency were investigated and optimized, including extraction temperature, sample pH, and ionic strength, agitation speed, extraction and desorption times. Under optimized conditions, the method was linear for over 4 orders of magnitude in concentration, with linear regression coefficients (R(2)) greater than 0.99 for all test compounds in both matrices. Method reproducibility, as determined by analysis of spiked grapes and strawberries, was better than ±20%. The limits of quantitation objective (LOQs) ranged from 0.25 to 5 ng g(-1) for both matrices, well below the maximum residues levels allowed for those compounds in both matrices. The method was successfully applied in the analysis of commercial samples of grapes and strawberries. Finally, the new SPME method was compared to a modified version of t QuEChERS AOAC method: the limits of quantitation reached by SPME were at least one order of magnitude lower than those achieved by the QuEChERS method, whereas precision and accuracy were comparable for both methods. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Solid-phase microextraction-based cuticular hydrocarbon profiling for intraspecific delimitation in Acyrthosiphon pisum.

    Directory of Open Access Journals (Sweden)

    Nan Chen

    Full Text Available Insect cuticular hydrocarbons (CHCs play critical roles in reducing water loss and chemical communication. Species-specific CHC profiles have been used increasingly as an excellent character for species classification. However, considerably less is known about their potential for population delimitation within species. The aims of this study were to develop a solid-phase microextraction (SPME-based CHC collection method and to investigate whether CHC profiles could serve as potential chemotaxonomic tools for intraspecific delimitation in Acyrthosiphon pisum. Optimization of fibers for SPME sampling revealed that 7 μm polydimethylsiloxane (PDMS demonstrated the most efficient adsorption of CHCs among five different tested fibers. SPME sampling showed good reproducibility with repeated collections of CHCs from a single aphid. Validation of SPME was performed by comparing CHC profiles with those from conventional hexane extractions. The two methods showed no qualitative differences in CHCs, although SPME appeared to extract relatively fewer short-chained CHCs. While CHC profiles of a given population differed among developmental stages, wing dimorphism types, and host plants, wingless adult aphids showed very low variance in relative proportions of individual CHC components. Reproducibility of CHC profiles was explored further to classify wingless adult morphs of A. pisum from five different geographic regions that showed no variation in mitochondrial COI gene sequences. Our results demonstrate that CHC profiles are useful in intraspecific delimitation in the field of insect chemotaxonomy.

  7. Solid-phase microextraction-based cuticular hydrocarbon profiling for intraspecific delimitation in Acyrthosiphon pisum

    Science.gov (United States)

    Chen, Nan; Bai, Yu; Fan, Yong-Liang

    2017-01-01

    Insect cuticular hydrocarbons (CHCs) play critical roles in reducing water loss and chemical communication. Species-specific CHC profiles have been used increasingly as an excellent character for species classification. However, considerably less is known about their potential for population delimitation within species. The aims of this study were to develop a solid-phase microextraction (SPME)-based CHC collection method and to investigate whether CHC profiles could serve as potential chemotaxonomic tools for intraspecific delimitation in Acyrthosiphon pisum. Optimization of fibers for SPME sampling revealed that 7 μm polydimethylsiloxane (PDMS) demonstrated the most efficient adsorption of CHCs among five different tested fibers. SPME sampling showed good reproducibility with repeated collections of CHCs from a single aphid. Validation of SPME was performed by comparing CHC profiles with those from conventional hexane extractions. The two methods showed no qualitative differences in CHCs, although SPME appeared to extract relatively fewer short-chained CHCs. While CHC profiles of a given population differed among developmental stages, wing dimorphism types, and host plants, wingless adult aphids showed very low variance in relative proportions of individual CHC components. Reproducibility of CHC profiles was explored further to classify wingless adult morphs of A. pisum from five different geographic regions that showed no variation in mitochondrial COI gene sequences. Our results demonstrate that CHC profiles are useful in intraspecific delimitation in the field of insect chemotaxonomy. PMID:28859151

  8. Combination of solid phase extraction and dispersive liquid-liquid microextraction for separation/preconcentration of ultra trace amounts of uranium prior to its fiber optic-linear array spectrophotometry determination.

    Science.gov (United States)

    Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji; Shakerian, Farid; Shiralian Esfahani, Golnaz

    2013-12-15

    A simple and sensitive method for the separation and preconcentration of the ultra trace amounts of uranium and its determination by spectrophotometry was developed. The method is based on the combination of solid phase extraction and dispersive liquid-liquid microextraction. Thus, by passing the sample through the basic alumina column, the uranyl ion and some cations are separated from the sample matrix. The retained uranyl ion along with the cations are eluted with 5 mL of nitric acid (2 mol L(-1)) and after neutralization of the eluent, the extracted uranyl ion is converted to its anionic benzoate complex and is separated from other cations by extraction of its ion pair with malachite green into small volume of chloroform using dispersive liquid-liquid microextraction. The amount of uranium is then determined by the absorption measurement of the extracted ion pair at 621 nm using flow injection spectrophotometry. Under the optimum conditions, with 500 mL of the sample, a preconcentration factor of 1980, a detection limit of 40 ng L(-1), and a relative standard deviation of 4.1% (n=6) at 400 ng L(-1) were obtained. The method was successfully applied to the determination of uranium in mineral water, river water, well water, spring water and sea water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Solid phase microextraction: measurement of volatile organic compounds (VOCs) in Dhaka City air pollution.

    Science.gov (United States)

    Hussam, A; Alauddin, M; Khan, A H; Chowdhury, D; Bibi, H; Bhattacharjee, M; Sultana, S

    2002-08-01

    A solid phase microextraction (SPME) technique was applied for the sampling of volatile organic compounds (VOCs) in ambient air polluted by two stroke autorickshaw engines and automobile exhausts in Dhaka city, Bangladesh. Analysis was carried out by capillary gas chromatography (GC) and GC-mass spectrometry (MS). The methodology was tested by insitu sampling of an aromatic hydrocarbon mixture gas standard with a precision of +/-5% and an average accuracy of 1-20%. The accuracy for total VOCs concentration measurement was about 7%. VOC's in ambient air were collected by exposing the SPME fiber at four locations in Dhaka city. The chromatograms showed signature similar to that of unburned gasoline (petrol) and weathered diesel containing more than 200 organic compounds; some of these compounds were positively identified. These are normal hydrocarbons pentane (n-C5H2) through nonacosane (n-C29H60), aromatic hydrocarbons: benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, 1,3,5-trimethylbenzene, xylenes, and 1-isocyanato-3-methoxybenzene. Two samples collected near an autorickshaw station contained 783000 and 1479000 microg/m3 of VOCs. In particular, the concentration of toluene was 50-100 times higher than the threshold limiting value of 2000 microg/m3. Two other samples collected on street median showed 135000 microg/m3 and 180000 microg/m3 of total VOCs. The method detection limit of the technique for most semi-volatile organic compounds was 1 microg/m3.

  10. Analysis of lignocellulose derived phenolic monomers by headspace solid-phase microextraction and gas chromatography.

    Science.gov (United States)

    Kolb, Michaela; Schieder, Doris; Faulstich, Martin; Sieber, Volker

    2013-09-13

    A headspace solid-phase microextraction method with subsequent GC-MS (HS-SPME/GC-MS) was established for the quantitative analysis of volatile lignin derived phenolic monomers in complex aqueous solutions. Extraction was done using a polyacrylate fiber. The optimization of HS-SPME - parameters was performed using a multi component model solution of six representative phenolic monomers identified in liquid hot water (LHW) supernatants of hydrothermally treated lignocellulosic biomass: p-coumaric acid, guaiacol, vanillin, acetosyringone, 4-hydroxy-3-methoxyphenylacetone, and acetophenone. Plackett-Burman design was applied for pre-evaluation and 2(3) central composite designs with star points for parameter optimization. LOQ (S/N>10) and LOD (S/N>3) were determined for 12 phenols yielding LOQ of <0.005-618nM and LOD of <0.005-412nM. Within-day and between-day tests (n=6) showed different results for the tested phenols. RSD ranged from 2% to 30% and recovery rates from 99% to 160% in LHW matrix. Tests on storage of LHW supernatants for several weeks indicated a considerable influence of temperature on the stability of the solutions which may even have to be taken into account for auto sampler handling. All in all the method allows a fast and solvent free analysis requiring low sample volumes making it a powerful tool for screening or high-throughput analysis of aqueous solutions of lignin derived aromatics. Copyright © 2013. Published by Elsevier B.V.

  11. Application of solid-phase microextraction for determining phenylurea herbicides and their homologous anilines from vegetables.

    Science.gov (United States)

    Berrada, H; Font, G; Moltó, J C

    2004-07-09

    Residues of metobromuron, monolinuron and linuron herbicides and their aniline homologous were analyzed in carrots, onions and potatoes by solid-phase microextraction (SPME) performed with a polyacrylate fiber. A juice was obtained from food samples that were further diluted, and an aliquot was extracted after sodium chloride (14%) addition and pH control. At pH 4 only the phenylureas were extracted. A new extraction at pH 11 allowed the extraction of phenylureas plus homologous aniline metabolites. Determination was carried out by gas chromatography with nitrogen-phosporus detection (NPD) the identity of the determined compounds was studied by gas chromatography-mass spectrometry. Limits of quantification (LOQs) obtained with NPD and MS (selected-ion monitoring) were in the microg/kg order allowing determination of maximum residue levels (MRLs) established in the Spanish regulations. MRLs ranged from 0.02 to 0.1 mg/kg depending on the kind of food and herbicide. Under the proposed conditions matrix effects were low enough to permit calibration with samples proceeding from ecological (non-pesticide treated) crops. Twelve commercial samples of each carrots, onions and potatoes were analyzed and only three samples of potatoes contained residues of linuron at levels below MRLs.

  12. Study of complex matrix effect on solid phase microextraction for biological sample analysis.

    Science.gov (United States)

    Jiang, Ruifen; Xu, Jianqiao; Zhu, Fang; Luan, Tiangang; Zeng, Feng; Shen, Yong; Ouyang, Gangfeng

    2015-09-11

    Solid phase microextraction (SPME) has become a useful tool for in vivo monitoring the behavior of environmental organic pollutants in biological species due to its simplicity, relatively non-invasive, and cost-effective manner. However, the complex matrices in biological samples could significantly influence the extraction kinetic, and bias the quantification result. In this study, we investigated the effect of complex matrix on the extraction kinetic of SPME for biological sample analysis. Two sample matrices, phosphate-buffered saline (PBS) with bovine serum albumin (BSA) and agarose gel with BSA were used to simulate the biological fluid and tissue. Results showed that the addition of BSA significantly enhanced the mass transfer of organic compounds onto SPME fiber in both PBS buffer and gel sample. Enhancement factors ranging from 1.3 to 27, and 2.0 to 80 were found for all selected polyaromatic hydrocarbons (PAHs) in PBS buffer and agarose gel with BSA concentration of 0.1-5%, respectively. Then, an improved theoretical model was applied to quantify the observed enhancement effect, and the result showed that the predicted sampling time constant agreed well with the experimental one in complex matrix. Furthermore, a simplified equation was proposed for the real biological sample analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Determining octanol-water partition coefficients for extremely hydrophobic chemicals by combining "slow stirring" and solid-phase microextraction.

    Science.gov (United States)

    Jonker, Michiel T O

    2016-06-01

    Octanol-water partition coefficients (KOW ) are widely used in fate and effects modeling of chemicals. Still, high-quality experimental KOW data are scarce, in particular for very hydrophobic chemicals. This hampers reliable assessments of several fate and effect parameters and the development and validation of new models. One reason for the limited availability of experimental values may relate to the challenging nature of KOW measurements. In the present study, KOW values for 13 polycyclic aromatic hydrocarbons were determined with the gold standard "slow-stirring" method (log KOW 4.6-7.2). These values were then used as reference data for the development of an alternative method for measuring KOW . This approach combined slow stirring and equilibrium sampling of the extremely low aqueous concentrations with polydimethylsiloxane-coated solid-phase microextraction fibers, applying experimentally determined fiber-water partition coefficients. It resulted in KOW values matching the slow-stirring data very well. Therefore, the method was subsequently applied to a series of 17 moderately to extremely hydrophobic petrochemical compounds. The obtained KOW values spanned almost 6 orders of magnitude, with the highest value measuring 10(10.6) . The present study demonstrates that the hydrophobicity domain within which experimental KOW measurements are possible can be extended with the help of solid-phase microextraction and that experimentally determined KOW values can exceed the proposed upper limit of 10(9) . Environ Toxicol Chem 2016;35:1371-1377. © 2015 SETAC. © 2015 SETAC.

  14. Steam distillation-solid-phase microextraction for the detection of Ephedra sinica in herbal preparations.

    Science.gov (United States)

    Tellez, Mari R; Khan, Ikhlas A; Schaneberg, Brian T; Crockett, Sara L; Rimando, Agnes M; Kobaisy, Mozaina

    2004-01-30

    A new method involving concurrent solid-phase microextraction combined with continuous hydrodistillation of essential oil was developed. This new methodology allowed for the detection by GC-MS of very small amounts of a diagnostic peak for the authentication of Ephedra sinica, in a short period of time and using only small sample sizes. This diagnostic peak was identified as 4-vinylanisole, and elucidated from the chromatographic profile allowed for the identification of a sample as E. sinica among other species investigated in this study. To the best of our knowledge this is the first report on using continuous solid-phase microextraction coupled to hydrodistillation for the investigation of essential oil components, and the first report of 4-vinylanisole as a marker compound for E. sinica. A total of 46 collections representing 21 species of Ephedra were studied.

  15. Optimization of the solid-phase microextraction method in the determination of Ixodes ricinus (L.) volatiles

    Czech Academy of Sciences Publication Activity Database

    Zahradníčková, Helena; Bouman, Edwin Arien Poul

    2006-01-01

    Roč. 29, č. 2 (2006), s. 236-241 ISSN 1615-9306 R&D Projects: GA ČR(CZ) GA206/04/0751 Institutional research plan: CEZ:AV0Z50070508; CEZ:AV0Z60220518 Keywords : GC/MS * Ixodes ricinus * solid-phase microextraction Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.535, year: 2006

  16. Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry.

    Science.gov (United States)

    Spietelun, Agata; Marcinkowski, Łukasz; de la Guardia, Miguel; Namieśnik, Jacek

    2013-12-20

    Solid phase microextraction find increasing applications in the sample preparation step before chromatographic determination of analytes in samples with a complex composition. These techniques allow for integrating several operations, such as sample collection, extraction, analyte enrichment above the detection limit of a given measuring instrument and the isolation of analytes from sample matrix. In this work the information about novel methodological and instrumental solutions in relation to different variants of solid phase extraction techniques, solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE) and magnetic solid phase extraction (MSPE) is presented, including practical applications of these techniques and a critical discussion about their advantages and disadvantages. The proposed solutions fulfill the requirements resulting from the concept of sustainable development, and specifically from the implementation of green chemistry principles in analytical laboratories. Therefore, particular attention was paid to the description of possible uses of novel, selective stationary phases in extraction techniques, inter alia, polymeric ionic liquids, carbon nanotubes, and silica- and carbon-based sorbents. The methodological solutions, together with properly matched sampling devices for collecting analytes from samples with varying matrix composition, enable us to reduce the number of errors during the sample preparation prior to chromatographic analysis as well as to limit the negative impact of this analytical step on the natural environment and the health of laboratory employees. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Analysis of tetramethylene disulfotetramine in foods using solid-phase microextraction-gas chromatography-mass spectrometry.

    Science.gov (United States)

    De Jager, Lowri S; Perfetti, Gracia A; Diachenko, Gregory W

    2008-05-23

    An automated solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method for the determination of tetramethylene disulfotetramine in foods was developed. A comparison of direct immersion (DI) and headspace (HS) extraction techniques using a 70microm carbowax/divinylbenzene (CW/DVB) fiber is presented. The optimized DI-SPME method provided an aqueous extraction limit of detection (LOD) of 9.0ng/g while the HS-SPME LOD was 2.7ng/g. In both SPME modes, recovery was highly matrix dependent and quantification requires standard addition calibrations. Analysis of foods using DI-SPME encountered many obstacles including fiber fouling, low recovery and poor reproducibility. HS-SPME was successfully applied to food analysis with minimal interferences. Standard addition calibration curves for foods gave high linearity (R2>0.98), reproducibility (RSD<12%) and sensitivity with LODs ranging from 0.9 to 4.3ng/g.

  18. Rapid analysis of malathion in blood using head space-solid phase microextraction and selected ion monitoring.

    Science.gov (United States)

    Namera, A; Yashiki, M; Nagasawa, N; Iwasaki, Y; Kojima, T

    1997-08-04

    A simple and rapid method for analysis of malathion in blood was developed using head space-solid phase microextraction (HS-SPME) and gas chromatography mass spectrometry/ electron impact ionization-selected ion monitoring (GC-MS/EI-SIM). A vial containing a blood sample, ammonium sulphate, sulphuric acid and fenitrothion as an internal standard, was heated at 90 degrees C for 15 min. The extraction fiber of the SPME was exposed for 5 min in the head space of the vial. The compounds absorbed on the fiber were detached by exposing the fibre in the injection port of GC-MS. A straight calibration curve was obtained between malathion concentrations of 2.5 to 50.0 micrograms g-1 in blood. No interfering substances were found, and the time for analysis was 40 min for one sample.

  19. Ordered mesoporous carbon film as an effective solid-phase microextraction coating for determination of benzene series from aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Hui [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); School of Geography Science, Nantong University, Nantong 226001 (China); Li, Jiansheng, E-mail: lijsh@mail.njust.edu.cn [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Jiang, Mingyue; Lu, Rui; Shen, Jinyou; Sun, Xiuyun; Han, Weiqing [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Wang, Lianjun, E-mail: wanglj@mail.njust.edu.cn [Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China)

    2015-08-12

    The present work reports preparation of ordered mesoporous carbon (OMC) film supported on a graphite fiber as a new type of solid-phase microextraction (SPME) fiber for determination of benzene series from aqueous media. The strategy for the supported OMC film preparation was combined dip-coating technology with solvent evaporation-induced self-assembly (EISA) approach. A graphite fiber was immersed in an ethanol solution containing phenolic resin and Pluronic triblock copolymer. Upon solvent evaporation and subsequent pyrolysis under 700 °C, the phenolic resin and the surfactant self-assembled on the surface of the graphite fiber to form smooth OMC film. X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen isothermal adsorption results indicate that the resultant OMC film possesses well-ordered two dimensional hexagonal mesostructure with pore diameters of 4.5 nm and BET surfaces of 630 m{sup 2}/g. Scanning electron microscopy (SEM) studies show the supported OMC film with thickness at 8.5 μm is continuous and defect-free. The SPME efficiency of the OMC fiber was evaluated by analysis of five benzene series (benzene, toluene, ethylbenzene, p-xylene and m-xylene) from water samples by gas chromatography-flame ionization detection (GC-FID). The analysis results indicate that the prepared OMC fiber has wide linear ranges (0.5–500 μg/L), low detection limits (0.01–0.05 μg/L) and good repeatabilities (4.0–5.8% for one fiber, 2.9–8.7% for fiber-to-fiber). Compared with commercial counterparts, the OMC fiber exhibits improved extraction efficiency for benzene series and PAHs. - Highlights: • Ordered mesoporous carbon film supported on graphite fiber was first reported as solid-phase microextraction coating. • The strategy for the film preparation was combined dip-coating technology with evaporation-induced self-assembly approach. • The obtained fiber showed enhanced thermal stability and organic solvents resistance. • The

  20. Recent Developments and Applications of Solid Phase Microextraction (SPME in Food and Environmental Analysis—A Review

    Directory of Open Access Journals (Sweden)

    Sybille Merkle

    2015-06-01

    Full Text Available Solid-phase microextraction (SPME is a simple, sensitive, rapid and solvent-free technique for the extraction of analytes from gaseous, liquid and solid samples and takes a leading position among microextraction methods. Application of SPME in sample preparation has been increasing continuously over the last decade. It is most often used as an automatized fiber injection system coupled to chromatographic separation modules for the extraction of volatile and semivolatile organic compounds and also allows for the trace analysis of compounds in complex matrices. Since SPME was first introduced in the early 1990s, several modifications have been made to adapt the procedure to specific application requirements. More robust fiber assemblies and coatings with higher extraction efficiencies, selectivity and stability have been commercialized. Automation and on-line coupling to analytical instruments have been achieved in many applications and new derivatization strategies as well as improved calibration procedures have been developed to overcome existing limitations regarding quantitation. Furthermore, devices using tubes, needles or tips for extraction instead of a fiber have been designed. In the field of food analysis, SPME has been most often applied to fruit/vegetables, fats/oils, wine, meat products, dairy and beverages whereas environmental applications focus on the analysis of air, water, soil and sediment samples.

  1. Determination of parathion in biological fluids by means of direct Solid Phase Microextraction.

    OpenAIRE

    Gallardo, Eugenia; Barroso, Mário; Margalho, C.; Cruz, Angelines; Vieira, Duarte Nuno; López-Rivadulla, Manuel

    2010-01-01

    A new and simple procedure for the determination of parathion in human whole blood and urine using direct immersion (DI) solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) is presented. This technique was developed using only 100 ìL of sample, and ethion was used as internal standard (IS). A 65-ìm Carbowax/divinylbenzene (CW/DVB) SPME fibre was selected for sampling, and the main parameters affecting the SPME process such as extraction ...

  2. Identification of Flavor Components in Perfumes by Headspace Solid-Phase Microextraction and Gas Chromatography-Mass Spectrometry

    Science.gov (United States)

    Knupp, Gerd; Kusch, Peter; Neugebauer, Michael

    2002-01-01

    An experiment for identification of flavor components in Original Eau de Cologne by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS) with electron impact ionization was developed. A new SPME fiber with a dual coating of divinylbenzene and Carboxen, each suspended in polydimethylsiloxane, was used. The compounds were identified by search of the NIST 98 MS Library or by comparison with pure standards. The experiment was developed for second-year chemistry students to learn the principles of analytical instrumentation (GC-MS) and sample preparation techniques (HS-SPME). The students are able to complete this experiment in a single four-hour laboratory session.

  3. Headspace-solid-phase microextraction in the analysis of the volatile fraction of aromatic and medicinal plants.

    Science.gov (United States)

    Belliardo, Flavio; Bicchi, Carlo; Cordero, Chiara; Liberto, Erica; Rubiolo, Patrizia; Sgorbini, Barbara

    2006-08-01

    Headspace (HS)-solid-phase microextraction (SPME) has assumed an ever increasing importance as a technique for HS sampling to study the composition of the HS of medicinal and aromatic plants. HS-SPME has mainly been applied for (a) studying the composition of the volatile fraction, including in addition to or as an alternative to other sampling techniques; (b) monitoring the biological phenomena involved with the volatile fraction of a plant; (c) discriminating between species, subspecies, varieties, cultivars, or chemotypes; and (d) quality control of plant samples. A review of 108 articles published during 2000-2005 is presented covering the use of HS-SPME in the field of aromatic and medicinal plants, selection of the most effective fiber and sampling conditions, comparison of HS-SPME and other volatile fraction sample preparation techniques, and the advantages and limits of HS-SPME when applied to medicinal and aromatic plants.

  4. Determination of 2,5-hexanedione in urine by headspace solid-phase microextraction and gas chromatography.

    Science.gov (United States)

    Oliveira, Antônio Felipe F; Maia, Patrícia P; Paiva, Maria José N; Siqueira, Maria Elisa P B

    2009-05-01

    2,5-Hexanedione (2,5-HD) is the most important metabolite of n-hexane and methyl ethyl ketone in human urine. Urinary 2,5-HD is used as a biomarker for biological monitoring of workers exposed to n-hexane. A simple method using headspace solid-phase microextraction (HS-SPME) and gas chromatography (GC) equipped with a flame-ionization detector (FID) was developed. The parameters that affect the HS-SPME-GC-FID process were optimized (i.e., fiber coating, sample volume, adsorption and heating time, salt addition, and extraction temperature). The assay presented linearity in the range of 0.075 to 20.0 mg/L, precision (coefficient of variation L for 2,5-HD in urine. The method was successfully applied to the analysis of 2,5-HD in urine samples from eight workers occupationally exposed to n-hexane in shoemaker's glue.

  5. Field measurements of biogenic volatile organic compounds in the atmosphere using solid-phase microextraction Arrow

    Science.gov (United States)

    Feijó Barreira, Luís Miguel; Duporté, Geoffroy; Rönkkö, Tuukka; Parshintsev, Jevgeni; Hartonen, Kari; Hyrsky, Lydia; Heikkinen, Enna; Jussila, Matti; Kulmala, Markku; Riekkola, Marja-Liisa

    2018-02-01

    Biogenic volatile organic compounds (BVOCs) emitted by terrestrial vegetation participate in a diversity of natural processes. These compounds impact both short-range processes, such as on plant protection and communication, and long-range processes, for example by participating in aerosol particle formation and growth. The biodiversity of plant species around the Earth, the vast assortment of emitted BVOCs, and their trace atmospheric concentrations contribute to the substantial remaining uncertainties about the effects of these compounds on atmospheric chemistry and physics, and call for the development of novel collection devices that can offer portability with improved selectivity and capacity. In this study, a novel solid-phase microextraction (SPME) Arrow sampling system was used for the static and dynamic collection of BVOCs from a boreal forest, and samples were subsequently analyzed on site by gas chromatography-mass spectrometry (GC-MS). This system offers higher sampling capacity and improved robustness when compared to traditional equilibrium-based SPME techniques, such as SPME fibers. Field measurements were performed in summer 2017 at the Station for Measuring Ecosystem-Atmosphere Relations (SMEAR II) in Hyytiälä, Finland. Complementary laboratory tests were also performed to compare the SPME-based techniques under controlled experimental conditions and to evaluate the effect of temperature and relative humidity on their extraction performance. The most abundant monoterpenes and aldehydes were successfully collected. A significant improvement on sampling capacity was observed with the new SPME Arrow system over SPME fibers, with collected amounts being approximately 2 × higher for monoterpenes and 7-8 × higher for aldehydes. BVOC species exhibited different affinities for the type of sorbent materials used (polydimethylsiloxane (PDMS)-carbon wide range (WR) vs. PDMS-divinylbenzene (DVB)). Higher extraction efficiencies were obtained with dynamic

  6. Silicon carbide nanomaterial as a coating for solid-phase microextraction.

    Science.gov (United States)

    Tian, Yu; Feng, Juanjuan; Wang, Xiuqin; Sun, Min; Luo, Chuannan

    2018-01-26

    Silicon carbide has excellent properties, such as corrosion resistance, high strength, oxidation resistance, high temperature, and so on. Based on these properties, silicon carbide was coated on stainless-steel wire and used as a solid-phase microextraction coating, and polycyclic aromatic hydrocarbons were employed as model analytes. Using gas chromatography, some important factors that affect the extraction efficiency were optimized one by one, and an analytical method was established. The analytical method showed wide linear ranges (0.1-30, 0.03-30, and 0.01-30 μg/L) with satisfactory correlation coefficients (0.9922-0.9966) and low detection limits (0.003-0.03 μg/L). To investigate the practical application of the method, rainwater and cigarette ash aqueous solution were collected as real samples for extraction and detection. The results indicate that silicon carbide has excellent application in the field of solid-phase microextraction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Quantification of synthetic organic chemicals in biological treatment process effluent using solid-phase microextraction and gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Magbanua, B.S. Jr.; Mitchell, D.R.; Fehniger, S.M.; Bowyer, R.L.; Grady, C.P.L. Jr.

    2000-02-01

    Solid-phase microextraction (SPME), a technique that uses a polymer-coated, fused-silica fiber to selectively extract organic analyses from a sample matrix, followed by gas chromatography (GC), was used to quantify selected synthetic organic chemicals (SOCs) in biological reactor effluent. By selecting an appropriate combination of SPME fiber, GC column, and GC detector, assays to quantify either a suite of SOCs or single selected SOCs were developed. Phenol, 4-chlorophenol, 2-nitrophenol, 4-nitrophenol, 2,4,-dinitrophenol, isophorone, m-toluate, m-sylene, and di-n-butylphthalate were quantified simultaneously using an 85-{micro}m polyacrylate SPME fiber, a 5% diphenyl-95% dimethyl polysiloxane capillary column, and a flame ionization detector. m-Xylene was quantified using a 100-{micro}m polydimethylsiloxane SPME fiber, a 5% diphenyl-95% dimethyl polysiloxane capillary column, and a mass spectrometric detector. Dichloromethane was quantified using an 85-{micro}m polyacrylate SPME fiber, a Carbopack B/1% SP-1000 packed column, and an electron capture detector. All three assays enabled detection of the target analyses to low concentrations ({micro}g/L) with minimal sample volume and processing requirements.

  8. SOLID PHASE MICROEXTRACTION SAMPLING OF HIGH EXPLOSIVE RESIDUES IN THE PRESENCE OF RADIONUCLIDES AND RADIONUCLIDE SURROGATE METALS

    Energy Technology Data Exchange (ETDEWEB)

    Duff, M; S Crump, S; Robert02 Ray, R; Donna Beals, D

    2007-04-13

    The Federal Bureau of Investigation (FBI) Laboratory currently does not have on site facilities for handling radioactive evidentiary materials and there are no established FBI methods or procedures for decontaminating high explosive (HE) evidence while maintaining evidentiary value. One experimental method for the isolation of HE residue involves using solid phase microextraction or SPME fibers to remove residue of interest. Due to their high affinity for organics, SPME fibers should have little affinity for most metals. However, no studies have measured the affinity of radionuclides for SPME fibers. The focus of this research was to examine the affinity of dissolved radionuclide ({sup 239/240}Pu, {sup 238}U, {sup 237}Np, {sup 85}Sr, {sup 133}Ba, {sup 137}Cs, {sup 60}Co and {sup 226}Ra) and stable radionuclide surrogate metals (Sr, Co, Ir, Re, Ni, Ba, Cs, Nb, Zr, Ru, and Nd) for SPME fibers at the exposure conditions that favor the uptake of HE residues. Our results from radiochemical and mass spectrometric analyses indicate these metals have little measurable affinity for these SPME fibers during conditions that are conducive to HE residue uptake with subsequent analysis by liquid or gas phase chromatography with mass spectrometric detection.

  9. Ordered mesoporous carbon film as an effective solid-phase microextraction coating for determination of benzene series from aqueous media.

    Science.gov (United States)

    Jiang, Hui; Li, Jiansheng; Jiang, Mingyue; Lu, Rui; Shen, Jinyou; Sun, Xiuyun; Han, Weiqing; Wang, Lianjun

    2015-08-12

    The present work reports preparation of ordered mesoporous carbon (OMC) film supported on a graphite fiber as a new type of solid-phase microextraction (SPME) fiber for determination of benzene series from aqueous media. The strategy for the supported OMC film preparation was combined dip-coating technology with solvent evaporation-induced self-assembly (EISA) approach. A graphite fiber was immersed in an ethanol solution containing phenolic resin and Pluronic triblock copolymer. Upon solvent evaporation and subsequent pyrolysis under 700 °C, the phenolic resin and the surfactant self-assembled on the surface of the graphite fiber to form smooth OMC film. X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen isothermal adsorption results indicate that the resultant OMC film possesses well-ordered two dimensional hexagonal mesostructure with pore diameters of 4.5 nm and BET surfaces of 630 m(2)/g. Scanning electron microscopy (SEM) studies show the supported OMC film with thickness at 8.5 μm is continuous and defect-free. The SPME efficiency of the OMC fiber was evaluated by analysis of five benzene series (benzene, toluene, ethylbenzene, p-xylene and m-xylene) from water samples by gas chromatography-flame ionization detection (GC-FID). The analysis results indicate that the prepared OMC fiber has wide linear ranges (0.5-500 μg/L), low detection limits (0.01-0.05 μg/L) and good repeatabilities (4.0-5.8% for one fiber, 2.9-8.7% for fiber-to-fiber). Compared with commercial counterparts, the OMC fiber exhibits improved extraction efficiency for benzene series and PAHs. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Determination of multi-class herbicides in soil by liquid-solid extraction coupled with headspace solid phase microextraction method

    Directory of Open Access Journals (Sweden)

    Đurović-Pejčev Rada

    2016-01-01

    Full Text Available A method is described for simultaneous determination of five herbicides (metribuzin, acetochlor, clomazone, oxyfluorfen and dimethenamid belonging to different pesticides groups in soil samples. Developed headspace solid phase microextraction method (HS-SPME in combination with liquid-solid sample preparation (LS was optimized and applied in the analysis of some agricultural samples. Optimization of microextraction conditions, such as temperature, extraction time and sodium chloride (NaCl content was perfor-med using 100 μm polydimethyl-siloxane (PDMS fiber. The extraction effi-ciencies of methanol, methanol:acetone=1:1 and methanol:acetone:hexane= =2:2:1 and the optimum number of extraction steps during the sample prepa-ration, were tested, as well. Gas chromatography-mass spectrometry (GC-MS was used for detection and quantification, obtaining relative standard deviation (RSD below 13%, and recovery values higher than 83% for multiple analyses of soil samples fortified at 30 μg kg-1 of each herbicide. Limits of detection (LOD were less than 1.2 μg kg-1 for all the studied herbicides. [Projekat Ministarstva nauke Republike Srbije, br. TR31043 i br. III43005

  11. A strategy to enhance the thermal stability of a nanostructured polypyrrole-based coating for solid phase microextraction

    International Nuclear Information System (INIS)

    Mehdinia, A.; Bashour, F.; Roohi, F.; Jabbari, A.

    2012-01-01

    We report on a nanostructured self-doped polypyrrole (SPPy) film that was prepared by an electrochemical technique in an electrolyte containing fluorosulfonic acid as the sulfonation reagent. The film was applied as a new fiber material for solid-phase microextraction (SPME) of the pesticides lindane, heptachlor, aldrin, endosulfans I and II prior to their quantitation by GC with electron capture detection. The SPPy nanoparticles have a diameter of 0 C) and satisfactory extraction efficiency. The thermal stability of the SPPy fiber is superior to common polypyrrole fibers. Extraction was optimized by means of the Taguchi orthogonal array experimental design with an OA 16 (4 5 ) matrix including extraction temperature, extraction time, salt concentration, stirring rate, and headspace volume. The method displays good repeatability (RSD -1 ; with an R 2 of >0. 998. The detection limits are -1 . The method was successfully applied to the analysis of the pesticides in skimmed milk and fruit juice samples, and recoveries are from 84 ± 1 to 105 ± 1%. (author)

  12. Improving the Sensitivity of Solid-Phase Microextraction by Reducing the Volume of Off-Line Elution Solvent.

    Science.gov (United States)

    Xu, Jianqiao; Liu, Xiwen; Wang, Qi; Huang, Shuyao; Yin, Li; Xu, Jing; Liu, Xianguo; Jiang, Ruifen; Zhu, Fang; Ouyang, Gangfeng

    2018-02-06

    Solid-phase microextraction (SPME) coupled with liquid chromatograph (LC) is widely used to detect polar and ionic organic compounds, including various pharmaceuticals and endogenous bioactive compounds. In this study, a small-sized insert tube for use in the commercial autosampler vial was designed for eluting the extracted analytes from SPME fibers for LC analysis. By using this custom-made insert tube as an alternative to the commercial insert tube, the volume of the elution solvent was reduced by four-fifths. Even though smaller fractions of the analytes were eluted from the fiber coatings, the analyte concentrations in the elution solutions were substantially increased by using the custom-made insert tube. Therefore, larger amounts of the analytes could be injected to LC and higher signal-to-noise ratios could be achieved, even at smaller injection volumes. Since the elution in the custom-made insert tube was nonexhaustive, four strategies were developed to figure out the extracted amounts in the fiber coatings. In combination with the sampling-rate calibration method, these strategies were successfully used to determine the concentrations of fluoxetine in living tilapias. This study provides a simple but effect way for improving the analytical sensitivity when coupling SPME with LC.

  13. Rapid Determination of Clenbuterol in Pork by Direct Immersion Solid-Phase Microextraction Coupled with Gas Chromatography-Mass Spectrometry.

    Science.gov (United States)

    Ye, Diru; Wu, Susu; Xu, Jianqiao; Jiang, Ruifen; Zhu, Fang; Ouyang, Gangfeng

    2016-02-01

    Direct immersion solid-phase microextraction (DI-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was developed for rapid analysis of clenbuterol in pork for the first time. In this work, a low-cost homemade 44 µm polydimethylsiloxane (PDMS) SPME fiber was employed to extract clenbuterol in pork. After extraction, derivatization was performed by suspending the fiber in the headspace of the 2 mL sample vial saturated with a vapor of 100 µL hexamethyldisilazane. Lastly, the fiber was directly introduced to GC-MS for analysis. All parameters that influenced absorption (extraction time), derivatization (derivatization reagent, time and temperature) and desorption (desorption time) were optimized. Under optimized conditions, the method offered a wide linear range (10-1000 ng g(-1)) and a low detection limit (3.6 ng g(-1)). Finally, the method was successfully applied in the analysis of pork from the market, and recoveries of the method for spiked pork were 97.4-105.7%. Compared with the traditional solvent extraction method, the proposed method was much cheaper and fast. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  14. Hydrophobic coating of polyaniline-poly(propylene oxide) copolymer for direct immersion solid phase microextraction of carbamate pesticides.

    Science.gov (United States)

    Ai, Youhong; Zhang, Jingqiang; Zhao, Faqiong; Zeng, Baizhao

    2015-08-14

    A nanostructural polyaniline-poly(propylene oxide) (PANI-PPO) composite coating was electrochemically synthesized on a stainless steel wire, by using acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate as supporting electrolyte. The coating showed strong hydrophobicity and allowed for the direct immersion solid-phase microextraction of carbamate pesticides (i.e. 2-(1-methylethoxy) phenyl methylcarbamate, m-tolyl-n-methylcarbamate, 2-(1-methylethyl) phenyl methylcarbamate, 2-(1-methylpropyl) phenol methylcarbamate and 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate) in complex matrices. Moreover, this coating could be used for at least 120 times of extraction. When it was coupled with gas chromatography for the determination of these carbamate pesticides the linear ranges were about 0.1-100 μg L(-1) and the detection limits were 0.012-0.048 μg L(-1). It also displayed acceptable repeatability and reproducibility. When a fiber was used for five successive measurements the relative standard deviations (RSDs) were smaller than 8.7%, and the RSDs for fiber-to-fiber were 5.7-12.9% (n=5). The practical feasibility of the proposed method was evaluated by determining carbamate pesticides in vegetable samples and the recoveries for standards added were 79.8-108.8%. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Rapid determination of volatile organic compounds in environmentally hazardous wastewaters using solid phase microextraction

    Energy Technology Data Exchange (ETDEWEB)

    James, K.J.; Stack, M.A. [Ecotoxicology Research Unit, Chemistry Department, Cork RTC, Bishopstown, Cork (Ireland)

    1997-08-01

    Solid phase micro-extraction (SPME) was applied to the determination of volatile organic compounds (VOC) in wastewater discharges. Environmentally significant samples, typical of those subject to regulatory control, were examined and included discharges from pharmaceutical, petrochemical and municipal sewerage treatment plants. Analysis was performed using gas chromatography - mass spectrometry (GC-MS) following sampling using headspace or immersion SPME. Fused silica fibres, coated with either poly(dimethylsiloxane) or poly(acrylate), were examined to determine VOC which included chloroform, saturated carboxylic acids, alkylbenzenes, phenol, benzonitrile and benzofuran. Detection limits varied from 10 to 170 ng/ml and satisfactory relative standard deviations (%RSD < 10) were obtained. For most samples, headspace sampling was preferred to immersion. SPME was found to be a useful technique for the rapid screening of wastewaters for VOC. (orig.) With 2 figs., 3 tabs.

  16. Headspace solid-phase microextraction procedures for gas chromatographic analysis of biological fluids and materials.

    Science.gov (United States)

    Mills, G A; Walker, V

    2000-12-01

    Solid-phase microextraction (SPME) is a new solventless sample preparation technique that is finding wide usage. This review provides updated information on headspace SPME with gas chromatographic separation for the extraction and measurement of volatile and semivolatile analytes in biological fluids and materials. Firstly the background to the technique is given in terms of apparatus, fibres used, extraction conditions and derivatisation procedures. Then the different matrices, urine, blood, faeces, breast milk, hair, breath and saliva are considered separately. For each, methods appropriate for the analysis of drugs and metabolites, solvents and chemicals, anaesthetics, pesticides, organometallics and endogenous compounds are reviewed and the main experimental conditions outlined with specific examples. Then finally, the future potential of SPME for the analysis of biological samples in terms of the development of new devices and fibre chemistries and its coupling with high-performance liquid chromatography is discussed.

  17. Direct solid-phase microextraction combined with gas and liquid chromatography for the determination of lidocaine in human urine

    NARCIS (Netherlands)

    Koster, E.H M; Hofman, N.S K; de Jong, G.J.

    Solid-phase microextraction (SPME) has been combined with gas chromatography (GC) and liquid chromatography (LC) for the determination of lidocaine in human urine. A polydimethylsiloxane (PDMS) coated fibre was directly immersed into buffered urine. Extraction conditions such as time, pH, ionic

  18. Application of head-space solid-phase microextraction for the analysis of volatile metabolites emitted by Penicillium species

    DEFF Research Database (Denmark)

    Nilsson, Torben; Larsen, Thomas Ostenfeld; Montanarella, Luca

    1996-01-01

    Head-space solid-phase microextraction (HS-SPME) has been used to collect volatile organic compounds (VOCs) emitted from fungi of the genus Penicillium. Gas chromatography combined with mass spectrometry (GC-MS) was employed for the analysis of the profiles of volatile metabolites characteristic ......-SPME has a great potential use in the analysis of biogenic VOC emissions, including chemotaxonomical studies....

  19. Sample preparation with solid phase microextraction and exhaustive extraction approaches: Comparison for challenging cases.

    Science.gov (United States)

    Boyacı, Ezel; Rodríguez-Lafuente, Ángel; Gorynski, Krzysztof; Mirnaghi, Fatemeh; Souza-Silva, Érica A; Hein, Dietmar; Pawliszyn, Janusz

    2015-05-11

    In chemical analysis, sample preparation is frequently considered the bottleneck of the entire analytical method. The success of the final method strongly depends on understanding the entire process of analysis of a particular type of analyte in a sample, namely: the physicochemical properties of the analytes (solubility, volatility, polarity etc.), the environmental conditions, and the matrix components of the sample. Various sample preparation strategies have been developed based on exhaustive or non-exhaustive extraction of analytes from matrices. Undoubtedly, amongst all sample preparation approaches, liquid extraction, including liquid-liquid (LLE) and solid phase extraction (SPE), are the most well-known, widely used, and commonly accepted methods by many international organizations and accredited laboratories. Both methods are well documented and there are many well defined procedures, which make them, at first sight, the methods of choice. However, many challenging tasks, such as complex matrix applications, on-site and in vivo applications, and determination of matrix-bound and free concentrations of analytes, are not easily attainable with these classical approaches for sample preparation. In the last two decades, the introduction of solid phase microextraction (SPME) has brought significant progress in the sample preparation area by facilitating on-site and in vivo applications, time weighted average (TWA) and instantaneous concentration determinations. Recently introduced matrix compatible coatings for SPME facilitate direct extraction from complex matrices and fill the gap in direct sampling from challenging matrices. Following introduction of SPME, numerous other microextraction approaches evolved to address limitations of the above mentioned techniques. There is not a single method that can be considered as a universal solution for sample preparation. This review aims to show the main advantages and limitations of the above mentioned sample

  20. Multiple headspace-solid-phase microextraction: An application to quantification of mushroom volatiles

    International Nuclear Information System (INIS)

    Costa, Rosaria; Tedone, Laura; De Grazia, Selenia; Dugo, Paola; Mondello, Luigi

    2013-01-01

    Highlights: ► Multiple headspace extraction-solid phase microextraction (MHS-SPME) has been applied to the analysis of Agaricus bisporus. ► Mushroom flavor is characterized by the presence of compounds with a 8-carbon atoms skeleton. ► Formation of 8-carbon compounds involves a unique fungal biochemical pathway. ► The MHS-SPME allowed to determine quantitatively 5 target analytes of A. bisporus for the first time. -- Abstract: Multiple headspace-solid phase microextraction (MHS-SPME) followed by gas chromatography/mass spectrometry (GC–MS) and flame ionization detection (GC–FID) was applied to the identification and quantification of volatiles released by the mushroom Agaricus bisporus, also known as champignon. MHS-SPME allows to perform quantitative analysis of volatiles from solid matrices, free of matrix interferences. Samples analyzed were fresh mushrooms (chopped and homogenized) and mushroom-containing food dressings. 1-Octen-3-ol, 3-octanol, 3-octanone, 1-octen-3-one and benzaldehyde were common constituents of the samples analyzed. Method performance has been tested through the evaluation of limit of detection (LoD, range 0.033–0.078 ng), limit of quantification (LoQ, range 0.111–0.259 ng) and analyte recovery (92.3–108.5%). The results obtained showed quantitative differences among the samples, which can be attributed to critical factors, such as the degree of cell damage upon sample preparation, that are here discussed. Considerations on the mushrooms biochemistry and on the basic principles of MHS analysis are also presented

  1. Multiple headspace-solid-phase microextraction: An application to quantification of mushroom volatiles

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Rosaria; Tedone, Laura; De Grazia, Selenia [Dipartimento Farmaco-chimico, University of Messina, viale Annunziata, 98168 Messina (Italy); Dugo, Paola [Dipartimento Farmaco-chimico, University of Messina, viale Annunziata, 98168 Messina (Italy); Centro Integrato di Ricerca (C.I.R.), Università Campus-Biomedico, Via Álvaro del Portillo, 21, 00128 Roma (Italy); Mondello, Luigi, E-mail: lmondello@unime.it [Dipartimento Farmaco-chimico, University of Messina, viale Annunziata, 98168 Messina (Italy); Centro Integrato di Ricerca (C.I.R.), Università Campus-Biomedico, Via Álvaro del Portillo, 21, 00128 Roma (Italy)

    2013-04-03

    Highlights: ► Multiple headspace extraction-solid phase microextraction (MHS-SPME) has been applied to the analysis of Agaricus bisporus. ► Mushroom flavor is characterized by the presence of compounds with a 8-carbon atoms skeleton. ► Formation of 8-carbon compounds involves a unique fungal biochemical pathway. ► The MHS-SPME allowed to determine quantitatively 5 target analytes of A. bisporus for the first time. -- Abstract: Multiple headspace-solid phase microextraction (MHS-SPME) followed by gas chromatography/mass spectrometry (GC–MS) and flame ionization detection (GC–FID) was applied to the identification and quantification of volatiles released by the mushroom Agaricus bisporus, also known as champignon. MHS-SPME allows to perform quantitative analysis of volatiles from solid matrices, free of matrix interferences. Samples analyzed were fresh mushrooms (chopped and homogenized) and mushroom-containing food dressings. 1-Octen-3-ol, 3-octanol, 3-octanone, 1-octen-3-one and benzaldehyde were common constituents of the samples analyzed. Method performance has been tested through the evaluation of limit of detection (LoD, range 0.033–0.078 ng), limit of quantification (LoQ, range 0.111–0.259 ng) and analyte recovery (92.3–108.5%). The results obtained showed quantitative differences among the samples, which can be attributed to critical factors, such as the degree of cell damage upon sample preparation, that are here discussed. Considerations on the mushrooms biochemistry and on the basic principles of MHS analysis are also presented.

  2. Graphene-doped electrochemical copolymer coating of 2,2-bithiophene and 3-methylthiophene for the highly effective solid-phase microextraction of volatile benzene homologues.

    Science.gov (United States)

    Guo, Xiafei; Zhao, Faqiong; Zeng, Baizhao

    2018-02-13

    We report the electrochemical fabrication of a poly(2,2-bithiophene-co-3-methylthiophene)-graphene composite coating and its application in the headspace solid-phase microextraction and gas chromatography determination of benzenes (i.e., bromobenzene, 4-bromotoluene, 2-nitrotoluene, 3-nitrotoluene, 1,2,4-trichlorobenzene). The coating was uniform and showed cauliflower-like microstructure. It had high thermal stability (up to 375°C) and could be used for at least 180 times of solid-phase microextraction without a decrease of extraction performance. Furthermore, it presented high extraction capacity for the benzenes due to the hydrophobic effect and π-π interaction between the analytes and the coating. Under optimized extraction conditions, good linearity (correlation coefficients higher than 0.9946), wide linear range (0.01-50 μg L -1 ), low limits of detection (5.25-12.5 ng L -1 ) were achieved for these analytes. The relative standard deviation was lower than 5.7% for five successive measurements with one fiber, and the relative standard deviation for fiber-to-fiber was 4.9-6.8% (n = 5). The solid-phase microextraction and gas chromatography method was successfully applied for the determination of three real samples, and the recoveries for standards added were 89.6-106% for nail polish, 85.8-110% for hair dye and 90-106.2% for correction fluid, respectively. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  3. Improved detection limits for phthalates by selective solid-phase micro-extraction

    KAUST Repository

    Zia, Asif I.

    2016-03-30

    Presented research reports on an improved method and enhanced limits of detection for phthalates; a hazardous additive used in the production of plastics by solid-phase micro-extraction (SPME) polymer in comparison to molecularly imprinted solid-phase extraction (MISPE) polymer. The polymers were functionalized on an interdigital capacitive sensor for selective binding of phthalate molecules from a complex mixture of chemicals. Both polymers owned predetermined selectivity by formation of valuable molecular recognition sites for Bis (2-ethylhexyl) phthalate (DEHP). Polymers were immobilized on planar electrochemical sensor fabricated on a single crystal silicon substrate with 500 nm sputtered gold electrodes fabricated using MEMS fabrication techniques. Impedance spectra were obtained using electrochemical impedance spectroscopy (EIS) to determine sample conductance for evaluation of phthalate concentration in the spiked sample solutions with various phthalate concentrations. Experimental results revealed that the ability of SPME polymer to adsorb target molecules on the sensing surface is better than that of MISPE polymer for phthalates in the sensing system. Testing the extracted samples using high performance liquid chromatography with photodiode array detectors validated the results.

  4. Determination of Atrazine, Acetochlor, Clomazone, Pendimethalin and Oxyfluorfen in Soil by a Solid Phase Microextraction Method

    Directory of Open Access Journals (Sweden)

    Rada Đurović

    2008-01-01

    Full Text Available A solid phase microextraction (SPME method for simultaneous determination of atrazine, acetochlor, clomazone, pendimethalin and oxyfluorfen in soil samples was developed. The method is based on a combination of conventional liquid-solid procedure and a following SPME determination of the selected pesticides. Initially, various microextraction conditions, such as the fibre type, desorption temperature and time, extraction time and NaCl content, were investigated and optimized. Then, extraction efficiencies of severalsolvents (water, hexane, acetonitrile, acetone and methanol and the optimum number of extraction steps within the sample preparation step were optimized. According to the results obtained in these two sets of experiments, two successive extractions with methanol as the extraction solvent were the optimal sample preparation procedure, while the following conditions were found to be most efficient for SPME measurements: 100 μm PDMS fibre, desorption for 7 min at 2700C, 30 min extraction time and 5% NaCl content (w/v. Detection and quantification were done by gas chromatography-mass spectrometry(GC/MS. Relative standard deviation (RSD values for multiple analysis of soil samples fortified at 30 μg/kg of each pesticide were below 19%. Limits of detection (LOD for all the compounds studied were less than 2 μg/kg.

  5. Dynamic solid phase microextraction for sampling of airborne sarin with gas chromatography-mass spectrometry for rapid field detection and quantification.

    Science.gov (United States)

    Hook, Gary L; Jackson Lepage, Carmela; Miller, Stephen I; Smith, Philip A

    2004-08-01

    A portable dynamic air sampler and solid phase microextraction were used to simultaneously detect, identify, and quantify airborne sarin with immediate analysis of samples using a field portable gas chromatography-mass spectrometry system. A mathematical model was used with knowledge of the mass of sarin trapped, linear air velocity past the exposed sampling fiber, and sample duration allowing calculation of concentration estimates. For organizations with suitable field portable instrumentation, these methods are potentially useful for rapid onsite detection and quantification of high concern analytes, either through direct environmental sampling or through sampling of air collected in bags.

  6. Rapid detection of five anesthetics in tilapias by in vivo solid phase microextraction coupling with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Huang, Shuyao; Xu, Jianqiao; Wu, Jiayi; Hong, Haojia; Chen, Guosheng; Jiang, Ruifen; Zhu, Fang; Liu, Yuan; Ouyang, Gangfeng

    2017-06-01

    The concentration of five rapidly metabolized anesthetics in living tilapias was determined in this study, by the presented method coupling in vivo solid phase microextraction (SPME) to gas chromatography-mass spectrometry (GC-MS), which was the first time that in vivo sampling method was adapted in detecting the anesthetic residue in the living aquatic product. The analytical performance of the developed method was evaluated in homogenized tilapia dorsal muscle, and the results demonstrated that the present method possessed low detection limits 1.7-9.4ngg -1 ), wide linear ranges (10 or 30-5000ngg -1 ), and satisfactory reproducibility (relative standard deviations no more than 8.1% and 10.8% for inter-fiber and intra-fiber assays, respectively). Standard curves were established in homogenized tilapia dorsal muscle for calibrating in vivo SPME in living tilapias. And the concentrations determined by in vivo SPME were close to those determined by the liquid extraction. By using the present method, one anesthetic residue was detected above the detection limit in tilapias from the local markets. Comparing to traditional methods, the present one exhibited superior time-efficiency and cost performance, as the extraction time was only ten minutes, which was short to successfully avoid the possible loss of analytes caused by elimination and sample storage. In addition, owing to the time-efficiency of the present method, the elimination of the anesthetics in tilapias was traced successfully in the laboratory. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. [Determination of five synthetic musks in perfume by headspace solid-phase microextraction and gas chromatography-mass spectrometry].

    Science.gov (United States)

    Wang, Guannan; Tang, Hua; Chen, Dazhou; Feng, Jie; Li, Lei

    2012-02-01

    A method for headspace solid-phase microextraction (HS-SPME), followed by gas chromatography-mass spectrometry (GC-MS) analysis was established for the determination of five commonly used synthetic musks in perfume. Two polycyclic musks (celestolide and tonalide) and three nitro musks (musk ambrette, musk xylene and musk ketone) were used as analytes in the optimization of the analytical method. Six parameters, such as the extraction temperature, equilibrium time, extraction time, desorption time, injector temperature and solution of salting out, were optimized by exposing the 65 microm polydimethylsiloxane-divinyl-benzene (PDMS-DVB) fiber to the headspace of magnetically stirred (600 r/min) sample. According to the results of the optimization experiments, the following conclusion can be drawn: The water-diluted sample in a 10 mL headspace-vial was efficiently extracted for 20 min after the system was equilibrated for 3 min at 60 degrees C. After extraction, the fiber was immediately inserted into the GC injector and desorbed at 250 degrees C for 3 min. The spiked recoveries were in the range of 82.0% - 103.3% and the relative standard deviations (RSDs) were between 1.8% and 9.4%. Meanwhile, the limits of detection (LODs) ranged from 0.6 ng/g to 2.1 ng/g. This method is characterized by rapidity, high sensitivity, good linearity and repeatability for all the target compounds. It is applicable to the analysis of synthetic musks in perfumes.

  8. Microwave-assisted headspace solid-phase microextraction for the analysis of bioemissions from Eucalyptus citriodora leaves.

    Science.gov (United States)

    Xiong, Guohua; Goodridge, Carolyn; Wang, Limei; Chen, Yong; Pawliszyn, Janusz

    2003-12-31

    Microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) was developed as a simple and effective method for fast sampling of volatile organic compounds (VOCs) from Eucalyptus citriodora Hook (E. citriodora) leaves. During microwave heating, a simple shielding device made of aluminum foil was used to protect the SPME fiber from microwave irradiation while allowing the sample to be heated. A room temperature water bath was also used to allow microwave heating to be conducted in a more controlled manner. The inner heating caused by microwave irradiation dramatically accelerated the emission of VOCs from the sample, but no marked change in headspace temperature in the sample vial was found. Under optimum conditions, the extraction efficiencies obtained with microwave heating were much higher than those obtained without microwave heating for all fibers used, namely, 7-microm polydimethylsiloxane (PDMS), 100-microm polydimethylsiloxane (PDMS), 65-microm polydimethylsiloxane/divinylbenzene (PDMS/DVB), and 75-microm carboxen/polydimethylsiloxane (CAR/PDMS). The improvement of extraction efficiency using MA-HS-SPME allowed more VOC events to be detected, with more balanced extraction of VOCs of lower and higher molecular masses. Moreover, a good linear relationship was found between sample size and GC-FID response (total peak area of VOCs), indicating the usefulness of MA-HS-SPME for quantitative analysis of individual volatile compounds in E. citriodora leaves.

  9. Fabrication of cross-linked hydrazone covalent organic frameworks by click chemistry and application to solid phase microextraction.

    Science.gov (United States)

    Wu, Mingxue; Chen, Gang; Ma, Jiutong; Liu, Ping; Jia, Qiong

    2016-12-01

    Covalent organic frameworks (COFs) are an emerging class of porous organic frameworks with diverse promising applications. Herein, we presented the first example of cross-linked hydrazone COFs (cross-linked COFs) coating via thiol-ene click chemistry for solid phase microextraction (SPME). Strong covalent bonds and interlayer of the prepared networks ensured the adsorption capacity and durability of the novel SPME fiber. π-π conjugated structure existed because of abundant phenyl rings and -C=N groups in the cross-lined COFs. A series of characterizations indicated that the cross-linked COFs possessed large surface areas, high porosities and stabilities as well as hydrophobicities. The fiber was applied to SPME of pesticide residues coupled with gas chromatography with an electron capture detector (GC-ECD). Under the optimum experimental conditions, enhancement factors in the range of 2190-10,998 were obtained, illustrating that the cross-linked COFs possessed remarkable preconcentration ability. The low detection limits of 0.0003-0.0023ngkg -1 were achieved with relative standard deviations (RSDs) in the range of 3.4-7.6% (intra-batch) and 5.7-11.6% (inter-batch), respectively. Recovery values in the range of 78.2-107.0% were obtained when the SPME-GC method was applied to the analysis of pesticides in cucumber samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Identification of volatile compounds in Chrysanthemum morifolium by microwave distillation solid-phase microextraction coupled with GC/MS.

    Science.gov (United States)

    Zhou, Tao; Yang, Bei; Zhang, Haiying; Yu, Yingjia; Chen, Bin; Chen, Yile; Duan, Gengli

    2009-01-01

    Microwave distillation with concomitant solid-phase microextraction (MD-SPME) coupled with GC/MS was developed for identifying volatile compounds in the dried flowers of Chrysanthemum morifolium (CM). Different experimental parameters, including SPME fiber coating, microwave power, irradiation time, and water volume were optimized. The best results were obtained using carboxen/polydimethylsiloxane fiber with microwave irradiation at 400 W for 3 min and the addition of 1 mL water into 1.0 g sample. The proposed method allowed the isolation, extraction, and concentration of volatile compounds to be completed in a single step. This MD-SPME-GC/MS method has also been compared to the conventional steam distillation method followed by GC/MS for this identification. Thirty-two volatile compounds were identified using the newly developed MD-SPME-GC/MS process. Relative standard deviation values of steam distillation-GC/MS. Therefore, the proposed MD-SPME-GC/MS method is simple, rapid, and efficient for identifying volatile compounds in CM.

  11. Rapid Separation of Elemental Species by Fast Multicapillary Gas Chromatography with Multichannel Optical Spectrometry Detection following Headspace Solid Phase Microextraction

    Directory of Open Access Journals (Sweden)

    Jacek Giersz

    2015-05-01

    Full Text Available A method for conducting fast and efficient gas chromatography based on short multicapillaries in straight alignment combined with atomic emission detection was developed for field analysis. The strategy enables for speciation analysis of organometallic compounds. The analytes are simultaneously ethylated and preconcentrated on a solid phase microextraction (SPME fiber placed in the headspace over the sample for 25 min. The ethylated species are then completely separated and selectively quantified within 25 s under isothermal conditions. A new miniaturized speciation analyzer has been constructed and evaluated. The system consists of a GC injection port and a lab-made miniaturized GC unit directly coupled with miniaturized plasma excitation source. The emitted light is transferred via optical fiber and registered with a miniaturized charged coupled device (CCD based spectrometer. Working parameters for multicapillary column gas chromatography with atomic emission detector, including carrier gas flow rate, desorption temperature, and GC column temperature, were optimized to achieve good separation of analytes. Basic investigations of the fundamental properties of 5 cm-long multicapillary column, to evaluate its potential and limitations as a rapid separation unit, are presented. The adaptation of the technique for use with a SPME system and with a multichannel element-selective plasma-emission detector is highlighted.

  12. Direct solid phase microextraction combined with gas chromatography - Mass spectrometry for the determination of biogenic amines in wine.

    Science.gov (United States)

    Papageorgiou, Myrsini; Lambropoulou, Dimitra; Morrison, Calum; Namieśnik, Jacek; Płotka-Wasylka, Justyna

    2018-06-01

    A direct method based on immersion solid phase microextraction (DI-SPME) gas chromatography mass-spectrometry (GC-MS) was optimized and validated for the determination of 16 biogenic amines in Polish wines. In the analysis two internal standards were used: 1,7-diaminoheptane and bis-3-aminopropylamine. The method allows for simultaneous extraction and derivatization, providing a simple and fast mode of extraction and enrichment. Different parameters which affect the extraction procedure were studied and optimized including ionic strength (0-25%), fiber materials (PDMS/DVB, PDMS/DVD + OC, Polyacrylate, Carboxen/PDMS and DVB/CAR/PDMS) and timings of the extraction, derivatization and desorption processes. Validation studies confirmed the linearity, sensitivity, precision and accuracy of the method. The method was successfully applied to the analysis of 44 wine samples originating from several regions of Poland and 3 wine samples from other countries. Analysis showed that many of the samples contained all examined biogenic amines. The method, assessed using an Eco-Scale tool with satisfactory results, was found to be green in terms of hazardous chemicals and solvents usage, energy consumption and production of waste. Therefore the proposed method can be safely used in the wine industry for routine analysis of BAs in wine samples with a minimal detrimental impact on human health and the environment. Copyright © 2018 Elsevier B.V. All rights reserved.

  13. Second order kinetic modeling of headspace solid phase microextraction of flavors released from selected food model systems.

    Science.gov (United States)

    Zhang, Jiyuan; Cheong, Mun-Wai; Yu, Bin; Curran, Philip; Zhou, Weibiao

    2014-09-04

    The application of headspace-solid phase microextraction (HS-SPME) has been widely used in various fields as a simple and versatile method, yet challenging in quantification. In order to improve the reproducibility in quantification, a mathematical model with its root in psychological modeling and chemical reactor modeling was developed, describing the kinetic behavior of aroma active compounds extracted by SPME from two different food model systems, i.e., a semi-solid food and a liquid food. The model accounted for both adsorption and release of the analytes from SPME fiber, which occurred simultaneously but were counter-directed. The model had four parameters and their estimated values were found to be more reproducible than the direct measurement of the compounds themselves by instrumental analysis. With the relative standard deviations (RSD) of each parameter less than 5% and root mean square error (RMSE) less than 0.15, the model was proved to be a robust one in estimating the release of a wide range of low molecular weight acetates at three environmental temperatures i.e., 30, 40 and 60 °C. More insights of SPME behavior regarding the small molecule analytes were also obtained through the kinetic parameters and the model itself.

  14. A Headspace Solid Phase Microextraction (HS-SPME method for the chromatographic determination of alkylpyrazines in cocoa samples

    Directory of Open Access Journals (Sweden)

    Pini Gláucia F.

    2004-01-01

    Full Text Available A Headspace Solid Phase Microextraction (HS-SPME procedure for isolation and determination of alkylpyrazines in cocoa liquor, using Gas Chromatography with Flame Ionization Detection (GC-FID for the separation and detection of the analytes, is presented here. The HS-SPME operational conditions were optimized using extractions of samples spiked with known amounts of alkylpyrazines typically found on cocoa products. The maximum extraction efficiency was obtained using SPME fibers coated with 65 µm Carbowax/divinylbenzene. Additionally, the best results were achieved with extraction temperature of 60 ºC, 15 min of sample/headspace equilibration time and 45 min extraction time. It was also observed that suspending the samples in saturated aqueous NaCl solution during extractions resulted in a significant increment on the peak areas. This procedure was found to be effective to determine the so-called pyrazinic ratios (quotient between peak areas of alkylpyrazines, which are useful as quality parameters for cocoa liquor.

  15. Second Order Kinetic Modeling of Headspace Solid Phase Microextraction of Flavors Released from Selected Food Model Systems

    Directory of Open Access Journals (Sweden)

    Jiyuan Zhang

    2014-09-01

    Full Text Available The application of headspace-solid phase microextraction (HS-SPME has been widely used in various fields as a simple and versatile method, yet challenging in quantification. In order to improve the reproducibility in quantification, a mathematical model with its root in psychological modeling and chemical reactor modeling was developed, describing the kinetic behavior of aroma active compounds extracted by SPME from two different food model systems, i.e., a semi-solid food and a liquid food. The model accounted for both adsorption and release of the analytes from SPME fiber, which occurred simultaneously but were counter-directed. The model had four parameters and their estimated values were found to be more reproducible than the direct measurement of the compounds themselves by instrumental analysis. With the relative standard deviations (RSD of each parameter less than 5% and root mean square error (RMSE less than 0.15, the model was proved to be a robust one in estimating the release of a wide range of low molecular weight acetates at three environmental temperatures i.e., 30, 40 and 60 °C. More insights of SPME behavior regarding the small molecule analytes were also obtained through the kinetic parameters and the model itself.

  16. Characterization of the Key Aroma Compounds in Proso Millet Wine Using Headspace Solid-Phase Microextraction and Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Jingke Liu

    2018-02-01

    Full Text Available The volatile compounds in proso millet wine were extracted by headspace solid-phase microextraction (85 μm polyacrylate (PA, 100 μm polydimethylsiloxane (PDMS, 75 μm Carboxen (CAR/PDMS, and 50/30 μm divinylbenzene (DVB/CAR/PDMS fibers, and analyzed using gas chromatography-mass spectrometry; the odor characteristics and intensities were analyzed by the odor activity value (OAV. Different sample preparation factors were used to optimize this method: sample amount, extraction time, extraction temperature, and content of NaCl. A total of 64 volatile compounds were identified from the wine sample, including 14 esters, seven alcohols, five aldehydes, five ketones, 12 benzene derivatives, 12 hydrocarbons, two terpenes, three phenols, two acids, and two heterocycles. Ethyl benzeneacetate, phenylethyl alcohol, and benzaldehyde were the main volatile compounds found in the samples. According to their OAVs, 14 volatile compounds were determined to be odor-active compounds (OAV > 1, and benzaldehyde, benzeneacetaldehyde, 1-methyl-naphthalene, 2-methyl-naphthalene, and biphenyl were the prominent odor-active compounds (OAV > 50, having a high OAV. Principal component analysis (PCA showed the difference of distribution of the 64 volatile compounds and 14 odor-active compounds with four solid-phase microextraction (SPME fibers.

  17. Solid-phase microextraction of volatile compounds from the chopped leaves of three species of Eucalyptus.

    Science.gov (United States)

    Zini, Cláudia A; Zanin, Kelen D; Christensen, Eva; Caramão, Elina B; Pawliszyn, Janusz

    2003-04-23

    Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography and ion-trap mass spectrometry has been used to identify biogenic volatile organic compounds present in the headspace of chopped leaves of Eucalyptus (E.) dunnii, E. citriodora, and E. saligna. A simple HS-SPME method entailing 30 min of extraction at 30 degrees C was developed for this purpose. Thirty compounds were identified in the headspace of 60 juvenile chopped Eucalyptus leaves, and another 30 were tentatively identified. The presence of compounds such as (E)-4,8-dimethyl-1,3,7-nonatriene (DMNT), (E,E)-4,8,12-trimethyl-1,3,7,11-tridecatetraene (TMNT), (E,E)-alpha-farnesene, (E,E,E)-3,7,11,15-tetramethyl-1,3,6,10,14-hexadecapentaene (TMHP), beta-caryophyllene, alpha-humulene, germacrene D, and beta-cubebene in the headspace of the leaves but not in the essential oils from the same Eucalyptus trees and information about the infochemical roles of some of these compounds in other living plant systems suggest they might play a bioactive role in Eucalyptus leaves.

  18. Knitting aromatic polymers for efficient solid-phase microextraction of trace organic pollutants.

    Science.gov (United States)

    Liu, Shuqin; Hu, Qingkun; Zheng, Juan; Xie, Lijun; Wei, Songbo; Jiang, Ruifen; Zhu, Fang; Liu, Yuan; Ouyang, Gangfeng

    2016-06-10

    A series of knitting aromatic polymers (KAPs) were successfully synthesized using a simple one-step Friedel-Crafts alkylation of aromatic monomers and were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Then, as-synthesized KAPs with large surface areas, unique pore structures and high thermal stability were prepared as solid-phase microextraction (SPME) coatings that exhibited good extraction abilities for a series of benzene compounds (i.e., benzene, toluene, ethylbenzene and m-xylene, which are referred to as BTEX) and polycyclic aromatic hydrocarbons (PAHs). Under the optimized conditions, the methodologies established for the determination of BTEX and PAHs using the KAPs-triPB and KAPs-B coatings, respectively, possessed wide linear ranges, low limits of detection (LODs, 0.10-1.13ngL(-1) for BTEX and 0.05-0.49ngL(-1) for PAHs) and good reproducibility. Finally, the proposed methods were successfully applied to the determination of BTEX and PAHs in environmental water samples, and satisfactory recoveries (93.6-124.2% for BTEX and 77.2-113.3% for PAHs) were achieved. This study provides a benchmark for exploiting novel microporous organic polymers (MOPs) for SPME applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Quantification of VOC emissions from paint spraying on a construction site using solid phase microextraction devices.

    Science.gov (United States)

    Cheng, Wen-Hsi; Huang, Hsiao-Lin; Chen, Kang-Shin; Chang, Yu-Jen

    2017-10-15

    The objective of this study was to measure the emission of, and personal exposure to workers, volatile organic compound (VOC) during paint spraying on a construction site. Needle trap samplers (NTSs), which are a green solid phase microextraction sampling technology, were used to obtain air samples at a large music exhibition center. The standard active sampling method using charcoal tubes and a personal air pump, Method 1501, was simultaneously utilized at the sampling sites to assess the workers' VOC exposures. Analysis of the data thus obtained showed that benzene, toluene, ethylenebenzene, and xylenes (BTEXs) were the main emission compounds. Acetone and isobutyl alcohol, which are used as thinning solvents, were detected as minor emission compounds. The emitted concentrations of most compounds were lower than the legal emission limits in Taiwan except that of benzene, for which the 2-ppm time weighted average short-term exposure limit was exceeded. The packed divinylbenzene (DVB) in the NTS was observed under an environmental scanning electron microscope, and many fine aerosols were found to be deposited on the surface of the DVB adsorbents, causing VOC extraction efficiencies after the fifth sampling in the field to decline. Workers on construction sites should be protected from emissions of VOC and fine particulates to preserve their occupational health.

  20. Identification of volatile compounds in soybean at various developmental stages using solid phase microextraction.

    Science.gov (United States)

    Boué, Stephen M; Shih, Betty Y; Carter-Wientjes, Carol H; Cleveland, Thomas E

    2003-08-13

    Soybean (Glycine max) seed volatiles were analyzed using a solid phase microextraction (SPME) method combined with gas chromatography-mass spectrometry (GC-MS). Thirty volatile compounds already reported for soybean were recovered, and an additional 19 compounds not previously reported were identified or tentatively identified. The SPME method was utilized to compare the volatile profile of soybean seed at three distinct stages of development. Most of the newly reported compounds in soybean seed were aldehydes and ketones. During early periods of development at maturity stage R6, several volatiles were present at relatively high concentrations, including 3-hexanone, (E)-2-hexenal, 1-hexanol, and 3-octanone. At maturity stage R7 and R8, decreased amounts of 3-hexanone, (E)-2-hexenal, 1-hexanol, and 3-octanone were observed. At maturity stage R8 hexanal, (E)-2-heptenal, (E)-2-octenal, ethanol, 1-hexanol, and 1-octen-3-ol were detected at relatively high concentrations. SPME offers the ability to differentiate between the three soybean developmental stages that yield both fundamental and practical information.

  1. Multiple headspace-solid-phase microextraction: an application to quantification of mushroom volatiles.

    Science.gov (United States)

    Costa, Rosaria; Tedone, Laura; De Grazia, Selenia; Dugo, Paola; Mondello, Luigi

    2013-04-03

    Multiple headspace-solid phase microextraction (MHS-SPME) followed by gas chromatography/mass spectrometry (GC-MS) and flame ionization detection (GC-FID) was applied to the identification and quantification of volatiles released by the mushroom Agaricus bisporus, also known as champignon. MHS-SPME allows to perform quantitative analysis of volatiles from solid matrices, free of matrix interferences. Samples analyzed were fresh mushrooms (chopped and homogenized) and mushroom-containing food dressings. 1-Octen-3-ol, 3-octanol, 3-octanone, 1-octen-3-one and benzaldehyde were common constituents of the samples analyzed. Method performance has been tested through the evaluation of limit of detection (LoD, range 0.033-0.078 ng), limit of quantification (LoQ, range 0.111-0.259 ng) and analyte recovery (92.3-108.5%). The results obtained showed quantitative differences among the samples, which can be attributed to critical factors, such as the degree of cell damage upon sample preparation, that are here discussed. Considerations on the mushrooms biochemistry and on the basic principles of MHS analysis are also presented. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Study of aged cognac using solid-phase microextraction and partial least-squares regression.

    Science.gov (United States)

    Watts, Vivian A; Butzke, Christian E; Boulton, Roger B

    2003-12-17

    Headspace solid-phase microextraction (SPME) and GC-MS were used to analyze 17 commercial French Cognac brandies (9 young and 8 well-aged, ranging in age from 3 to 55 years). Sixty-four volatiles were chosen on the basis of chromatographic separation and/or known odor importance. Chromatographic peaks were manually integrated and the peak area data analyzed using partial least-squares (PLS) regression to study relationships between volatile composition (X variables) and age (Y variable). When only those compounds with the highest significance were included and from these selected the variables (a total of 33) with the highest correlation loadings on the first two principal components, principal component 1 explained 82% of the variance of the measured compounds and 85% of the variance in age. These were considered the most important volatiles to distinguish products of different ages because young and old samples were separated along principal component 1. Norisoprenoids, terpenes, and acetate esters had weaker positive and negative loadings and were therefore left out. The PLS model could predict sample age accurately with the optimum 33 volatiles as well as with a smaller subset consisting of ethyl esters and methyl ketones.

  3. A Longitudinal Study of Decomposition Odour in Soil Using Sorbent Tubes and Solid Phase Microextraction

    Directory of Open Access Journals (Sweden)

    Katelynn A. Perrault

    2014-07-01

    Full Text Available Odour profiling of decomposed remains is important for understanding the mechanisms that cadaver dogs and forensically-relevant insects use to locate decomposed remains. The decomposition odour profile is complex and has been documented in outdoor terrestrial environments. The purpose of this study was to perform longitudinal analysis of the volatile organic compound (VOC profile in soils associated with decomposed remains across all stages of decomposition. Two VOC collection techniques (sorbent tubes and solid phase microextraction were used to collect a wider analyte range and to investigate differences in collection techniques. Pig carcasses were placed in an outdoor research facility in Australia to model the decomposition process and VOCs were collected intermittently over two months. VOCs of interest were identified over the duration of the trial, showing distinct trends in compound evolution and disappearance. The collection techniques were complementary, representing different subsets of VOCs from the overall profile. Sorbent tubes collected more decomposition-specific VOCs and these compounds were more effective at characterising the matrix over an extended period. Using both collection techniques improves the likelihood of identifying the complete VOC profile of decomposition odour. Such information is important for the search and recovery of victim remains in various stages of decomposition.

  4. SIMPLE METHOD FOR ESTIMATING POLYCHLORINATED BIPHENYL CONCENTRATIONS ON SOILS AND SEDIMENTS USING SUBCRITICAL WATER EXTRACTION COUPLED WITH SOLID-PHASE MICROEXTRACTION. (R825368)

    Science.gov (United States)

    A rapid method for estimating polychlorinated biphenyl (PCB) concentrations in contaminated soils and sediments has been developed by coupling static subcritical water extraction with solid-phase microextraction (SPME). Soil, water, and internal standards are placed in a seale...

  5. Novel Electrosorption-Enhanced Solid-Phase Microextraction Device for Ultrafast In Vivo Sampling of Ionized Pharmaceuticals in Fish.

    Science.gov (United States)

    Qiu, Junlang; Wang, Fuxin; Zhang, Tianlang; Chen, Le; Liu, Yuan; Zhu, Fang; Ouyang, Gangfeng

    2018-01-02

    Decreasing the tedious sample preparation duration is one of the most important concerns for the environmental analytical chemistry especially for in vivo experiments. However, due to the slow mass diffusion paths for most of the conventional methods, ultrafast in vivo sampling remains challenging. Herein, for the first time, we report an ultrafast in vivo solid-phase microextraction (SPME) device based on electrosorption enhancement and a novel custom-made CNT@PPY@pNE fiber for in vivo sampling of ionized acidic pharmaceuticals in fish. This sampling device exhibited an excellent robustness, reproducibility, matrix effect-resistant capacity, and quantitative ability. Importantly, the extraction kinetics of the targeted ionized pharmaceuticals were significantly accelerated using the device, which significantly improved the sensitivity of the SPME in vivo sampling method (limits of detection ranged from 0.12 ng·g -1 to 0.25 ng·g -1 ) and shorten the sampling time (only 1 min). The proposed approach was successfully applied to monitor the concentrations of ionized pharmaceuticals in living fish, which demonstrated that the device and fiber were suitable for ultrafast in vivo sampling and continuous monitoring. In addition, the bioconcentration factor (BCF) values of the pharmaceuticals were derived in tilapia (Oreochromis mossambicus) for the first time, based on the data of ultrafast in vivo sampling. Therefore, we developed and validated an effective and ultrafast SPME sampling device for in vivo sampling of ionized analytes in living organisms and this state-of-the-art method provides an alternative technique for future in vivo studies.

  6. Glass bottle sampling solid phase microextraction gas chromatography mass spectrometry for breath analysis of drug metabolites.

    Science.gov (United States)

    Lu, Yan; Niu, Wenqi; Zou, Xue; Shen, Chengyin; Xia, Lei; Huang, Chaoqun; Wang, Hongzhi; Jiang, Haihe; Chu, Yannan

    2017-05-05

    Breath analysis is a non-invasive approach which may be applied to disease diagnosis and pharmacokinetic study. In the case of offline analysis, the exhaled gas needs to be collected and the sampling bag is often used as the storage vessel. However, the sampling bag usually releases some extra compounds, which may interfere with the result of the breath test. In this study, a novel breath sampling glass bottle was developed with a syringe needle sampling port for solid phase microextraction (SPME). Such a glass bottle scarcely liberates compounds and can be used to collect exhaled gas for ensuing analysis by gas chromatography-mass spectrometry (GC-MS). The glass bottle sampling SPME-GC-MS analysis was carried out to investigate the breath metabolites of myrtol, a multicompound drug normally used in the treatment of bronchitis and sinusitis. Four compounds, α-pinene, 2,3-dehydro-1,8-cineole, d-limonene and 1,8-cineole were found in the exhaled breath of all eight volunteers who had taken the myrtol. While for other ten subjects who had not used the myrtol, these compounds were undetectable. In the SPME-GC-MS analysis of the headspace of myrtol, three compounds were detected including α-pinene, d-limonene and 1,8-cineole. Comparing the results of breath and headspace analysis, it indicates that 2,3-dehydro-1,8-cineole in the breath is the metabolite of 1,8-cineole. It is the first time that this metabolite was identified in human breath. The study demonstrates that the glass bottle sampling SPME-GC-MS method is applicable to exhaled gas analysis including breath metabolites investigation of drugs like myrtol. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Determination of parathion in biological fluids by means of direct solid-phase microextraction.

    Science.gov (United States)

    Gallardo, E; Barroso, M; Margalho, C; Cruz, A; Vieira, D N; López-Rivadulla, M

    2006-11-01

    A new and simple procedure for the determination of parathion in human whole blood and urine using direct immersion (DI) solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) is presented. This technique was developed using only 100 microL of sample, and ethion was used as internal standard (IS). A 65-microm Carbowax/divinylbenzene (CW/DVB) SPME fibre was selected for sampling, and the main parameters affecting the SPME process such as extraction temperature, adsorption and desorption time, salt addition, agitation and pH effect were optimized to enhance the sensitivity of the method. This optimization was also performed to allow the qualitative determination of parathion's main metabolite, paraoxon, in blood. The limits of detection and quantitation for parathion were 3 and 10 ng/mL for urine and 25 and 50 ng/mL for blood, respectively. For paraoxon, the limit of detection was 50 ng/mL in blood. The method showed linearity between the LOQ and 50 microg/mL for both matrices, with correlation coefficients ranging from 0.9954 to 0.9999. Precision and accuracy were in conformity with the criteria normally accepted in bioanalytical method validation. The mean absolute recoveries were 35.1% for urine and 6.7% for blood. Other parameters such as dilution of sample and stability were also validated. Its simplicity and the fact that only 100 microL of sample is required to accomplish the analysis make this method useful in forensic toxicology laboratories to determine this compound in intoxications, and it can be considered an alternative to other methods normally used for the determination of this compound in biological media.

  8. Estimation of bioavailability and potential risks of naphthalene in soils with solid phase microextraction.

    Science.gov (United States)

    Liu, Hsiang-Chao; Hwu, Ching-Shyung; Chu, Ko-Chiao; Lu, Chih-Jen

    2010-07-01

    A series of batch experiments were conducted to observe the variations of bioavailability of naphthalene in different types of soil with indigenous microorganisms. Solid phase microextraction (SPME) was employed to estimate the bioavailability of naphthalene in the soils. Various soil properties were attained by artificially modifying soil organic matter (SOM) with the addition of bagasse compost and textures with the addition of original silt and clay to determine the correlation between the amount of biodegraded naphthalene after 300 h and the amount of extractable naphthalene by SPME. Experimental results indicated that the biodegradation rate increased from 0.30 (sandy loam) to 0.48 (silty loam) μg g(-1) h(-1) when soils had more silt/clay. In contrast, the biodegradation rate slightly decreased from 0.30 (1.3% SOM) to 0.20 (5.2% SOM) μg g(-1) h(-1) when the SOM was high. Distributions of naphthalene in soils after biodegradation were affected by the addition of bagasse compost. It showed that the bioavailability of naphthalene in soils decreased with an increase in SOM. Sequestration as measured by ultrasonic extractability evidently occurred within 4 months in aged soil samples. However, the amounts extracted by sonication after 4 and 16 months of aging did not statistically differ from each other. The SPME measurements correlated well with the amount of biodegraded naphthalene by indigenous microorganisms. Results of this study demonstrate that SPME is a promising method to estimate the bioremediation efficacy of naphthalene-contaminated soils with various properties.

  9. Quantitative solid phase microextraction--gas chromatography mass spectrometry analysis of five megastigmatrienone isomers in aged wine.

    Science.gov (United States)

    Slaghenaufi, Davide; Perello, Marie-Claire; Marchand-Marion, Stéphanie; Tempere, Sophie; de Revel, Gilles

    2014-02-27

    Megastigmatrienone is a key flavor compound in tobacco. It has also been detected in wine, where it may contribute to a tobacco/incense aroma, but its importance and concentration in wines had never previously been evaluated. A method was developed and validated for quantifying the five megastigmatrienone isomers in red and white wines. Megastigmatrienone isomers were extracted by headspace solid-phase microextraction (HS-SPME), with a 65 μm film thickness polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber and analyzed using gas chromatography-mass spectrometry (GC/MS) in selected ion monitoring mode (SIM). Several parameters affecting the length of the adsorption process (i.e., adding salt, extraction time and extraction temperature) were tested. The optimum analytical conditions were established. The LOQ were between 0.06 μg L(-1) and 0.49 μg L(-1) for white wine and 0.11 μg L(-1) and 0.98 μg L(-1) for red wine, repeatability in both types of wine was less than 10% and recovery ranged from 96% for white wine to 94% for red wine. The five isomers of megastigmatrienone were quantified in red and white wines for the first time. Concentrations ranged from 2 μg L(-1) to 41 μg L(-1) in both red and white wines. Initial results revealed a link between wine aging and megastigmatrienone levels, indicating that megastigmatrienone may be a component in wine "bouquet". Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Ultrasensitive Speciation Analysis of Mercury in Rice by Headspace Solid Phase Microextraction Using Porous Carbons and Gas Chromatography-Dielectric Barrier Discharge Optical Emission Spectrometry.

    Science.gov (United States)

    Lin, Yao; Yang, Yuan; Li, Yuxuan; Yang, Lu; Hou, Xiandeng; Feng, Xinbin; Zheng, Chengbin

    2016-03-01

    Rice consumption is a primary pathway for human methylmercury (MeHg) exposure in inland mercury mining areas of Asia. In addition, the use of iodomethane, a common fumigant that significantly accelerates the methylation of mercury in soil under sunlight, could increase the MeHg exposure from rice. Conventional hyphenated techniques used for mercury speciation analysis are usually too costly for most developing countries. Consequently, there is an increased interest in the development of sensitive and inexpensive methods for the speciation of mercury in rice. In this work, gas chromatography (GC) coupled to dielectric barrier discharge optical emission spectrometry (DBD-OES) was developed for the speciation analysis of mercury in rice. Prior to GC-DBD-OES analysis, mercury species were derivatized to their volatile species with NaBPh4 and preconcentrated by headspace solid phase microextraction using porous carbons. Limits of detection of 0.5 μg kg(-1) (0.16 ng), 0.75 μg kg(-1) (0.24 ng), and 1.0 μg kg(-1) (0.34 ng) were obtained for Hg(2+), CH3Hg(+), and CH3CH2Hg(+), respectively, with relative standard deviations (RSDs) better than 5.2% and 6.8% for one fiber or fiber-to-fiber mode, respectively. Recoveries of 90-105% were obtained for the rice samples, demonstrating the applicability of the proposed technique. Owing to the small size, low power, and low gas consumption of DBD-OES as well as efficient extraction of mercury species by porous carbons headspace solid phase micro-extraction, the proposed technique provides several advantages including compactness, cost-effectiveness, and potential to couple with miniature GC to accomplish the field speciation of mercury in rice compared to conventional hyphenated techniques.

  11. Sampling gaseous compounds from essential oils evaporation by solid phase microextraction devices

    Science.gov (United States)

    Cheng, Wen-Hsi; Lai, Chin-Hsing

    2014-12-01

    Needle trap samplers (NTS) are packed with 80-100 mesh divinylbenzene (DVB) particles to extract indoor volatile organic compounds (VOCs). This study compared extraction efficiency between an NTS and a commercially available 100 μm polydimethylsiloxane-solid phase microextration (PDMS-SPME) fiber sampler used to sample gaseous products in heated tea tree essential oil in different evaporation modes, which were evaporated respectively by free convection inside a glass evaporation dish at 27 °C, by evaporation diffuser at 60 °C, and by thermal ceramic wicks at 100 °C. The experimental results indicated that the NTS performed better than the SPME fiber samplers and that the NTS primarily adsorbed 5.7 ng ethylbenzene, 5.8 ng m/p-xylenes, 11.1 ng 1,2,3-trimethylbenzene, 12.4 ng 1,2,4-trimethylbenzene and 9.99 ng 1,4-diethylbenzene when thermal ceramic wicks were used to evaporate the tea tree essential oil during a 1-hr evaporation period. The experiment also indicated that the temperature used to heat the essential oils should be as low as possible to minimize irritant VOC by-products. If the evaporation temperature does not exceed 100 °C, the concentrations of main by-products trimethylbenzene and diethylbenzene are much lower than the threshold limit values recommended by the National Institute for Occupational Safety and Health (NIOSH).

  12. Recent progress, challenges and trends in trace determination of drug analysis using molecularly imprinted solid-phase microextraction technology.

    Science.gov (United States)

    Ansari, Saeedeh; Karimi, Majid

    2017-03-01

    The quantification of drugs in biological samples is a significant task for determination of the physiological efficiency in evaluated drugs in the drug discovery. To analysis of the chemical compounds at the trace and ultratrace levels, adequate analytical procedures should be applied. Therefore, sample preparation method undoubtedly is the most important stage in the trace determination process. In spite of the great growth of analytical instrumentation during the recent years, sample preparation is still nowadays considered the impasse of the all analytical procedure, especially in drugs analysis. Because of the low concentration level of drugs in blood, plasma, and the diversity of the metabolites, the chosen extraction technique should be almost perfect. Solid-phase microextraction (SPME) is a powerful, simple, fast and an equilibrium-based sample preparation method that permits integration of sampling, sample clean-up, and pre-concentration in a single solvent-free step for chemical analysis. Molecularly imprinted polymers (MIPs) that provided by the presence of a template during their synthesis are the stable polymers with molecular recognition abilities and excellent materials which provide selectivity to sample preparation. Because of its characteristics such as easy preparation, high selectivity, and chemical stability, MIP is widely utilized in many analytical fields. Accordingly, the molecular imprinting and SPME methods combination would prepare a strong analytical instrumentation which comprises simplicity, flexibility, and the selectivity characteristics of both methods. This review focuses on the application of solid-phase microextraction method coupled with molecularly imprinted polymers, namely molecularly imprinted solid-phase microextraction (MISPME), for trace determination in drug analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Time-weighted average sampling of airborne propylene glycol ethers by a solid-phase microextraction device.

    Science.gov (United States)

    Shih, H C; Tsai, S W; Kuo, C H

    2012-01-01

    A solid-phase microextraction (SPME) device was used as a diffusive sampler for airborne propylene glycol ethers (PGEs), including propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and dipropylene glycol monomethyl ether (DPGME). Carboxen-polydimethylsiloxane (CAR/PDMS) SPME fiber was selected for this study. A polytetrafluoroethylene (PTFE) tubing was used as the holder, and the SPME fiber assembly was inserted into the tubing as a diffusive sampler. The diffusion path length and area of the sampler were 0.3 cm and 0.00086 cm(2), respectively. The theoretical sampling constants at 30°C and 1 atm for PGME, PGMEA, and DPGME were 1.50 × 10(-2), 1.23 × 10(-2) and 1.14 × 10(-2) cm(3) min(-1), respectively. For evaluations, known concentrations of PGEs around the threshold limit values/time-weighted average with specific relative humidities (10% and 80%) were generated both by the air bag method and the dynamic generation system, while 15, 30, 60, 120, and 240 min were selected as the time periods for vapor exposures. Comparisons of the SPME diffusive sampling method to Occupational Safety and Health Administration (OSHA) organic Method 99 were performed side-by-side in an exposure chamber at 30°C for PGME. A gas chromatography/flame ionization detector (GC/FID) was used for sample analysis. The experimental sampling constants of the sampler at 30°C were (6.93 ± 0.12) × 10(-1), (4.72 ± 0.03) × 10(-1), and (3.29 ± 0.20) × 10(-1) cm(3) min(-1) for PGME, PGMEA, and DPGME, respectively. The adsorption of chemicals on the stainless steel needle of the SPME fiber was suspected to be one of the reasons why significant differences between theoretical and experimental sampling rates were observed. Correlations between the results for PGME from both SPME device and OSHA organic Method 99 were linear (r = 0.9984) and consistent (slope = 0.97 ± 0.03). Face velocity (0-0.18 m/s) also proved to have no effects on the sampler

  14. Headspace solid phase microextraction (HSSPME) for the determination of volatile and semivolatile pollutants in soils

    Energy Technology Data Exchange (ETDEWEB)

    Llompart, Maria [Departamento de Quimica Analitica Nutricion y Bromatologia, Facultad de Quimica, Universidad de Santiago de Compostela, E-15706 Santiago de Compostela (Spain); Li, Ken; Fingas, Merv [Emergencies Science Division, Environment Canada, Environmental Technology Centre, 3439 River Road, Ottawa, ON (Canada)

    1999-02-08

    We have investigated the use of headspace solid phase microextraction (HSSPME) as a sample concentration and preparation technique for the analysis of volatile and semivolatile pollutants in soil samples. Soil samples were suspended in solvent and the SPME fibre suspended in the headspace above the slurry. Finally, the fibre was desorbed in the Gas Chromatograph (GC) injection port and the analysis of the samples was carried out. Since the transfer of contaminants from the soil to the SPME fibre involves four separate phases (soil-solvent-headspace and fibre coating), parameters affecting the distribution of the analytes were investigated. Using a well-aged artificially spiked garden soil, different solvents (both organic and aqueous) were used to enhance the release of the contaminants from the solid matrix to the headspace. It was found that simple addition of water is adequate for the purpose of analysing the target volatile organic chemicals (VOCs) in soil. The addition of 1 ml of water to 1 g of soil yielded maximum response. Without water addition, the target VOCs were almost not released from the matrix and a poor response was observed. The effect of headspace volume on response as well as the addition of salt were also investigated. Comparison studies between conventional static headspace (HS) at high temperature (95C) and the new technology HSSPME at room temperature (=20C) were performed. The results obtained with both techniques were in good agreement. HSSPME precision and linearity were found to be better than automated headspace method and HSSPME also produced a significant enhancement in response. The detection and quantification limits for the target VOCs in soils were in the sub-ng g{sup -1} level. Finally, we tried to extend the applicability of the method to the analysis of semivolatiles. For these studies, two natural soils contaminated with diesel fuel and wood preservative, as well as a standard urban dust contaminated with polyaromatic

  15. Solid phase microextraction, sand flies, oviposition pheromones, plaster of Paris and siloxanes-What is in common?

    Science.gov (United States)

    Goulart, Thais Marchi; Tosta, Christiann Davis; Machado, Vicente Estevam; da Rocha Silva, Flávia Benini; de Castro, Camila Feitosa; Ortiz, Dennys Ghenry Samillan; Oliveira, Wanderson Henrique Cruz; Pinto, Mara Cristina

    2017-04-01

    Sand flies are natural hosts of various microorganisms. Due to their epidemiological importance, sand fly colonies are kept in laboratories to be studied in terms of their biology and vector/host/parasite interactions. In order to investigate the presence of oviposition pheromones in Nyssomyia neivai, experiments using Solid Phase Microextraction (SPME) were performed. However, siloxanes which is an external class of contamination, present in breeding containers made by plaster used to maintain sand flies in colonies, may be hindered the experiments. Published by Elsevier B.V.

  16. Applicability of solid-phase microextraction combined with gas chromatography atomic emission detection (GC-MIP AED) for the determination of butyltin compounds in sediment samples

    Energy Technology Data Exchange (ETDEWEB)

    Carpinteiro, J.; Rodriguez, I.; Cela, R. [Universidad de Santiago de Compostela, Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Santiago de Compostela 15782 (Spain)

    2004-11-01

    The performance of solid-phase microextraction (SPME) applied to the determination of butyltin compounds in sediment samples is systematically evaluated. Matrix effects and influence of blank signals on the detection limits of the method are studied in detail. The interval of linear response is also evaluated in order to assess the applicability of the method to sediments polluted with butyltin compounds over a large range of concentrations. Advantages and drawbacks of including an SPME step, instead of the classic liquid-liquid extraction of the derivatized analytes, in the determination of butyltin compounds in sediment samples are considered in terms of achieved detection limits and experimental effort. Analytes were extracted from the samples by sonication using glacial acetic acid. An aliquot of the centrifuged extract was placed on a vial where compounds were ethylated and concentrated on a PDMS fiber using the headspace mode. Determinations were carried out using GC-MIP AED. (orig.)

  17. Direct-immersion solid-phase microextraction coupled to fast gas chromatography mass spectrometry as a purification step for polycyclic aromatic hydrocarbons determination in olive oil.

    Science.gov (United States)

    Purcaro, Giorgia; Picardo, Massimo; Barp, Laura; Moret, Sabrina; Conte, Lanfranco S

    2013-09-13

    The aim of the present work was to optimize a preparation step for polycyclic aromatic hydrocarbons in a fatty extract. Solid-phase microextraction is an easy preparation technique, which allows to minimize solvent consumption and reduce sample manipulation. A Carbopack Z/polydimethylsiloxane fiber, particularly suitable for extraction of planar compounds, was employed to extract polycyclic aromatic hydrocarbons from a hexane solution obtained after a previous extraction with acetonitrile from oil, followed by a liquid-liquid partition between acetonitrile and hexane. The proposed method was a rapid and sensitive solution to reduce the interference of triglycerides saving the column life and avoiding frequent cleaning of the mass spectrometer ion source. Despite the non-quantitative extraction of polycyclic aromatic hydrocarbons from oil using acetonitrile, the signal-to-noise ratio was significantly improved obtaining a limit of detection largely below the performance criteria required by the European Union legislation. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Determination of Xylene and Toluene by Solid-Phase Microextraction Using Au Nanoparticles-Thiol Silane Film Coupled to Ion Mobility Spectrometry.

    Science.gov (United States)

    Allafchian, Ali Reza; Akhgar, Ava; Ielbeigi, Vahideh; Tabrizchi, Mahmoud

    2016-11-01

    A simple, rapid and sensitive method for analysis of xylene and toluene was developed using the solid-phase microextraction (SPME) combined with ion mobilityspectrometry (IMS). Gold nanoparticles-thiol silane film (Au NPs-TSF) was applied as a newsorbent for SPME. Thiol silane film was formed on the surface of a stainless steel wire through incorporating Au nanoparticles during synthesis using sol-gel technique. The extraction properties of the fiber to xylene and toluene were examined, using a SPME device and thermal desorption ininjection port of IMS. The calibration graphs were linear in the range of 1.10-32.0 and 16.0-112.0 ppb for xylene and toluene, respectively. The detection limits for xylene and toluene were 0.7 and 8.0 ppb, respectively. The proposed method was applied without any considerable sample pretreatment and it was found to be simple enough to be strongly recommended for real sample analysis.

  19. Cadmium(II)-based metal-organic nanotubes as solid-phase microextraction coating for ultratrace-level analysis of polychlorinated biphenyls in seawater samples.

    Science.gov (United States)

    Sheng, Wan-Ru; Chen, Yue; Wang, Shan-Shan; Wang, Xiao-Li; Wang, Ming-Lin; Zhao, Ru-Song

    2016-11-01

    In this study, stable cadmium(II)-based metal-organic nanotubes (Cd-MONTs) were prepared and used as a coating material for solid-phase microextraction (SPME) of polychlorinated biphenyls (PCBs) from environmental water samples. The as-prepared Cd-MONT SPME coating material was characterized by thermal gravimetric analysis, scanning electron microscopy, and X-ray diffraction. The synthesized Cd-MONTs exhibited high thermal stability (385 °C) and excellent extraction performance toward PCBs. The important conditions were optimized systematically by the response surface method. Under the optimal conditions, the new fiber achieved high enrichment factors (938-3417), low limits of detection (1.80-8.73 pg L -1 ), and wide linearity (10-5000 pg L -1 ). The method developed was used in ultratrace-level analysis of PCBs in seawater samples, with satisfactory results for each sample.

  20. Comparison of solid-phase microextraction, supercritical fluid extraction, steam distillation, and solvent extraction techniques for analysis of volatile consituents in Fructus Amomi.

    Science.gov (United States)

    Shen, Shun; Sha, Yunfei; Deng, Chunhui; Fu, Daxi; Chen, Jiakuan; Zhang, Xiangmin

    2005-01-01

    Four sampling techniques, solid-phase microextraction (SPME), supercritical fluid extraction (SFE), steam distillation (SD), and solvent extraction (SE), were compared for the analysis of volatile constituents from a traditional Chinese medicine (TCM) of the dried ripe fruit of Fructus Amomi (Sha Ren). A total of 38 compounds were identified by gas chromatography/mass spectrometry. Different SFE and SPME parameters (modifier content, extraction pressure, and temperature for SFE and fibers, extraction temperature, and time for SPME) were studied. The results by SFE and SPME were compared with those obtained by conventional SD and SE methods. The results showed that SFE and SPME are better sample preparation techniques than SD and SE. Due to SFE's requirement for expensive specialized instrumentation, the simplicity, low cost, and speed of SPME make it a more appropriate technique for extraction of volatile constituents in TCMs.

  1. Use of headspace solid-phase microextraction coupled to liquid chromatography for the analysis of polycyclic aromatic hydrocarbons in tea infusions.

    Science.gov (United States)

    Viñas, Pilar; Campillo, Natalia; Aguinaga, Nerea; Pérez-Cánovas, Eva; Hernández-Córdoba, Manuel

    2007-09-14

    A sensitive and solvent-free procedure for the determination of 11 polycyclic aromatic hydrocarbons in tea infusions using headspace solid-phase microextraction coupled to liquid chromatography with fluorimetric detection is described. A medium polarity polydimethylsiloxane-divinylbenzene 60 microm fiber was found to be suitable for extraction at 90 degrees C and with an extraction time of 60 min under continuous stirring. Desorption was carried out using the static mode for 5 min. Under the optimized conditions, when 1.75 g of tea sample were extracted with boiling water, the precision ranged from 4 to 16% (RSD) and detection limits were between 4 and 145 ngL(-1), depending on the compound. The reliability of the procedure was corroborated by means of GC-MS. The results obtained for a standard reference material were within the range indicated by the supplier.

  2. Electrospun decyl-3-methylimidazolium mono bromate/polyamide nanofibers as solid-phase microextraction coating.

    Science.gov (United States)

    Roostaie, Ali; Rastegar, Sorosh; Najarzadegan, Hamid; Ehteshami, Shokooh

    2017-09-22

    In the current study, electrospun-based ionic liquid (IL) doped polyamide (PA) nanofibers were prepared and used as the coating material of solid phase microextration device in the fiber geometry. Addition of IL, decyl-3-methylimidazolium mono bromate, increased the conductivity of the PA solution facilitating the electrospining process. The scanning electron microscopy images of decyl-3-methylimidazolium mono bromated/polyamide nanofibers showed the decreased diameter of the nanofibers in the range of 35-160nm compared to the PA nanofiber. The factors affecting the structure of nanofibers (e.g. ratio of decyl-3-methylimidazolium mono bromate to PA, coating time and applied voltage) were studied. In addition, influential parameters of extraction/desorption performance such as ionic strength, extraction time, and desorption time and temperature were studied. The limit of detections and limit of quantifications were obtained in the range of 0.75-0.9 and 2-5ngL -1 , respectively, demonstrating high efficiency of the prepared nanofiber. The developed method also showed good repeatability, RSD 4-9% (n=3), for the spiked aqueous solution at concentration level 150ngL -1 of chlorobenzenes, and linearity,R=0.996, in the range of 5-5000ngL -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Comparative evaluation of liquid-liquid extraction, solid-phase extraction and solid-phase microextraction for the gas chromatography-mass spectrometry determination of multiclass priority organic contaminants in wastewater.

    Science.gov (United States)

    Robles-Molina, José; Gilbert-López, Bienvenida; García-Reyes, Juan F; Molina-Díaz, Antonio

    2013-12-15

    The European Water Framework Directive (WFD) 2000/60/EC establishes guidelines to control the pollution of surface water by sorting out a list of priority substances that involves a significant risk to or via the aquatic systems. In this article, the analytical performance of three different sample preparation methodologies for the GC-MS/MS determination of multiclass organic contaminants-including priority comprounds from the WFD-in wastewater samples using gas chromatography-mass spectrometry was evaluated. The methodologies tested were: (a) liquid-liquid extraction (LLE) with n-hexane; (b) solid-phase extraction (SPE) with C18 cartridges and elution with ethyl acetate:dichloromethane (1:1 (v/v)), and (c) headspace solid-phase microextraction (HS-SPME) using two different fibers: polyacrylate and polydimethylsiloxane/carboxen/divinilbenzene. Identification and confirmation of the selected 57 compounds included in the study (comprising polycyclic aromatic hydrocarbons (PAHs), pesticides and other contaminants) were accomplished using gas chromatography tandem mass spectrometry (GC-MS/MS) with a triple quadrupole instrument operated in the multiple reaction monitoring (MRM) mode. Three MS/MS transitions were selected for unambiguous confirmation of the target chemicals. The different advantages and pitfalls of each method were discussed. In the case of both LLE and SPE procedures, the method was validated at two different concentration levels (15 and 150 ng L(-1)) obtaining recovery rates in the range 70-120% for most of the target compounds. In terms of analyte coverage, results with HS-SPME were not satisfactory, since 14 of the compounds tested were not properly recovered and the overall performance was worse than the other two methods tested. LLE, SPE and HS-SPME (using polyacrylate fiber) procedures also showed good linearity and precision. Using any of the three methodologies tested, limits of quantitation obtained for most of the detected compounds were in

  4. Electrochemical solid-phase microextraction of anions and cations using polypyrrole coatings and an integrated three-electrode device.

    Science.gov (United States)

    Liljegren, Gustav; Pettersson, Jean; Markides, Karin E; Nyholm, Leif

    2002-05-01

    A method for the extraction, transfer and desorption of anions and cations under controlled potential conditions employing a new integrated three-electrode device is described. The device, containing working, reference and counter electrodes, was prepared from tubes that could be moved vertically with respect to each other. In this way, a small amount of solvent, held by capillary force, remained between the electrodes when the device was lifted out of a solution after an extraction. This design allowed the potential control to be maintained at all times. With the new integrated device, it was possible to perform potential controlled desorption into vials containing as little as 200 microl of solution. The required ion exchange capacity was obtained by electrodeposition of a polypyrrole coating on the surface of the glassy carbon working electrode. Solid-phase microextractions of several cations or anions were performed simultaneously under potentiostatic control by doping the polypyrrole coating with different anions such as perchlorate and p-toluenesulfonate. The efficiency of the extractions, which could be altered by varying the potential of the working electrode, could be increased by 150 to 200% compared to extractions using normal solid-phase microextraction conditions under open circuit conditions. A constant potential of +1.0 V and -0.5 V with respect to the silver pseudo reference electrode, was found to be well-suited for the extraction of samples containing ppm concentrations of anions (chloride, nitrite, bromide, nitrate, sulfate and phosphate) and cations (cadmium, cobalt and zinc), respectively.

  5. Preparation of a polyacrylonitrile/multi-walled carbon nanotubes composite by surface-initiated atom transfer radical polymerization on a stainless steel wire for solid-phase microextraction.

    Science.gov (United States)

    Minet, Isabelle; Hevesi, Laszlo; Azenha, Manuel; Delhalle, Joseph; Mekhalif, Zineb

    2010-04-23

    We report on the fabrication and performances of a solid-phase microextraction (SPME) fiber based on a stainless steel wire coated with a covalently attached polyacrylonitrile (PAN)/multi-walled carbon nanotubes (MWCNTs) composite. This new coating is obtained by atom transfer radical polymerization (ATRP) of acrylonitrile mixed with MWCNTs. ATRP is initiated from 11-(2-bromo-2-methylpropionyloxy)-undecyl-phosphonic acid molecules grafted on the wire surface via the phosphonic acid group. The extraction performances of the fibers are assessed on different classes of compounds (polar, non-polar, aromatic, etc.) from water solutions by headspace extraction. The optimization of the parameters affecting the extraction efficiency of the target compounds was studied as well as the reproducibility and the repeatability of the fiber. The fibers sustain more than 200 extractions during which they remain chemically stable and maintain good performances (detection limits lower than 2 microg/l, repeatability, etc.). Considering their robustness together with their easy and inexpensive fabrication, these fibers could constitute promising alternatives to existing products. Copyright 2010 Elsevier B.V. All rights reserved.

  6. Evaluation of in vivo solid phase microextraction for minimally invasive analysis of nonvolatile phytochemicals in Amazonian plants.

    Science.gov (United States)

    Musteata, Florin Marcel; Sandoval, Manuel; Ruiz-Macedo, Juan C; Harrison, Kathleen; McKenna, Dennis; Millington, William

    2016-08-24

    Although solid phase microextraction (SPME) has been used extensively for fingerprinting volatile compounds emitted by plants, there are very few such reports for direct insertion SPME. In this research, direct contact of SPME probes with the interstitial fluid of plants was investigated as a method for phytochemical analysis. Medicinal plants from the Amazon have been the source of numerous drugs used in western medicine. However, a large number of species used in traditional medicine have not been characterized chemically, partly due to the difficulty of field work. In this project, the phytochemical composition of plants from several genera was fingerprinted by combining convenient field sampling by solid phase microextraction (SPME) with laboratory analysis by LC-MS. The new method was compared with classical sampling followed by liquid extraction (LE). SPME probes were prepared by coating stainless steel wires with a mixture of polyacrylonitrile and either RP-amide or HS-F5 silica particles. Sampling was performed by inserting the microextraction probes into various tissues of living plants in their natural environment. After in vivo extraction, the probes were sealed under vacuum and refrigerated until analyzed. The probes were desorbed in mobile phase and analyzed on a Waters Acquity UPLC with triple quadrupole mass spectrometer in positive ion mode. Twenty Amazonian plant species were sampled and unique metabolomic fingerprints were obtained. In addition, quantitative analysis was performed for previously identified compounds in three species. Comparison of the fingerprints obtained by in vivo SPME with those obtained by LE showed that 27% of the chromatographic features were unique to SPME, 57% were unique to LE, and 16% were common to both methods. In vivo SPME caused minimal damage to the plants, was much faster than traditional liquid extraction, and provided unique fingerprints for all investigated plants. SPME revealed unique chromatographic

  7. Carbon nanotubes@silicon dioxide nanohybrids coating for solid-phase microextraction of organophosphorus pesticides followed by gas chromatography-corona discharge ion mobility spectrometric detection.

    Science.gov (United States)

    Saraji, Mohammad; Jafari, Mohammad Taghi; Mossaddegh, Mehdi

    2016-01-15

    A high efficiency solid-phase microextraction (SPME) fiber coated with porous carbon nanotubes-silicon dioxide (CNTs-SiO2) nanohybrids was synthesized and applied for the determination of some organophosphorus pesticides (OPPs) in vegetables, fruits and water samples. Gas chromatography-corona discharge ion mobility spectrometry was used as the detection system. Glucose, as a biocompatible compound, was used for connecting CNT and SiO2 during a hydrothermal process. The electrospinning technique was also applied for the fiber preparation. The parameters affecting the efficiency of extraction, including stirring rate, salt effect, extraction temperature, extraction time, desorption temperature and desorption time, were investigated and optimized. The developed CNTs@SiO2 fiber presented better extraction efficiency than the commercial SPME fibers (PA, PDMS, and PDMS-DVB). The intra- and inter-day relative standard deviations were found to be lower than 6.2 and 9.0%, respectively. For water samples, the limits of detection were in the range of 0.005-0.020 μg L(-1) and the limits of quantification were between 0.010 and 0.050 μg L(-1). The results showed a good linearity in the range of 0.01-3.0 μg L(-1) for the analytes. The spiking recoveries ranged from 79 (± 9) to 99 (± 8). The method was successfully applied for the determination of OPPs in real samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Polydopamine-based immobilization of a hydrazone covalent organic framework for headspace solid-phase microextraction of pyrethroids in vegetables and fruits.

    Science.gov (United States)

    Wu, Mingxue; Chen, Gang; Liu, Ping; Zhou, Weihong; Jia, Qiong

    2016-07-22

    We designed a novel hydrazone covalent organic framework (COF) and developed a polydopamine (PDA) method to immobilize COF on a stainless steel fiber for headspace solid-phase microextraction (HS-SPME). A series of characterization studies was performed to validate the structure and property of the prepared fiber. The COF-PDA fiber was applied for the extraction of pyrethroids coupled with gas chromatography equipped with an electron capture detector (GC-ECD). Under the optimum experimental conditions, high enhancement factors of 307-2327 were achieved, indicating that the hydrazone COF possessed good extraction efficiency for pyrethroids. The detection limits ranged from 0.11 to 0.23μgkg(-1) with relative standard deviations varying in the range of 3.6-9.2% (intra-batch) and 6.9-12.1% (inter-batch), respectively. The developed method was applied to the determination of pyrethroids in fruit and vegetable samples and the accuracy was assessed through recovery experiments. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Volatile phytochemical composition of rhizome of ginger after extraction by headspace solid-phase microextraction, petrol ether extraction and steam distillation extraction

    Directory of Open Access Journals (Sweden)

    Zhan-nan Yang

    2009-06-01

    Full Text Available The sampling techniques headspace solid-phase microextraction (HS-SPME, petrol ether extraction (PEE and steam distillation extraction (SDE were compared for the GC-MS of volatile constituents present in ginger (Zingiber officinale. The effects of different parameters, such as extraction fibers, extraction time, extraction temperature and particle size ranges, on the HSSPME of rhizome of ginger were investigated. Zingiberene (53.12% were predominant components of ginger samples obtained by HS-SPME whereas those levels were 39.01% in the same samples by PEE and 35.05% in those by SDE, respectively. HS-SPME with polydimethylsiloxane (PDMS fiber was more selective and particularly efficient for the isolation of volatile phytochemical composition and afforded a higher yield of total compounds than PEE and SDE. The specifically compound isolated by SPME, which due to effective fiber, was much larger than that isolated by PEE or SDE. HS-SPME is a powerful tool for determining the volatile constitutes present in the traditional Chinese medicines.

  10. Simple and sensitive analysis of nereistoxin and its metabolites in human serum using headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Namera, A; Watanabe, T; Yashiki, M; Kojima, T; Urabe, T

    1999-03-01

    A simple method for the analysis of nereistoxin and its metabolites in human serum using headspace solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) is developed. A vial containing a serum sample, 5M sodium hydroxide, and benzylacetone (internal standard) is heated to 70 degrees C, and an SPME fiber is exposed for 30 min in the headspace of the vial. The compounds extracted by the fiber are desorbed by exposing the fiber in the injection port of the GC-MS. The calibration curves show linearity in the range of 0.05-5.0 micrograms/mL for nereistoxin and N-methyl-N-(2-methylthio-1-methylthiomethyl)ethylamine, 0.01-5.0 micrograms/mL for S,S'-dimethyl dihydronereistoxin, and 0.5-10 micrograms/mL for 2-methylthio-1-methylthiomethylethylamine in serum. No interferences are found, and the analysis time is 50 min for one sample. In addition, this proposed method is applied to a patient who attempted suicide by ingesting Padan 4R, a herbicide. Padan 4R contains 4% cartap hydrochloride, which is an analogue of nereistoxin. Nereistoxin and its metabolites are detected in the serum samples collected from the patient during hospitalization. The concentration ranges of nereistoxin in the serum are 0.09-2.69 micrograms/mL.

  11. In vitro evaluation of new biocompatible coatings for solid-phase microextraction: implications for drug analysis and in vivo sampling applications.

    Science.gov (United States)

    Vuckovic, Dajana; Shirey, Robert; Chen, Yong; Sidisky, Len; Aurand, Craig; Stenerson, Katherine; Pawliszyn, Janusz

    2009-04-13

    A new line of solid-phase microextraction (SPME) coatings suitable for use with liquid chromatography applications was recently developed to address the limitations of the currently available coatings. The proposed coatings were immobilized on the metal fiber core and consisted of a mixture of proprietary biocompatible binder and various types of coated silica (octadecyl, polar embedded and cyano) particles. The aim of this research was to perform in vitro assessment of these new SPME fibers in order to evaluate their suitability for drug analysis and in vivo SPME applications. The main parameters examined were extraction efficiency, solvent resistance, preconditioning, dependence of extraction kinetics on coating thickness, carryover, linear range and inter-fiber reproducibility. The performance of the proposed coatings was compared against commercial Carbowax-TPR (CW-TPR) coating, when applicable. The fibers were evaluated for the extraction of drugs of different classes (carbamazepine, propranolol, pseudoephedrine, ranitidine and diazepam) from plasma and urine. The analyses were performed using liquid chromatography-tandem mass spectrometry. The results show that the fibers perform very well for the extraction of biological fluids with no sample pre-treatment required and can also be used for in vivo sampling applications of flowing blood. A coating thickness of 45 microm was found to be a good compromise between extraction capacity and extraction kinetics. Due to the high extraction efficiency of these coatings, pre-equilibrium SPME with very short extraction times (2 min) can be employed to increase sample throughput. Inter-fiber reproducibility was drugs examined in plasma, which is a significant improvement over polypyrrole coatings reported in literature, and permits single fiber use for in vivo applications.

  12. Quantification of 31 volatile organic compounds in whole blood using solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Blount, Benjamin C; Kobelski, Robert J; McElprang, David O; Ashley, David L; Morrow, John C; Chambers, David M; Cardinali, Frederick L

    2006-03-07

    The prevalence of exposure to volatile organic compounds (VOCs) has raised concern about possible health effects resulting from chronic human exposure. To support studies exploring the relation between VOC exposure and health effects, we developed an automated analytical method using solid-phase microextraction (SPME), capillary gas chromatography (GC), and quadrupole mass spectrometry (MS). This method quantifies trace levels (low parts per trillion) of 14 halogenated alkanes, 5 halogenated alkenes, 10 aromatic compounds, and 2 other VOCs in human blood. Detection limits for the SPME-GC-MS method range from 0.005 to 0.12 microg/L, with linear calibration curves spanning three orders of magnitude. The improved throughput of this method will enable us to expand biomonitoring efforts to assess nonoccupational VOC exposure in large epidemiological studies.

  13. Determination of some volatile compounds in alcoholic beverage by headspace solid-phase microextraction gas chromatography - mass spectrometry

    Science.gov (United States)

    Schmutzer, G.; Avram, V.; Feher, I.; David, L.; Moldovan, Z.

    2012-02-01

    The volatile composition of alcoholic beverage was studied by headspace solid-phase microextraction (HSSPME) method and gas chromatography - mass spectrometry (GC-MS). Some volatile compounds, such as alcohols, esters, terpenes and other are mainly responsible for the flavor of fortified wines and their amounts specify the quality of the alcoholic beverages. From this perspective it is interesting to develop a rapid, selective and sensitive analytical method suitable for simultaneous quantification of the main molecules being responsible for the organoleptic characteristic of alcoholic beverages. Vermouth fortified drink was analyzed in order to characterize the volatile profile. Using the HS-SPME/GC-MS a number of twenty-six volatile compounds from a commercial market alcoholic beverage were identified. The most abundant compounds were m-thymol, o-thymol and eugenol, alongside of the ethyl ester compounds.

  14. Comparison of membrane assisted solvent extraction, stir bar sorptive extraction, and solid phase microextraction in analysis of tetramine in food.

    Science.gov (United States)

    De Jager, Lowri S; Perfetti, Gracia A; Diachenko, Gregory W

    2009-04-01

    Three environmentally friendly extraction techniques, membrane assisted solvent extraction (MASE), stir bar sorptive extraction (SBSE), and headspace solid phase microextraction (HS-SPME), were compared for the direct analysis of the highly toxic rodenticide tetramine in food. The optimized MASE method was applied to seven foods fortified with tetramine and compared to previously reported SBSE and HS-SPME results. Parameters such as the standard addition linearity (MASE (0.964-0.999), SBSE (0.966-0.999), HS-SPME (0.955-0.999)), recovery (MASE (12-86%), SBSE (36-130%), HS-SPME (50-200%)), reproducibility (MASE (3.0-30%), SBSE (4.4-9.6%), HS-SPME (1-12%)), and LOD (MASE (1.6-6.4 ng/g), SBSE (0.2-2.1 ng/g), HS-SPME (0.9-4.3 ng/g)) were compared.

  15. Headspace solid-phase microextraction with 1-pyrenyldiazomethane on-fibre derivatisation for analysis of fluoroacetic acid in biological samples.

    Science.gov (United States)

    Sporkert, Frank; Pragst, Fritz; Hübner, Sandra; Mills, Graham

    2002-05-25

    A new and in part automated headspace solid-phase microextraction method for quantitative determination of the highly toxic rodenticide fluoroacetic acid (FAA) in serum and other biological samples has been developed. FAA and deuterated acetic acid (internal standard) were extracted from acidified samples by a StableFlex divinylbenzene-Carboxen on polydimethylsiloxane fibre. The acids were derivatised on the fibre in-situ with 1-pyrenyldiazomethane and detected using gas chromatography-mass spectrometry with electron impact ionisation and selected ion monitoring. The calibration curve for FAA in serum was linear over the range from 0.02 to 5 microg/ml, with limits of detection and quantification of 0.02 and 0.07 microg/ml, respectively. The method was also tested with spiked whole blood, urine, stomach contents and kidney samples. It was sufficiently reliable, reproducible and sensitive for use in routine forensic toxicology applications.

  16. Headspace solid-phase microextraction-gas chromatography-mass spectrometry applied to quality control in multilayer-packaging manufacture.

    Science.gov (United States)

    Ezquerro, Oscar; Pons, Begoña; Tena, María Teresa

    2003-08-01

    A method based on headspace solid-phase microextraction-gas chromatography-mass spectrometry is proposed for the quality control of multilayer packaging and its manufacturing process. Volatile organic compounds (VOCs) are produced in the manufacturing process of the packaging. They can cause organoleptic problems or modify the properties of the packaging depending on the nature and the amount of the VOCs formed. The quantification using packaging samples with a known VOC concentration for the calibration is proposed in order to reduce the analysis time, and the method is validated using a statistical test. Finally, the method is applied to the determination of odour-responsible compounds in multilayer packaging samples obtained under different extrusion-coating conditions, i.e. type of extruder, type of polymer and extrusion speed.

  17. Analysis of volatiles in dehydrated carrot samples by solid-phase microextraction followed by GC-MS.

    Science.gov (United States)

    Soria, Ana Cristina; Sanz, Jesús; Villamiel, Mar

    2008-10-01

    A solid-phase microextraction (SPME)-based method for the GC-MS analysis of volatiles in dehydrated carrot root samples has been developed and the effect of the most important factors (fibre coating, extraction temperature, equilibrium time and extraction time) on the fractionation of different volatiles has been studied. GC-MS chromatograms showed terpenoids relevant to carrot aroma such as alpha-pinene, sabinene, beta-myrcene, limonene, gamma-terpinene, terpinolene, trans-caryophyllene and beta-bisabolene, and several furan derivatives whose origin is discussed in this paper. As an example of application, this methodology has been used for the characterization of volatile composition of industrially dehydrated carrots. SPME followed by GC-MS is shown as an affordable, fast and solvent-free technique which can be performed with low sample amounts and be easily implemented at an industry for quality control purposes.

  18. Screening for sarin in air and water by solid-phase microextraction-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Schneider, J F; Boparai, A S; Reed, L L

    2001-10-01

    A method of screening air and water samples for the chemical-warfare agent Sarin is developed using solid-phase microextraction (SPME)-gas chromatography (GC)-mass spectrometry (MS). The SPME field kit sampler is ideal for collecting air and water samples in the field and transporting samples safely to the laboratory. The sampler also allows the sample to be introduced into the GC-MS system without further sample preparation. Results of the tests with Sarin using the SPME technique indicate that a sample collection time of 5 min is sufficient to detect 100 ng/L of Sarin in air. For water samples, Sarin is detected at a concentration of 12 microg/mL or higher. This method is ideal for screening samples for quick response situations.

  19. Head-Space Solid Phase Micro-extraction Followed by GC/MS Analysis of the Volatile Components in Seeds of Cinnamonum camphora

    OpenAIRE

    Yang Yong; Tao Wenyi

    2005-01-01

    The volatile components in seeds of Cinnamomum camphora were analyzed by Solid Phase Micro-extraction (SPME) combined with GC/MS. Twenty four main kinds of volatile compounds, among which the Sesquiterpene (29%), 3-Hexen-2-one (25%) and Monoterpene (10.22%), were separated and analyzed.

  20. Negligible depletion solid-phase microextraction with radiolabeled analytes to study free concentrations and protein binding : an example with [3H]Estradiol

    NARCIS (Netherlands)

    Heringa, M.B.; Pastor, D.; Algra, J.; Vaes, W.H.J.; Hemmens, J.L.M.

    2002-01-01

    A new method is presented that enables sensitive measurement of free concentrations of radiolabeled ligands. Additionally, protein binding of radiochemicals in complex matrixes can be determined with this new technique that combines negligible depletion solid-phase microextraction (nd-SPME) with

  1. Freeze-thaw method improves the detection of volatile compounds in insects using Headspace Solid-Phase Microextraction (HS-SPME)

    Science.gov (United States)

    Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography–mass spectrometry (GC-MS) is commonly used in analyzing insect volatiles. In order to improve the detection of volatiles in insects, a freeze-thaw method was applied to insect samples before the HS-SPME-GC-MS analysis. ...

  2. Quantitative Analysis of Bisphenol A Leached from Household Plastics by Solid-Phase Microextraction and Gas Chromatography-Mass Spectrometry (SPME-GC-MS)

    Science.gov (United States)

    Johnson, Bettie Obi; Burke, Fernanda M.; Harrison, Rebecca; Burdette, Samantha

    2012-01-01

    The measurement of trace levels of bisphenol A (BPA) leached out of household plastics using solid-phase microextraction (SPME) with gas chromatography-mass spectrometry (GC-MS) is reported here. BPA is an endocrine-disrupting compound used in the industrial manufacture of polycarbonate plastic bottles and epoxy resin can liners. This experiment…

  3. Determination of amphetamine-type stimulants in oral fluid by solid-phase microextraction and gas chromatography-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Daniele Z., E-mail: daniele.dzs@dpf.gov.br [Setor Tecnico-Cientifico, Superintendencia Regional do Departamento de Policia Federal no Rio Grande do Sul, 1365 Ipiranga Avenue, Azenha, Zip Code 90160-093 Porto Alegre, Rio Grande do Sul (Brazil); Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, 2752 Ipiranga Avenue, Santana, Zip Code 90610-000 Porto Alegre, Rio Grande do Sul (Brazil); Boehl, Paula O.; Comiran, Eloisa; Mariotti, Kristiane C. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, 2752 Ipiranga Avenue, Santana, Zip Code 90610-000 Porto Alegre, Rio Grande do Sul (Brazil); Pechansky, Flavio [Centro de Pesquisa em Alcool e Drogas (CPAD), Hospital de Clinicas de Porto Alegre, Universidade Federal do Rio Grande do Sul, 2350, Ramiro Barcelos Street, Zip Code 90035-903 Porto Alegre, Rio Grande do Sul (Brazil); Duarte, Paulina C.A.V. [Secretaria Nacional de Politicas sobre Drogas (SENAD), Esplanada dos Ministerios, Block ' A' , 5th floor, Zip Code 70050-907 Brasilia, Distrito Federal (Brazil); De Boni, Raquel [Centro de Pesquisa em Alcool e Drogas (CPAD), Hospital de Clinicas de Porto Alegre, Universidade Federal do Rio Grande do Sul, 2350, Ramiro Barcelos Street, Zip Code 90035-903 Porto Alegre, Rio Grande do Sul (Brazil); Froehlich, Pedro E.; Limberger, Renata P. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, 2752 Ipiranga Avenue, Santana, Zip Code 90610-000 Porto Alegre, Rio Grande do Sul (Brazil)

    2011-06-24

    Graphical abstract: Highlights: > Propylchloroformate derivatization of amphetamine-type stimulants in oral fluid. > Direct immersion solid-phase microextraction/gas chromatography-mass spectrometry. > Linear range 2(4)-256 ng mL{sup -1}, detection limits 0.5-2 ng mL{sup -1}. > Accuracy 98-112%, precision <15% of RSD, recovery 77-112%. > Importance of residual evaluation in checking model goodness-of-fit. - Abstract: A method for the simultaneous identification and quantification of amphetamine (AMP), methamphetamine (MET), fenproporex (FEN), diethylpropion (DIE) and methylphenidate (MPH) in oral fluid collected with Quantisal{sup TM} device has been developed and validated. Thereunto, in-matrix propylchloroformate derivatization followed by direct immersion solid-phase microextraction and gas chromatography-mass spectrometry were employed. Deuterium labeled AMP was used as internal standard for all the stimulants and analysis was performed using the selected ion monitoring mode. The detector response was linear for the studied drugs in the concentration range of 2-256 ng mL{sup -1} (neat oral fluid), except for FEN, whereas the linear range was 4-256 ng mL{sup -1}. The detection limits were 0.5 ng mL{sup -1} (MET), 1 ng mL{sup -1} (MPH) and 2 ng mL{sup -1} (DIE, AMP, FEN), respectively. Accuracy of quality control samples remained within 98.2-111.9% of the target concentrations, while precision has not exceeded 15% of the relative standard deviation. Recoveries with Quantisal{sup TM} device ranged from 77.2% to 112.1%. Also, the goodness-of-fit concerning the ordinary least squares model in the statistical inference of data has been tested through residual plotting and ANOVA. The validated method can be easily automated and then used for screening and confirmation of amphetamine-type stimulants in drivers' oral fluid.

  4. Determination of amphetamine-type stimulants in oral fluid by solid-phase microextraction and gas chromatography-mass spectrometry

    International Nuclear Information System (INIS)

    Souza, Daniele Z.; Boehl, Paula O.; Comiran, Eloisa; Mariotti, Kristiane C.; Pechansky, Flavio; Duarte, Paulina C.A.V.; De Boni, Raquel; Froehlich, Pedro E.; Limberger, Renata P.

    2011-01-01

    Graphical abstract: Highlights: → Propylchloroformate derivatization of amphetamine-type stimulants in oral fluid. → Direct immersion solid-phase microextraction/gas chromatography-mass spectrometry. → Linear range 2(4)-256 ng mL -1 , detection limits 0.5-2 ng mL -1 . → Accuracy 98-112%, precision TM device has been developed and validated. Thereunto, in-matrix propylchloroformate derivatization followed by direct immersion solid-phase microextraction and gas chromatography-mass spectrometry were employed. Deuterium labeled AMP was used as internal standard for all the stimulants and analysis was performed using the selected ion monitoring mode. The detector response was linear for the studied drugs in the concentration range of 2-256 ng mL -1 (neat oral fluid), except for FEN, whereas the linear range was 4-256 ng mL -1 . The detection limits were 0.5 ng mL -1 (MET), 1 ng mL -1 (MPH) and 2 ng mL -1 (DIE, AMP, FEN), respectively. Accuracy of quality control samples remained within 98.2-111.9% of the target concentrations, while precision has not exceeded 15% of the relative standard deviation. Recoveries with Quantisal TM device ranged from 77.2% to 112.1%. Also, the goodness-of-fit concerning the ordinary least squares model in the statistical inference of data has been tested through residual plotting and ANOVA. The validated method can be easily automated and then used for screening and confirmation of amphetamine-type stimulants in drivers' oral fluid.

  5. Fabrication of a polymeric composite incorporating metal-organic framework nanosheets for solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Songbo; Lin, Wei; Xu, Jianqiao [MOE Key Laboratory of Aquatic Product of Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 (China); Wang, Ying [School of Pharmacy, Guiyang Medical University, Guiyang 550004 (China); Liu, Shuqin; Zhu, Fang [MOE Key Laboratory of Aquatic Product of Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 (China); Liu, Yuan, E-mail: yliu@shou.edu.cn [College of Food Science & Technology, Shanghai Ocean University, Shanghai 201306 (China); Ouyang, Gangfeng, E-mail: cesoygf@mail.sysu.edu.cn [MOE Key Laboratory of Aquatic Product of Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275 (China)

    2017-06-08

    In this contribution, it was discovered that even distribution of a metal-organic framework (MOF) [e.g. copper 1,4-benzenedicarboxylate (CBDC)] within polymeric matrixes (e.g. polyimide) resulted in a high-efficient coating material on the surface of a stainless steel wire (SSW). Consequently, a home-made solid phase microextraction (SPME) fiber was fabricated for fast determination of target analytes in real water samples. Scanning electron microscope images indicated that the coating possessed homogenously porous surface. Coupled with gas chromatography-mass spectrometry (GC-MS) and direct immersion SPME (DI-SPME) technique, the fiber was evaluated through the analysis of five polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Under optimized extraction and desorption conditions, the established method based on the home-made fiber exhibited good repeatability (4.2–12.7%, n = 6) and reproducibility (0.9–11.7%, n = 3), low limits of detection (LODs, 0.11–2.10 ng L{sup −1}), low limits of quantification (LOQs, 0.36–6.99 ng L{sup −1}) and wide linear ranges (20–5000 ng L{sup −1}). Eventually, the method was proven applicable in the determination of PAHs in real samples, as the recoveries were in a satisfactory range (81.7–116%). - Highlights: • A homogenously porous CBDC@polyimide-coated fiber was fabricated and characterized. • The fiber exhibited highly desired extraction performance towards PAHs. • The fiber was employed for the determination of PAHs in real aqueous samples.

  6. Fabrication of a polymeric composite incorporating metal-organic framework nanosheets for solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples

    International Nuclear Information System (INIS)

    Wei, Songbo; Lin, Wei; Xu, Jianqiao; Wang, Ying; Liu, Shuqin; Zhu, Fang; Liu, Yuan; Ouyang, Gangfeng

    2017-01-01

    In this contribution, it was discovered that even distribution of a metal-organic framework (MOF) [e.g. copper 1,4-benzenedicarboxylate (CBDC)] within polymeric matrixes (e.g. polyimide) resulted in a high-efficient coating material on the surface of a stainless steel wire (SSW). Consequently, a home-made solid phase microextraction (SPME) fiber was fabricated for fast determination of target analytes in real water samples. Scanning electron microscope images indicated that the coating possessed homogenously porous surface. Coupled with gas chromatography-mass spectrometry (GC-MS) and direct immersion SPME (DI-SPME) technique, the fiber was evaluated through the analysis of five polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Under optimized extraction and desorption conditions, the established method based on the home-made fiber exhibited good repeatability (4.2–12.7%, n = 6) and reproducibility (0.9–11.7%, n = 3), low limits of detection (LODs, 0.11–2.10 ng L −1 ), low limits of quantification (LOQs, 0.36–6.99 ng L −1 ) and wide linear ranges (20–5000 ng L −1 ). Eventually, the method was proven applicable in the determination of PAHs in real samples, as the recoveries were in a satisfactory range (81.7–116%). - Highlights: • A homogenously porous CBDC@polyimide-coated fiber was fabricated and characterized. • The fiber exhibited highly desired extraction performance towards PAHs. • The fiber was employed for the determination of PAHs in real aqueous samples.

  7. Headspace solid-phase microextraction gas chromatography-mass spectrometry analysis of volatiles in orujo spirits from a defined geographical origin.

    Science.gov (United States)

    Peña, Rosa M; Barciela, Julia; Herrero, Carlos; García-Martín, Sagrario

    2008-04-23

    A headspace solid-phase microextraction (HS-SPME) and gas chromatography-selective ion monitoring/mass spectrometry (GC-SIM/MS) method was optimized for analysis of 22 volatile compounds in orujo spirit samples from the Geographic Denomination "Orujo de Galicia/Augardente de Galicia". HS-SPME experimental conditions, such as fiber coating, extraction temperature, extraction and pre-equilibrium time, sample volume, and the presence of salt, were studied to improve the extraction process. The best results were obtained using a 65 microm Carbowax-divinylbenzene fiber during a headspace extraction at 40 degrees C with constant magnetic stirring for 15 min and after a 5 min period of pre-equilibrium time. The sample volume was 6 mL of orujo containing 25% of NaCl, placed in 12 mL glass vials equipped with a screw cap and PTFE/silicone septum. Desorption was performed directly in the gas chromatograph injector port for 5 min at 250 degrees C using the splitless mode. The proposed method is sensible (with detection limits between 0.0045 and 0.2399 mg/L), precise (with coefficients of variation in the range 0.99-8.18%), and linear over more than 1 order of magnitude. The developed method presented recoveries comprised between 76.0 and 112.4%. The applicability of the new method was demonstrated by determining the considered 22 volatile compounds in nine orujo commercial samples with quality and origin brands.

  8. Determination of phthalate esters in vegetable oils using direct immersion solid-phase microextraction and fast gas chromatography coupled with triple quadrupole mass spectrometry.

    Science.gov (United States)

    Barp, Laura; Purcaro, Giorgia; Franchina, Flavio A; Zoccali, Mariosimone; Sciarrone, Danilo; Tranchida, Peter Q; Mondello, Luigi

    2015-08-05

    Phthalates are a group of synthetic compounds mainly used as plasticizers, which have been classified as endocrine-disrupting chemicals and potential human-cancer causing agents. They can be found in high amounts in foods, deriving mainly from plastic packaging. The analytical determination of these compounds is very challenging since they are ubiquitous. Therefore, minimization of sample manipulation is highly desirable. The present work exploited the application of a solid-phase microextraction method for the analysis of phthalates in vegetable oil. A preliminary comparison between a polydimethylsiloxane (PDMS) and a Carbopack Z/PDMS fiber was carried out both in the headspace and direct immersion extraction modes. Before immersing the fiber, a rapid liquid-liquid extraction was performed using acetonitrile to remove the bulk of triglycerides. PDMS in the direct immersion mode showed the best performance. The method was fully validated obtaining a good linearity with a coefficient of correlation of over 0.9960 for all compounds, repeatability and accuracy values generally better than 10%, and very good limit of quantification values. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Dye-doped nanostructure polypyrrole film for electrochemically switching solid-phase microextraction of Ni(II) and ICP-OES analysis of waste water.

    Science.gov (United States)

    Shamaeli, Ehsan; Alizadeh, Naader

    2012-01-01

    A nanostructure fiber based on conducting polypyrrole synthesized by an electrochemical method has been developed, and used for electrochemically switching solid-phase microextraction (ES-SPME). The ES-SPME was prepared by the doping of eriochrome blue in polypyrrole (PPy-ECB) and used for selectively extracting the Ni(II) cation in the presence of some transition and heavy metal ions. The cation-exchange behavior of electrochemically prepared polypyrrole on stainless-steel with and without eriochrome blue (ECB) dye was characterized using ICP-OES analysis. The effects of the scan rate for electrochemical synthesis, uptake and the release potential on the extraction behavior of the PPy-ECB conductive fiber were studied. Uptake and release time profiles show that the process of electrically switched cation exchange could be completed within 250 s. The results of the present study point concerning the possibility of developing a selective extraction process for Ni(II) from waste water was explored using such a nanostructured PPy-ECB film through an electrically switched cation exchange. 2012 © The Japan Society for Analytical Chemistry

  10. In situ hydrothermal growth of polyaniline coating for in-tube solid-phase microextraction towards ultraviolet filters in environmental water samples.

    Science.gov (United States)

    Bu, Yanan; Feng, Juanjuan; Wang, Xiuqin; Tian, Yu; Sun, Min; Luo, Chuannan

    2017-02-03

    A facile, low cost, sensitive and environmentally friendly polyaniline (PANI) coating was prepared onto the basalt fibers (BFs) by in situ hydrothermal growth method. PANI functionalized BFs were placed into a poly(ether ether ketone) (PEEK) tube as a fibers-in-tube solid-phase microextraction (SPME) device. The extraction and analysis processes were carried out by connecting it to high performance liquid chromatography (HPLC). Three ultraviolet filters including 2-hydroxy-4-methoxybenzophenone, phenyl salicylate and 2,4-dihydroxybenzophenone were employed as model analytes. Under the optimal extraction and desorption conditions, online in-tube SPME-HPLC analysis method was established and afforded satisfactory enrichment factors (1323-1555), wide linear ranges (0.06-100μgL -1 ) with correlation coefficients ranging from 0.9995 to 0.9999, low limits of detection (0.02-0.05μgL -1 ) and acceptable extraction repeatability (RSD<7.8%, n=6) and preparation repeatability (RSD<9.7%, n=3). The proposed method was successfully applied to the determination of the three ultraviolet filters in two environmental water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Quantification of benzene, toluene, ethylbenzene and o-xylene in internal combustion engine exhaust with time-weighted average solid phase microextraction and gas chromatography mass spectrometry.

    Science.gov (United States)

    Baimatova, Nassiba; Koziel, Jacek A; Kenessov, Bulat

    2015-05-11

    A new and simple method for benzene, toluene, ethylbenzene and o-xylene (BTEX) quantification in vehicle exhaust was developed based on diffusion-controlled extraction onto a retracted solid-phase microextraction (SPME) fiber coating. The rationale was to develop a method based on existing and proven SPME technology that is feasible for field adaptation in developing countries. Passive sampling with SPME fiber retracted into the needle extracted nearly two orders of magnitude less mass (n) compared with exposed fiber (outside of needle) and sampling was in a time weighted-averaging (TWA) mode. Both the sampling time (t) and fiber retraction depth (Z) were adjusted to quantify a wider range of Cgas. Extraction and quantification is conducted in a non-equilibrium mode. Effects of Cgas, t, Z and T were tested. In addition, contribution of n extracted by metallic surfaces of needle assembly without SPME coating was studied. Effects of sample storage time on n loss was studied. Retracted TWA-SPME extractions followed the theoretical model. Extracted n of BTEX was proportional to Cgas, t, Dg, T and inversely proportional to Z. Method detection limits were 1.8, 2.7, 2.1 and 5.2 mg m(-3) (0.51, 0.83, 0.66 and 1.62 ppm) for BTEX, respectively. The contribution of extraction onto metallic surfaces was reproducible and influenced by Cgas and t and less so by T and by the Z. The new method was applied to measure BTEX in the exhaust gas of a Ford Crown Victoria 1995 and compared with a whole gas and direct injection method. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Determination of fluoroquinolones in eggs using in-tube solid-phase microextraction coupled to high-performance liquid chromatography.

    Science.gov (United States)

    Huang, Jing-Fang; Lin, Bo; Yu, Qiong-Wei; Feng, Yu-Qi

    2006-03-01

    A simple, rapid, and sensitive method using in-tube solid-phase microextraction (in-tube SPME) based on poly(methacrylic acid-ethylene glycol dimethacrylate) (MAA-EGDMA) monolith coupled to HPLC with fluorescence and UV detection was developed for the determination of five fluoroquinolones (FQs). Ofloxacin (OFL), norfloxacin (NOR), ciprofloxacin (CIP), enrofloxacin (ENRO), and sarafloxacin (SARA) can be enriched and determined in the spiked eggs and albumins. CIP/ENRO in eggs and albumins of ENRO-treated hens were also studied using the proposed method. Only homogenization, dilution, and centrifugation were required before the sample was supplied to the in-tube microextraction, and no organic solvents were consumed in the procedures. Under the optimized extraction conditions, good extraction efficiency for the five FQs was obtained with no matrix interference in the process of extraction and the subsequent chromatographic separation. The detection limits (S/N=3) were found to be 0.1-2.6 ng g(-1) and 0.2-2.4 ng g(-1) in whole egg and egg albumin, respectively. Good linearity could be achieved over the range 2-500 ng mL(-1) for the five FQs with regression coefficients above 0.9995 in both whole egg and albumin. The reproducibility of the method was evaluated at three concentration levels, with the resulting relative standard deviations (RSDs) less than 7%. The method was successfully applied to the analysis of ENRO and its primary metabolite CIP in the eggs and albumins of ENRO-treated hens.

  13. Application of response surface methodology to optimize solid-phase microextraction procedure for chromatographic determination of aroma-active monoterpenes in berries.

    Science.gov (United States)

    Chmiel, Tomasz; Kupska, Magdalena; Wardencki, Waldemar; Namieśnik, Jacek

    2017-04-15

    Most of scientific papers concern the qualitative or semi-quantitative analysis of aroma-active terpenes in liquid food matrices. Therefore, the procedure based on solid-phase microextraction and two-dimensional gas chromatography-time-of-flight mass spectrometry for determination of monoterpenes in fresh berries was developed. The optimal extraction conditions using divinylbenzene-carboxen-polydimethylsiloxane fiber were: temperature of 50°C, extraction time of 26min, equilibrium time of 29min. The developed procedure provides a high recovery (70.8-99.2%), good repeatability (CV0.9915) and offers practical advantages over currently used methods: reliability of compounds identification, simplicity of extraction and at least one order of magnitude lower detection limits (0.10-0.011μg/L). The method was successfully applied to determine monoterpenes in 27 berry samples of different varieties and 4 berry products. Tukey's test revealed that monoterpenes content is a reliable indicator of fruit maturity and origin. It suggests that the method may be of interest to researchers and food industry. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Combined solid-phase microextraction and high-performance liquid chromatography with ultroviolet detection for simultaneous analysis of clenbuterol, salbutamol and ractopamine in pig samples.

    Science.gov (United States)

    Du, Wei; Zhang, Siruo; Fu, Qiang; Zhao, Gang; Chang, Chun

    2013-12-01

    A simple and sensitive method based on the combination of solid-phase microextraction (SPME) and high-performance liquid chromatography with ultroviolet detection was developed for the simultaneous determination of clenbuterol, salbutamol and ractopamine in pig samples. Parameters of the SPME procedure affecting extraction efficiency, such as the type of fiber, extraction time, extraction temperature, ion strength, pH of sample and stirring rate, were optimized. The developed method was validated according to the International Conference on Harmonization guidelines. The calibration curves were linear over a range of 0.5-50 µg/L for clenbuterol and ractopamine, and 0.2-20 µg/L for salbutamol. The limits of detection were 0.1 µg/L for clenbuterol, 0.05 µg/L for salbutamol and 0.1 μg/L for ractopamine, respectively. The averages of intra- and inter-day accuracy ranged from 79.8 to 92.4%. The intra-day and inter-day precision were below 9.6% for the three analytes. This method exhibited the advantages of simplicity, rapidity and low solvent consumption, and was suitable for the monitoring of β2 -agonists residue in pig samples. Copyright © 2013 John Wiley & Sons, Ltd.

  15. Monitoring of gamma radiolytic degradation products of methoxychlor pesticide in water by solid phase micro-extraction using hplc and GC-MS (abstract)

    International Nuclear Information System (INIS)

    Butt, S.B.; Zafar, A.

    2011-01-01

    Monitoring, removal and management of toxic chemicals is an essential area of study regarding sustainable progress. Different approaches are adopted to eliminate these water born toxics from water and waste water. Among these gamma radiolytic is an emerging option. This ionization radiation generates highly reactive radicals that reacts with pollutants and hence eliminates these. A solid-phase micro-extraction (SPME) procedure has been developed for the successful preconcentration of organic pollutant irradiated water. A SPME fused-silica fiber coated with Polyacrylate was used as a probe to extract the organic pollutant after irradiation. In this reference, degradation of priority organic pollutant methoxychlor (1, 1, 1-Trichloro 2, 2-bis (p-methoxyphenyl) ethane, in water by gamma irradiation under varied experimental conditions has been investigated. The degree of gamma radiolytic degradation was monitored by HPLC-UV and GC-MS. For 4 kGy and 5 kGy gamma radiation dose at a rate of 200 kGyh/sup -1/ greater or equal to 95 % and 98 % MXC was degraded respectively. The degradation products were identified by Mass Spectrometry after comparing their MS spectras with the NIST 98 library. The major degradation occurs via dechlorination, dehydro chlorination, by the detachment of methoxyphenyl from MXC and by interaction of other radicals generated by the water radiolysis. (author)

  16. Optimization of the coating procedure for a high-throughput 96-blade solid phase microextraction system coupled with LC-MS/MS for analysis of complex samples.

    Science.gov (United States)

    Mirnaghi, Fatemeh S; Chen, Yong; Sidisky, Leonard M; Pawliszyn, Janusz

    2011-08-01

    Biocompatible C18-polyacrylonitrile (PAN) coating was used as the extraction phase for an automated 96-blade solid phase microextraction (SPME) system with thin-film geometry. Three different methods of coating preparation (dipping, brush painting, and spraying) were evaluated; the spraying method was optimum in terms of its stability and reusability. The high-throughput sample preparation was achieved by using a robotic autosampler that enabled simultaneous preparation of 96 samples in 96-well-plate format. The increased volume of the extraction phase of the C18-PAN thin film coating resulted in significant enhancement in the extraction recovery when compared with that of the C18-PAN rod fibers. Various factors, such as reusability, reproducibility, pH stability, and reliability of the coating were evaluated. The results showed that the C18-PAN 96-blade SPME coating presented good extraction recovery, long-term reusability, good reproducibility, and biocompatibility. The limits of detection and quantitation were in the ranges of 0.1-0.3 and 0.5-1 ng/mL for all four analytes.

  17. Determination of organotin compounds by headspace solid-phase microextraction-gas chromatography-pulsed flame-photometric detection (HS-SPME-GC-PFPD)

    Energy Technology Data Exchange (ETDEWEB)

    Bravo, Manuel [Universite de Pau et des Pays de L' Adour, Laboratoire de Chimie Analytique, LCABIE, UMR CNRS 5034, Pau (France); Pontificia Universidad Catolica de Valparaiso, Laboratorio de Quimica Analitica y Ambiental, Instituto de Quimica, Valparaiso (Chile); Lespes, Gaetane; Gautier, Martine Potin [Pontificia Universidad Catolica de Valparaiso, Laboratorio de Quimica Analitica y Ambiental, Instituto de Quimica, Valparaiso (Chile); Gregori, Ida de; Pinochet, Hugo [Universite de Pau et des Pays de L' Adour, Laboratoire de Chimie Analytique, LCABIE, UMR CNRS 5034, Pau (France)

    2005-12-01

    A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 {mu}m PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L{sup -1} in water and close to ng (Sn) kg{sup -1} in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME-GC-PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices. (orig.)

  18. Determination of organotin compounds by headspace solid-phase microextraction-gas chromatography-pulsed flame-photometric detection (HS-SPME-GC-PFPD).

    Science.gov (United States)

    Bravo, Manuel; Lespes, Gaëtane; De Gregori, Ida; Pinochet, Hugo; Gautier, Martine Potin

    2005-12-01

    A method based on Headspace solid-phase microextraction (HS-SPME, with a 100 mum PDMS-fiber) in combination with gas-chromatography and pulsed flame-photometric detection (GC-PFPD) has been investigated for simultaneous determination of eight organotin compounds. Monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPhT), and the semi-volatile diphenyltin (DPhT), triphenyltin (TPhT), monooctyltin (MOcT), and dioctyltin (DOcT) were determined after derivatization with sodium tetraethylborate. The conditions used for the extraction and preconcentration step were optimised by experimental design methodology. Tripropyltin (TPrT) and diheptyltin (DHepT) were used as internal standards for quantification of volatile and semi-volatile organotin compounds, respectively. The analytical precision (RSD) for ten successive injections of a standard mixture containing all the organic tin compounds ranged between 2 and 11%. The limits of detection for all the organotin compounds were sub ng (Sn) L(-1) in water and close to ng (Sn) kg(-1) in sediments. The accuracy of the method was evaluated by analysis of two certified reference material (CRM) sediment samples. The HS-SPME-GC-PFPD was then applied to the analysis of three harbour sediment samples. The results showed that headspace SPME is an attractive tool for analysis of organotin compounds in solid environmental matrices.

  19. Simultaneous in-vial acetylation solid-phase microextraction followed by gas chromatography tandem mass spectrometry for the analysis of multiclass organic UV filters in water.

    Science.gov (United States)

    Vila, Marlene; Celeiro, Maria; Lamas, J Pablo; Garcia-Jares, Carmen; Dagnac, Thierry; Llompart, Maria

    2017-02-05

    UV filters are a class of emerging contaminants that are widely used in personal care products (PCPs) and that can be detected at low concentrations in the aquatic environment (ngL -1 ). Sensitive modern analytical methods are then mandatory to accurately analyze them. A methodology based on solid-phase-microextraction (SPME), considered as a 'Green Chemistry' technique, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in environmental and recreational waters. In-vial low-cost derivatization was carried out to improve chromatographic performance of phenolic compounds. The extraction parameters (fiber coating, extraction mode, and salt addition) were optimized by means of experimental designs in order to achieve reliable conditions. Finally, the SPME-GC-MS/MS method was validated in terms of linearity, accuracy and precision with LODs in the low ngL -1 level. Its application to the analysis of 28 different samples including sea, river, spa, swimming pool, and aquapark waters, enabled the detection of 11 target UV filters at concentration levels up to 540μgL -1 , highlighting the presence of OCR in all analyzed samples and of 2EHMC (proposed to be considered as priority pollutant) in 79% of them. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Simultaneous optimization by neuro-genetic approach of a multiresidue method for determination of pesticides in Passiflora alata infuses using headspace solid phase microextraction and gas chromatography.

    Science.gov (United States)

    da Silva, Gilmare Antônia; Augusto, Fabio; Poppi, Ronei Jesus

    2007-01-05

    A simultaneous optimization strategy based on neuro-genetic approach has been applied to a HS-SPME-GC-ECD (Headspace Solid Phase Microextraction coupled to Gas Chromatography with Electron Capture Detection) method for simultaneous determination of the pesticides chlorotalonil, methyl parathion, malathion, alpha-endosulfan and beta-endosulfan in herbal infusions of Passiflora alata (Dryander). Two types of extractive fibers were used: a home-made device coated by sol-gel process with polydimethylsiloxane-poly(vinyl alcohol) (PDMS/PVA) and a commercial PDMS. The effects of extraction parameters such as dilution of the infusion, extraction temperature and time, as well as sample ionic strength were evaluated through the Doehlert design. To find a model that could relate these extraction parameters with the extraction efficiency of all pesticide simultaneously, a Bayesian Regularized Artificial Neural Network (BRANN) approach was employed. Subsequently, Genetic Algorithm (GA) was applied to attain the optimum values from the model developed by the neural network. The use of the proposed approach allowed the determination of a single extraction condition that maximized the peak areas of all pesticides simultaneously, showing a promising and a suitable new procedure to the optimization process of complex analytical problems.

  1. A novel poly(3,4-ethylenedioxythiophene)-ionic liquid composite coating for the headspace solid-phase microextraction and gas chromatography determination of several alcohols in soft drinks.

    Science.gov (United States)

    Wu, Mian; Zhang, Haibo; Zhao, Faqiong; Zeng, Baizhao

    2014-11-19

    A novel poly(3,4-ethylenedioxythiophene)-ionic liquid (i.e., 1-hydroxyethyl-3-methyl imidazolium-bis[(trifluoromethyl)sulfonyl]imide) composite film was electrodeposited on a Pt wire for headspace solid-phase microextraction. The film showed nodular structure and had large specific surface. In addition, it displayed high thermal stability (up to 300°C) and durable property (could be used for more than 200 times). Coupled with gas chromatography-flame ionization detection, the resulting fiber was applied to the headspace solid-phase microextraction and determination of several alcohols (i.e., linalool, nonanol, terpineol, geraniol, decanol and dodecanol). It presented higher extraction capability in comparison with the poly(3,4-ethylenedioxythiophene) and commercial polydimethylsiloxane/divinylbenzene fiber. Under the optimized conditions, the linear ranges exceeded three magnitudes with correlation coefficients above 0.9952 and the low limits of detection were 34.2-81.3ng L(-1). For different alcohols the repeatabilities (defined as RSD) were alcohols in real samples with acceptable recoveries from 81.1% to 106.6%. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Application of headspace solid-phase microextraction followed by gas chromatography coupled with mass spectrometry to determine esters of carboxylic acids and other volatile compounds in Dermestes maculatus and Dermestes ater lipids.

    Science.gov (United States)

    Cerkowniak, Magdalena; Boguś, Mieczysława I; Włóka, Emilia; Stepnowski, Piotr; Gołębiowski, Marek

    2018-02-01

    A constant problem in veterinary medicine, human healthcare, agriculture, forestry and horticulture is the large number of pests, and the lack of effective methods to combat them which cause no harm to the rest of the environment. It is recommended and desired to reduce the use of chemicals and increase the use of agents based on knowledge acquired in the fields of biology, chemistry and agrochemicals. To learn the defense mechanisms of insects we should consider not only the site of their physiological ability to protect against external factors (cuticle), but also the possibility of chemical protection, formed by all compounds on the surface and in the body of insects. In this study, a procedure was developed to determine the esters of carboxylic acids in insect lipids. Headspace solid-phase microextraction was followed by gas chromatography coupled with gas spectrometry. First, the best conditions were selected for the analysis to obtain the best chromatographic separation. An RTx-5 column was used for this purpose. Polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate fibers were used to isolate acid esters. PDMS/DVB fiber achieved the best conditions for the extraction; the extraction time was 50 min, the extraction temperature was 105°C and the desorption time was 10 min at 230°C. These solid-phase microextraction conditions were used to analyze volatile compounds extracted from insects belonging to the Dermestidae family. Copyright © 2017 John Wiley & Sons, Ltd.

  3. An Effective Method to Detect Volatile Intermediates Generated in the Bioconversion of Coal to Methane by Gas Chromatography-Mass Spectrometry after In-Situ Extraction Using Headspace Solid-Phase Micro-Extraction under Strict Anaerobic Conditions.

    Science.gov (United States)

    Liu, Jianmin; Wang, Baoyu; Tai, Chao; Wu, Li; Zhao, Han; Guan, Jiadong; Chen, Linyong

    2016-01-01

    Bioconversion of coal to methane has gained increased attention in recent decades because of its economic and environmental advantages. However, the mechanism of this process is difficult to study in depth, partly because of difficulties associated with the analysis of intermediates generated in coal bioconversion. In this investigation, we report on an effective method to analyze volatile intermediates generated in the bioconversion of coal under strict anaerobic conditions. We conduct in-situ extraction of intermediates using headspace solid-phase micro-extraction followed by detection by gas chromatography-mass spectrometry. Bioconversion simulation equipment was modified and combined with a solid-phase micro-extraction device. In-situ extraction could be achieved by using the combined units, to avoid a breakdown in anaerobic conditions and to maintain the experiment continuity. More than 30 intermediates were identified qualitatively in the conversion process, and the variation in trends of some typical intermediates has been discussed. Volatile organic acids (C2-C7) were chosen for a quantitative study of the intermediates because of their importance during coal bioconversion to methane. Fiber coating, extraction time, and solution acidity were optimized in the solid-phase micro-extraction procedure. The pressure was enhanced during the bioconversion process to investigate the influence of headspace pressure on analyte extraction. The detection limits of the method ranged from 0.0006 to 0.02 mmol/L for the volatile organic acids and the relative standard deviations were between 4.6% and 11.5%. The volatile organic acids (C2-C7) generated in the bioconversion process were 0.01-1.15 mmol/L with a recovery range from 80% to 105%. The developed method is useful for further in-depth research on the bioconversion of coal to methane.

  4. Determination of some selected pesticide residues in apple juice by solid-phase microextraction coupled to gas chromatography – mass spectrometry

    Directory of Open Access Journals (Sweden)

    Andrea Hercegová

    2011-01-01

    Full Text Available The performance of solid phase microextraction (SPME for enrichment of pesticides from apple juice was investigated. Samples were diluted with water, extracted by solid-phase microextraction and analysed by gas chromatography using mass-spectrometry detector (MSD in selected ion monitoring mode (SIM. The method was tested for the following pesticides used mostly in fruit culturing at Slovakia: tebuthylazine, fenitrothion, chlorpyrifos, myclobutanil, cyprodinil, phosalone, pyrimethanil, tebuconazole, kresoxim-methyl, methidathion, penconazole. All pesticides were extracted with polydimethylsiloxane fibre 100 μm thickness. The linear concentration range of application was 0.05 μg dm−3–10 μg dm−3. The method described provides detectabilities complying with the maximum residue levels (MRLs set by regulatory organizations for pesticides in apple juice matrices. The solvent – free SPME procedure was found to be quicker and more cost effective then the solvent extraction methods commonly used.

  5. Doping of three-dimensional porous carbon nanotube-graphene-ionic liquid composite into polyaniline for the headspace solid-phase microextraction and gas chromatography determination of alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Li, Lulu; Wu, Mian; Feng, Yingying; Zhao, Faqiong; Zeng, Baizhao, E-mail: bzzeng@whu.edu.cn

    2016-12-15

    In this work, ionic liquid (IL, i.e. 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate), carboxyl multiwall carbon nanotubes (MWCNTs) and reduced graphene oxide (rGO) were used to prepare three-dimensional porous material (MWCNTs-rGO-IL) by one-step self-assembly, then it was co-electrodeposited with polyaniline (PANI) on stainless steel wires by cyclic voltammetry. The resulting coating (PANI-MWCNTs-rGO-IL) was characterized by using FT-IR and scanning electron microscopy etc, and it showed porous structure and had high thermal stability. Furthermore, it was found to be very suitable for the headspace solid-phase microextraction of alcohols (i.e. octanol, nonanol, geraniol, decanol, undecanol and dodecanol). By coupling with gas chromatography, wide linear ranges and low limits of detection (i.e. 2.2–28.3 ng L{sup −1}) were obtained for the alcohols. The coating also presented good repeatability and reproducibility; the relative standard deviations for intra-fiber and fiber-to-fiber were less than 5.6% (n = 5) and 7.0% (n = 5) respectively. In addition, the proposed method was successfully applied to the determination of alcohols in tea drinks, and the recoveries for standards added were 85.6–114%. - Highlights: • A three-dimensional porous material (MWCNTs-rGO-IL) was synthesized by self-assembly. • A new PANI-MWCNTs-rGO-IL composite coating was prepared by electrochemical method. • It presented high thermal stability and extraction selectivity for alcohols.

  6. Doping of three-dimensional porous carbon nanotube-graphene-ionic liquid composite into polyaniline for the headspace solid-phase microextraction and gas chromatography determination of alcohols

    International Nuclear Information System (INIS)

    Li, Lulu; Wu, Mian; Feng, Yingying; Zhao, Faqiong; Zeng, Baizhao

    2016-01-01

    In this work, ionic liquid (IL, i.e. 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate), carboxyl multiwall carbon nanotubes (MWCNTs) and reduced graphene oxide (rGO) were used to prepare three-dimensional porous material (MWCNTs-rGO-IL) by one-step self-assembly, then it was co-electrodeposited with polyaniline (PANI) on stainless steel wires by cyclic voltammetry. The resulting coating (PANI-MWCNTs-rGO-IL) was characterized by using FT-IR and scanning electron microscopy etc, and it showed porous structure and had high thermal stability. Furthermore, it was found to be very suitable for the headspace solid-phase microextraction of alcohols (i.e. octanol, nonanol, geraniol, decanol, undecanol and dodecanol). By coupling with gas chromatography, wide linear ranges and low limits of detection (i.e. 2.2–28.3 ng L −1 ) were obtained for the alcohols. The coating also presented good repeatability and reproducibility; the relative standard deviations for intra-fiber and fiber-to-fiber were less than 5.6% (n = 5) and 7.0% (n = 5) respectively. In addition, the proposed method was successfully applied to the determination of alcohols in tea drinks, and the recoveries for standards added were 85.6–114%. - Highlights: • A three-dimensional porous material (MWCNTs-rGO-IL) was synthesized by self-assembly. • A new PANI-MWCNTs-rGO-IL composite coating was prepared by electrochemical method. • It presented high thermal stability and extraction selectivity for alcohols.

  7. Headspace solid-phase microextraction (HS-SPME) combined with GC-MS as a process analytical technology (PAT) tool for monitoring the cultivation of C. tetani.

    Science.gov (United States)

    Ghader, Masoud; Shokoufi, Nader; Es-Haghi, Ali; Kargosha, Kazem

    2018-02-06

    Vaccine production is a biological process in which variation in time and output is inevitable. Thus, the application of Process Analytical Technologies (PAT) will be important in this regard. Headspace solid - phase microextraction (HS-SPME) coupled with GC-MS can be used as a PAT for process monitoring. This method is suitable to chemical profiling of volatile organic compounds (VOCs) emitted from microorganisms. Tetanus is a lethal disease caused by Clostridium tetani (C. tetani) bacterium and vaccination is an ultimate way to prevent this disease. In this paper, SPME fiber was used for the investigation of VOCs emerging from C. tetani during cultivation. Different types of VOCs such as sulfur-containing compounds were identified and some of them were selected as biomarkers for bioreactor monitoring during vaccine production. In the second step, the portable dynamic air sampling (PDAS) device was used as an interface for sampling VOCs by SPME fibers. The sampling procedure was optimized by face-centered central composite design (FC-CCD). The optimized sampling time and inlet gas flow rates were 10 min and 2 m L s -1 , respectively. PDAS was mounted in exhausted gas line of bioreactor and 42 samples of VOCs were prepared by SPME fibers in 7 days during incubation. Simultaneously, pH and optical density (OD) were evaluated to cultivation process which showed good correlations with the identified VOCs (>80%). This method could be used for VOCs sampling from off-gas of a bioreactor to monitoring of the cultivation process. Copyright © 2018. Published by Elsevier B.V.

  8. Poly(o-anisidine)/graphene oxide nanosheets composite as a coating for the headspace solid-phase microextraction of benzene, toluene, ethylbenzene and xylenes.

    Science.gov (United States)

    Behzadi, Mansoureh; Mirzaei, Mohammad

    2016-04-22

    A poly(o-anisidine)/graphene oxide nanosheets (PoA/GONSs) coating is fabricated by a simple and efficient electrochemical deposition method on steel wire. The incorporation of PoA and GONSs allows preparing a nanocomposite that can successfully integrate the advantages of both. Then, the prepared fiber is applied to the headspace solid-phase microextraction (HS-SPME) and gas chromatographic analysis of benzene, toluene, ethylbenzene and xylenes. In order to obtain an adherent, stable and efficient fiber to extract target analytes, experimental parameters related to the coating process such as deposition potential, deposition time, concentration of the monomer and concentration of GONSs were studied. The prepared composite fiber were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction and scanning electron microscopy. The effect of various parameters on the efficiency of HS-SPME process consisting of desorption temperature and time, extraction temperature and time and ionic strength were also optimized. Under the optimal conditions, the method was linear for orders of magnitude with correlation coefficients varying from 0.9888 to 0.9993. Intra- and inter-day precisions of the method were determined from mixed aqueous solutions containing 5.0 ng mL(-1) of each BTEX. The intra-day precisions varied from 3.1% for toluene to 5.7% for ethylbenzene, while the inter-day precisions varied from 4.9% for o-xylene to 7.3% for m,p-xylene. Limits of detection were in the range 0.01-0.06 ng mL(-1). The proposed method was applied to monitor BTEX compounds in some water samples and the accuracies found through spiking river water samples showed high recoveries between 92.0 and 101.2%. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Characterization of volatile compounds in fermented milk using solid-phase microextraction methods coupled with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Dan, T; Wang, D; Jin, R L; Zhang, H P; Zhou, T T; Sun, T S

    2017-04-01

    Lactic acid bacteria (LAB) are industrially important bacteria that are widely used in the fermented food industry, especially in the manufacture of yogurt. Characteristic flavors are produced by LAB during fermentation and storage that affect the quality and acceptability of fermented milk products. In this study, the volatile compounds in milk fermented by Streptococcus thermophilus IMAU80842 alone, Lactobacillus delbrueckii ssp. bulgaricus IMAU20401 alone, or both species together were identified using solid-phase microextraction methods coupled with gas chromatography-mass spectrometry. A total of 53, 43, and 32 volatile compounds were identified in milk fermented by S. thermophilus alone, L. delbrueckii ssp. bulgaricus alone, or both species together, respectively. The presence of some important flavor compounds was confirmed: acetic acid, acetaldehyde, acetoin, 2,3-butanedione, ethanol, and 1-heptanol. Our results demonstrate that the composition of the volatile compounds in fermented milk depends on the species of LAB used and whether they are used alone or in combination. This is important for the selection of appropriate starter cultures for the production of different types of fermented milk product with particular flavors. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  10. Characterization of the volatile profiles of beer using headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Rossi, Serena; Sileoni, Valeria; Perretti, Giuseppe; Marconi, Ombretta

    2014-03-30

    The objective of this study was a multivariate characterization of the volatile profile of beers. Such a characterization is timely considering the increasing worldwide consumption of beer, the continuous growth of microbreweries and the importance of volatile compounds to beer flavour. A method employing solid-phase microextraction and gas chromatography-mass spectrometry (SPME-GC-MS) was optimized and then applied to a sample set of 36 industrial and craft beers of various styles and fermentation types. The volatile profiles of different beer styles is described, with particular attention paid to the volatile compounds characteristic of a spontaneously fermented lambic raspberry framboise beer. Furthermore, it was also possible to identify which specific volatile compounds are principally responsible for the differences in the volatile profiles of top- and bottom-fermented beers. Moreover, a volatile fingerprint of the craft top-fermented Italian beers was defined, as they show a very similar volatile profile. Finally, the volatile compounds that are characteristic of the bock-style beers are described. The SPME-GC-MS analytical method optimized in this study is suitable for characterizing the volatile fingerprint of different beers, especially on the basis of the kind of fermentation (top, bottom or spontaneous), the method of production and the style of the beer. © 2013 Society of Chemical Industry.

  11. Predicting PAH bioaccumulation and toxicity in earthworms exposed to manufactured gas plant soils with solid-phase microextraction

    Energy Technology Data Exchange (ETDEWEB)

    Michiel T.O. Jonker; Stephan A. van der Heijden; Joseph P. Kreitinger; Steven B. Hawthorne [Utrecht University, Utrecht (Netherlands). Institute for Risk Assessment Sciences

    2007-11-01

    Soils from former manufactured gas plant (MGP) sites are often heavily contaminated with polycyclic aromatic hydrocarbons (PAHs). Current risk assessment methods that rely on total PAH concentrations likely overstate adverse effects of such soils since bioavailability is ignored. In this study, solid-phase microextraction (SPME) was applied to estimate bioavailable PAH concentrations and toxicity in earthworms exposed to 15 MGP soils. In addition, PAH sorption to all soils (K{sub oc} values) was determined. The results showed a several orders of magnitude variation in K{sub oc} values, demonstrating that generic organic carbon-normalized sorption coefficients will typically be over-conservative at MGP sites. SPME-predicted bioaccumulation generally was within a factor of 10 of measured bioaccumulation (in earthworm bioassays), in contrast to current risk assessment model estimates that over predicted bioaccumulation 10-10,000 times. Furthermore, on the basis of estimated total body residues of narcotic PAHs, SPME correctly predicted worm mortality observed during bioassays in the majority of cases. For MGP sites where current risk assessment procedures indicate concerns, SPME thus provides a useful tool for performing a refined, site-specific assessment. 35 refs., 4 figs.

  12. Effect of Binding Components in Complex Sample Matrices on Recovery in Direct Immersion Solid-Phase Microextraction: Friends or Foe?

    Science.gov (United States)

    Alam, Md Nazmul; Pawliszyn, Janusz

    2018-02-20

    The development of matrix compatible coatings for solid-phase microextraction (SPME) has enabled direct extraction of analytes from complex sample matrices. The direct immersion (DI) mode of SPME when utilized in conjunction with such extraction phases facilitates extraction of a wide range of analytes from complex matrices without the incurrence of fouling or coating saturation. In this work, mathematical models and computational simulations were employed to investigate the effect of binding components present in complex samples on the recovery of small molecules varying in logP for extractions carried out using the direct immersion approach. The presented findings corroborate that the studied approach indeed enables the extraction of both polar and nonpolar analytes from complex matrices, provided a suitable sorbent is employed. Further results indicated that, in certain cases, the kinetics of extraction of a given analyte in its free form might be dependent on the desorption kinetics of their bound form from matrix components, which might lower total recoveries of analytes with high affinity for the matrix. However, the binding of analytes to matrix components also enables SPME to extract a balanced quantity of different logP analytes, facilitated by multiphase equilibria, with a single extraction device.

  13. Solid-phase microextraction for gas chromatographic/mass spectrometric analysis of dimethoate in human biological samples.

    Science.gov (United States)

    Gallardo, E; Barroso, M; Margalho, C; Cruz, A; Vieira, D N; López-Rivadulla, M

    2006-01-01

    A new, simple and rapid procedure for the determination of dimethoate in urine and blood samples was developed using direct immersion solid-phase microextraction and gas chromatography/mass spectrometry. This technique required only 0.1 mL of sample, and ethion was used as internal standard. Two types of coated fibre were compared (100 microm polydimethylsiloxane, and 65 microm Carbowax/divinylbenzene). Other parameters, such as extraction temperature, adsorption and desorption time, salt addition, agitation and pH, were optimized to enhance the sensitivity of the method. Limits of detection (LODs) and quantitation (LOQs) were 50 and 100 ng/mL for urine and 200 and 500 ng/mL for blood, respectively. The method was found to be linear between the LOQ and 40 microg/mL for urine, and between the LOQ and 50 microg/mL for blood, with correlation coefficients ranging from 0.9923-0.9996. Precision (intra- and interday) and accuracy were in conformity with the criteria normally accepted in bioanalytical method validation. The mean absolute recoveries of dimethoate were 1.24 and 0.50% for urine and blood, respectively. Because of its simplicity and the fact that small volumes of sample are used, the described method can be successfully used in the diagnosis of poisoning by this pesticide, namely in those situations where the sample volume is limited, as frequently occurs in forensic toxicology. Copyright 2006 John Wiley & Sons, Ltd.

  14. DETERMINATION AND CLASSIFICATION OF VOLATILE COMPOUNDS OF PASTIRMA USING SOLID PHASE MICROEXTRACTION/GAS CHROMATOGRAPHY/MASS SPECTROMETRY

    Directory of Open Access Journals (Sweden)

    Eda Demirok

    2013-10-01

    Full Text Available Pastırma, a traditional dry cured Turkish meat product, has a great number of specific aroma compounds, which occur as a result of lipid oxidation, protein degradation and formulation of çemen paste. These compounds give characteristic flavor to pastırma and the main objective of this study was to determine the nature of these compounds. Fifty-eight volatile compounds, grouped into nine chemical classes were identified using solid phase microextraction technique (SPME coupled to gas chromatography/mass spectrometry (GC-MS. Aldehydes, mostly lipid oxidation products, were determined as the major chemical group, representing 17.54-78.02% of total volatile compounds. The major volatile aldehyde was hexanal (2.36-55.41%, followed by 2-methyl-2-butenal (0.97-14.69% and then heptanal (0.29-4.77%. Sulfur compounds possibly derived from spices or formed by proteolysis of sulfur-containing amino acids, were the second most abundant group, with concentrations ranging between 6.04 and 50.60%. Other important volatile compounds of pastırma were aliphatic hydrocarbons, aromatic ketones, hydrocarbons, esters, alcohols, acids, terpenes, and furans.

  15. Sodium hyaluronate-functionalized urea-formaldehyde monolithic column for hydrophilic in-tube solid-phase microextraction of melamine.

    Science.gov (United States)

    Wang, Jiabin; Jiang, Nan; Cai, Zhengmiao; Li, Wenbang; Li, Jianhua; Lin, Xucong; Xie, Zenghong; You, Lijun; Zhang, Qiqing

    2017-09-15

    A novel sodium hyaluronate-functionalized urea-formaldehyde (UF) monolithic column has been developed by in-situ polycondensation of urea, formaldehyde and sodium hyaluronate (HA). HA plays both the roles of crosslinking and hydrophilic functionalization. The preparation factors including different molecular weights of HA and different amounts of HA were optimized, and then a uniform monolith with satisfactory permeability and hydrophilic binding capacity was obtained. Due to the excellent hydrophilicity of HA, HA-functionalized UF monolith showed higher hydrophilic extraction efficiency than UF monolith, and was applied for hydrophilic in-tube solid-phase microextraction (SPME) of melamine (MEL). Several factors for hydrophilic in-tube SPME, such as ACN percentage in the sampling solution, salt concentration and pH value of the sampling solution, elution volume, sampling and elution flow rate, were investigated with respect to the extraction efficiency of MEL. Under the optimized SPME conditions, the limit of detection (LOD) of MEL was found to be 0.2ng/mL in the milk formula samples, the recoveries of MEL spiked in milk formula samples ranged from 87.3% to 96.7% with relative standard deviations (RSDs) less than 5.1%. Owing to the excellent hydrophilic extraction ability, the novel HA-functionalized UF monolith could provide a promising tool for the sensitive analysis of polar analytes in complicated samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Identification and quantification of organic pollutants in the air of the city of Astana using solid phase microextraction

    Directory of Open Access Journals (Sweden)

    Dina Orazbayeva

    2017-06-01

    Full Text Available Solid-phase microextraction in combination with gas chromatography and mass-spectrometry (GC-MS was used for determination of benzene, toluene, ethylbenzene and o-xylene (BTEX, polycyclic aromatic hydrocarbons (PAH, and for identification of volatile organic compounds (VOCs in ambient air of the city of Astana, Kazakhstan. The screening of the samples showed the presence of mono- and polycyclic aromatic hydrocarbons, alkanes, alkenes, phenols, and benzaldehydes. The concentrations of naphthalene were 5-7 times higher than the permissible value, it was detected in all studied air samples. Average concentration of naphthalene was 18.4 μg/m3, acenaphthylene – 0.54 μg/m3, acenaphthene – 1.63 μg/m3, fluorene – 0.79 μg/m3, anthracene – 3.27 μg/m3, phenanthrene – 0.22 μg/m3, fluorantene – 0.74 μg/m3, pyrene – 0.73 μg/m3. Average concentrations of BTEX in the studied samples were 31.1, 84.9, 10.8 and 11.6 μg/m3, respectively. Based on the statistical analysis of the concentrations of BTEX and PAH, the main source of city air pollution with them was assumed to be vehicle emissions.

  17. Novel polystyrene/antibody nanoparticle-coated capillary for immunoaffinity in-tube solid-phase microextraction.

    Science.gov (United States)

    Xu, Bei; Cheng, Shuai; Wang, Xianhua; Wang, Dongmei; Xu, Liang

    2015-04-01

    Antibody-coated polystyrene (PS) nanoparticles (denoted as PS/IgG) were prepared and chemically immobilized for the first time onto a capillary inner wall for immunoaffinity in-tube solid-phase microextraction (SPME) of β2-microglobin (β2MG) and cystatin C (Cys-C). Scanning electron microscopy images of the prepared capillary showed that the nanoparticles were evenly coated onto the capillary inner surface, resulting in the undulating surface of the capillary inner wall. The extraction capacity of the nanoparticle-coated capillary was nearly five times higher than that of a monolayer antibody-immobilized capillary. The in-tube SPME recovery of β2MG (or Cys-C) by the nanoparticle-functionalized capillary was more than 97.8%, whereas that by the monolayer antibody-immobilized tube was 30.5%. In addition, the method quantitation limit obtained by using the nanoparticle-coated capillary was ten times lower than that by the monolayer capillary. Therefore, the capillary coated by PS/IgG nanoparticles is more suitable for immunoaffinity in-tube SPME compared with the commonly used monolayer antibody-immobilized capillary.

  18. Surfactant-enhanced liquid-liquid microextraction coupled to micro-solid phase extraction onto highly hydrophobic magnetic nanoparticles

    International Nuclear Information System (INIS)

    Giannoulis, Kiriakos M.; Giokas, Dimosthenis L.; Tsogas, George Z.; Vlessidis, Athanasios G.; Zhu, Qing; Pan, Qinmin

    2013-01-01

    We are presenting a simplified alternative method for dispersive liquid-liquid microextraction (DLLME) by resorting to the use of surfactants as emulsifiers and micro solid-phase extraction (μ-SPE). In this combined procedure, DLLME of hydrophobic components is initially accomplished in a mixed micellar/microemulsion extractant phase that is prepared by rapidly mixing a non-ionic surfactant and 1-octanol in aqueous medium. Then, and in contrast to classic DLLME, the extractant phase is collected by highly hydrophobic polysiloxane-coated core-shell Fe 2 O 3 (at)C magnetic nanoparticles. Hence, the sample components are the target analyte in the DLLME which, in turn, becomes the target analyte of the μ-SPE step. This 2-step approach represents a new and simple DLLME procedure that lacks tedious steps such as centrifugation, thawing, or delicate collection of the extractant phase. As a result, the analytical process is accelerated and the volume of the collected phase does not depend on the volume of the extraction solvent. The method was applied to extract cadmium in the form of its pyrrolidine dithiocarbamate chelate from spiked water samples prior to its determination by FAAS. Detection limits were brought down to the low μg L −1 levels by preconcentrating 10 mL samples with satisfactory recoveries (96.0–108.0 %). (author)

  19. Solid-phase microextraction and gas chromatography-mass spectrometry of volatile compounds from avocado puree after microwave processing.

    Science.gov (United States)

    López, Mercedes G; Guzmán, G R; Dorantes, A L

    2004-05-14

    Microwave processing offers an alternative to blanch fruits and vegetables, since the application of high temperature and short time often results in minimum damage. An experimental design was used to investigate the effect of microwave time, pH, and avocado leaves (independent variables) on avocado flavor (response) using solid-phase microextraction (SPME)-GC-MS. Among the fully characterized flavor volatiles, 19 compounds were derived from lipid oxidation and only 4 from the avocado leaves. The main components derived from lipids were aldehydes, ketones and alcohols. Terpenoids, estragole, and 2-hexenal [E] were volatiles derived from avocado leaves. When leaves were added to fresh and microwaved avocado terpenoids and 2-hexenal [E]/hexanal ratio increased, this behavior was considered to have a positive effect on the sensorial quality of the product. From the statistical analysis of the experimental design, it was possible to determinate that the most important factors influencing the abundance of flavor compounds derived from lipids were microwave time and pH. Maximum values of these compounds were detected at high levels of microwave time and low values of pH. On the other hand, response surface of terpenoids and estragole showed an increment when microwave time and avocado leaf was increased. The region of optimum response was 30 s microwave time, pH 5.5, and 1% of avocado leaf.

  20. Determination of amphetamine-type stimulants in oral fluid by solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Souza, Daniele Z; Boehl, Paula O; Comiran, Eloisa; Mariotti, Kristiane C; Pechansky, Flavio; Duarte, Paulina C A V; De Boni, Raquel; Froehlich, Pedro E; Limberger, Renata P

    2011-06-24

    A method for the simultaneous identification and quantification of amphetamine (AMP), methamphetamine (MET), fenproporex (FEN), diethylpropion (DIE) and methylphenidate (MPH) in oral fluid collected with Quantisal™ device has been developed and validated. Thereunto, in-matrix propylchloroformate derivatization followed by direct immersion solid-phase microextraction and gas chromatography-mass spectrometry were employed. Deuterium labeled AMP was used as internal standard for all the stimulants and analysis was performed using the selected ion monitoring mode. The detector response was linear for the studied drugs in the concentration range of 2-256 ng mL(-1) (neat oral fluid), except for FEN, whereas the linear range was 4-256 ng mL(-1). The detection limits were 0.5 ng mL(-1) (MET), 1 ng mL(-1) (MPH) and 2 ng mL(-1) (DIE, AMP, FEN), respectively. Accuracy of quality control samples remained within 98.2-111.9% of the target concentrations, while precision has not exceeded 15% of the relative standard deviation. Recoveries with Quantisal™ device ranged from 77.2% to 112.1%. Also, the goodness-of-fit concerning the ordinary least squares model in the statistical inference of data has been tested through residual plotting and ANOVA. The validated method can be easily automated and then used for screening and confirmation of amphetamine-type stimulants in drivers' oral fluid. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Simultaneous analysis of amphetamine-type stimulants in plasma by solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Mariotti, Kristiane de Cássia; Schuh, Roselena S; Ferranti, Priscila; Ortiz, Rafael S; Souza, Daniele Z; Pechansky, Flavio; Froehlich, Pedro E; Limberger, Renata P

    2014-09-01

    Brazil is considered one of the countries with the highest number of amphetamine-type stimulant (ATS) users worldwide, mainly diethylpropion (DIE) and fenproporex (FEN). The use of ATS is mostly linked to diverted prescription stimulants and this misuse is widely associated with (ab)use by drivers. A validated method was developed for the simultaneous analysis of amphetamine (AMP), DIE and FEN in plasma samples employing direct immersion-solid-phase microextraction, and gas chromatographic/mass spectrometric analysis. Trichloroacetic acid 10% was used for plasma deproteinization. In situ derivatization with propylchloroformate was employed. The linear range of the method covered from 5.0 to 100 ng/mL. The detection limits were 1.0 (AMP), 1.5 (DIE) and 2.0 ng/mL (FEN). The accuracy assessment of the control samples was within 85.58-108.33% of the target plasma concentrations. Recoveries ranged from 46.35 to 84.46% and precision was <15% of the value of relative standard deviation. This method is appropriate for screening and confirmation in plasma forensic toxicology analyses of these basic drugs. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  2. Analysis of volatile compositions of Magnolia biondii pamp by steam distillation and headspace solid phase micro-extraction.

    Science.gov (United States)

    Zeng, Zhi; Xie, Runqian; Zhang, Tao; Zhang, Han; Chen, Jie Yu

    2011-01-01

    The chemical compositions of volatile components from Magnolia biondii Pamp were determined by steam distillation (SD) and headspace solid phase micro-extraction (HS-SPME) followed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) analysis. Fifty-six compounds were identified and the major volatile components were d-camphor (0.18-43.26%), 1,8-cineol (13.23-38.02%), α-terpineol (6.57-12.29%) and α-cadinene (5.53-15.15%). The comparison of the volatile components from M. biondii Pamp harvested in three regions of China was investigated. Also, the comparison of volatile components by SD and HS-SPME methods in term of isolation time, plant-consuming and chemical compositions was discussed as well. The percentages of the volatile components by HS-SPME method were found to be large difference from the corresponding one by SD method. HS-SPME technique was much faster than SD (60 min (HS-SPME)/420 min (SD)). Although the aromatic profiles between HS-SPME and SD methods showed several quantitative differences, HS-SPME may be applied routinely to analyze aromatic and medicinal plants.

  3. Analysis of Volatile Components of Adenosma indianum (Lour. Merr. by Steam Distillation and Headspace Solid-Phase Microextraction

    Directory of Open Access Journals (Sweden)

    Zhi Zeng

    2013-01-01

    Full Text Available The essential oil of Adenosma indianum (Lour. Merr. plays an important role in its antibacterial and antiphlogistic activities. In this work, the volatile components were extracted by steam distillation (SD and headspace solid-phase microextraction (HS-SPME and analysed by gas chromatography-mass spectrometry (GC-MS. A total of 49 volatile components were identified by GC-MS, and the major volatile components were α-limonene (20.59–35.07%, fenchone (15.79–31.81%, α-caryophyllene (6.98–10.32%, β-caryophyllene (6.98–10.19%, and piperitenone oxide (1.96–11.63%. The comparison of the volatile components from A. indianum (Lour. Merr. grown in two regions of China was reported. Also, the comparison of the volatile components by SD and HS-SPME was discussed. The results showed that the major volatile components of A. indianum (Lour. Merr. from two regions of China were similar but varied with different extraction methods. These results were indicative of the suitability of HS-SPME method for simple, rapid, and solvent-free analysis of the volatile components of the medicinal plants.

  4. Influence of fibre coating in headspace solid-phase microextraction-gas chromatographic analysis of aromatic and medicinal plants.

    Science.gov (United States)

    Bicchi, C; Drigo, S; Rubiolo, P

    2000-09-15

    Solid-phase microextraction (SPME) is a solvent-free technique, which is well established in headspace analysis since it is sensitive, because of the concentration factor achieved by the fibres, and selective, because of different coating materials which can be used. The performance of eight commercially available SPME fibres was compared to evaluate the recoveries of some characteristic components with different polarities and structures present in the headspace of four aromatic and medicinal plants: rosemary (Rosmarinus officinalis L.), sage (Salvia officinalis L.), thyme (Thymus vulgaris L.) and valerian (Valeriana officinalis L.). The relative concentration capacity of each fibre on the same components of each plant was also determined by comparing their abundance with that obtained by classical static-headspace GC. The partition coefficient, K1, between the headspace gaseous phase and SPME polymeric coating, and the relative concentration factors, of some of the characteristic components of the plant investigated dissolved in dibutyl phtalate, were also determined, under rigorously standardised analysis conditions. The results showed that the most effective fibres were those consisting of two components, i.e., a liquid phase (polydimethylsiloxane) and a porous solid (carboxen or divinylbenzene, or both).

  5. Screening of volatile composition of Lavandula hybrida Reverchon II honey using headspace solid-phase microextraction and ultrasonic solvent extraction.

    Science.gov (United States)

    Jerković, Igor; Marijanović, Zvonimir

    2009-03-01

    The volatiles of unifloral Lavandula hybrida Reverchon II honey were isolated by means of headspace solid-phase microextraction (HS-SPME) and ultrasonic solvent extraction (USE) and analyzed by gas chromatography and mass spectrometry (GC, GC/MS). A total of 23 compounds were identified in the headspace with hexan-1-ol, hexanal, acetic acid, hotrienol, and 2-phenylacetaldehyde as the principal components. Three solvents of different polarity were used for USE, and a total of 53 compounds were identified. The extracts with pentane/Et(2)O 1 : 2 (v/v) were the most representative for USE method containing the majority of the honey floral origin compounds and potential biomarkers (hexanol, acetic acid, butane-1,3-diol, butane-2,3-diol, benzoic acid, coumarin, and 2-phenylacetic acid). The total number of identified compounds (USE and HS-SPME) was 59. In general, the comparison with volatiles of other lavandin honeys of different geographic origins indicated several similarities, while acetic and formic acids were identified with high percentages in L. hybrida Reverchon II honey.

  6. Determination of Volatile Compounds in Four Commercial Samples of Japanese Green Algae Using Solid Phase Microextraction Gas Chromatography Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Masayoshi Yamamoto

    2014-01-01

    Full Text Available Green algae are of great economic importance. Seaweed is consumed fresh or as seasoning in Japan. The commercial value is determined by quality, color, and flavor and is also strongly influenced by the production area. Our research, based on solid phase microextraction gas chromatography mass spectrometry (SPME-GC-MS, has revealed that volatile compounds differ intensely in the four varieties of commercial green algae. Accordingly, 41 major volatile compounds were identified. Heptadecene was the most abundant compound from Okayama (Ulva prolifera, Tokushima (Ulva prolifera, and Ehime prefecture (Ulva linza. Apocarotenoids, such as ionones, and their derivatives were prominent volatiles in algae from Okayama (Ulva prolifera and Tokushima prefecture (Ulva prolifera. Volatile, short chained apocarotenoids are among the most potent flavor components and contribute to the flavor of fresh, processed algae, and algae-based products. Benzaldehyde was predominant in seaweed from Shizuoka prefecture (Monostroma nitidum. Multivariant statistical analysis (PCA enabled simple discrimination of the samples based on their volatile profiles. This work shows the potential of SPME-GC-MS coupled with multivariant analysis to discriminate between samples of different geographical and botanical origins and form the basis for development of authentication methods of green algae products, including seasonings.

  7. Determination of volatile compounds in four commercial samples of Japanese green algae using solid phase microextraction gas chromatography mass spectrometry.

    Science.gov (United States)

    Yamamoto, Masayoshi; Baldermann, Susanne; Yoshikawa, Keisuke; Fujita, Akira; Mase, Nobuyuki; Watanabe, Naoharu

    2014-01-01

    Green algae are of great economic importance. Seaweed is consumed fresh or as seasoning in Japan. The commercial value is determined by quality, color, and flavor and is also strongly influenced by the production area. Our research, based on solid phase microextraction gas chromatography mass spectrometry (SPME-GC-MS), has revealed that volatile compounds differ intensely in the four varieties of commercial green algae. Accordingly, 41 major volatile compounds were identified. Heptadecene was the most abundant compound from Okayama (Ulva prolifera), Tokushima (Ulva prolifera), and Ehime prefecture (Ulva linza). Apocarotenoids, such as ionones, and their derivatives were prominent volatiles in algae from Okayama (Ulva prolifera) and Tokushima prefecture (Ulva prolifera). Volatile, short chained apocarotenoids are among the most potent flavor components and contribute to the flavor of fresh, processed algae, and algae-based products. Benzaldehyde was predominant in seaweed from Shizuoka prefecture (Monostroma nitidum). Multivariant statistical analysis (PCA) enabled simple discrimination of the samples based on their volatile profiles. This work shows the potential of SPME-GC-MS coupled with multivariant analysis to discriminate between samples of different geographical and botanical origins and form the basis for development of authentication methods of green algae products, including seasonings.

  8. Determination of amphetamine-type stimulants (ATSs) and synthetic cathinones in urine using solid phase micro-extraction fibre tips and gas chromatography-mass spectrometry

    OpenAIRE

    Alsenedi, Khalid A.; Morrison, Calum

    2018-01-01

    In recent years, an increasing number of stimulant drugs and new psychoactive substances (NPSs) have caused concern in scientific communities and therefore innovative methods to extract compounds from complex biological samples are required. This work is aimed at developing and validating a clean, convenient and straightforward extraction procedure with microliter amounts of organic solvent using Solid Phase Micro-Extraction tips (SPME tips) and analysis using Gas Chromatography-Mass Spectrom...

  9. Ultrapreconcentration and determination of organophosphorus pesticides in water by solid-phase extraction combined with dispersive liquid-liquid microextraction and high-performance liquid chromatography.

    Science.gov (United States)

    Chen, Junhua; Zhou, Guangming; Deng, Yongli; Cheng, Hongmei; Shen, Jie; Gao, Yi; Peng, Guilong

    2016-01-01

    Solid-phase extraction coupled with dispersive liquid-liquid microextraction was developed as an ultra-preconcentration method for the determination of four organophosphorus pesticides (isocarbophos, parathion-methyl, triazophos and fenitrothion) in water samples. The analytes considered in this study were rapidly extracted and concentrated from large volumes of aqueous solutions (100 mL) by solid-phase extraction coupled with dispersive liquid-liquid microextraction and then analyzed using high performance liquid chromatography. Experimental variables including type and volume of elution solvent, volume and flow rate of sample solution, salt concentration, type and volume of extraction solvent and sample solution pH were investigated for the solid-phase extraction coupled with dispersive liquid-liquid microextraction with these analytes, and the best results were obtained using methanol as eluent and ethylene chloride as extraction solvent. Under the optimal conditions, an exhaustive extraction for four analytes (recoveries >86.9%) and high enrichment factors were attained. The limits of detection were between 0.021 and 0.15 μg/L. The relative standard deviations for 0.5 μg/L of the pesticides in water were in the range of 1.9-6.8% (n = 5). The proposed strategy offered the advantages of simple operation, high enrichment factor and sensitivity and was successfully applied to the determination of four organophosphorus pesticides in water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Analysis of carbamate and phenylurea pesticide residues in fruit juices by solid-phase microextraction and liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Sagratini, Gianni; Mañes, Jordi; Giardiná, Dario; Damiani, Pietro; Picó, Yolanda

    2007-04-20

    A new analysis method to detect carbamates and phenylurea pesticide residues in fruit juices was developed using solid-phase microextraction (SPME) coupled with liquid chromatography-single quadrupole mass spectrometry (LC/MS) and liquid chromatography-quadrupole ion trap mass spectrometry (LC/QIT-MS). The pesticide residues present in watery matrices as fruit juices were extracted using three types of fibers: 50-microm Carbowax/templated resin (CW/TPR), 60-mum poly(dimethylsiloxane)/divinylbenzene (PDMS/DVB) and 85-microm polyacrylate. The different extraction conditions were evaluated choosing as the best parameters 90 min (time), 20 degrees C (temperature) and 1 ml (volume). After extraction, the desorption (in a static mode) was performed in the specific interface chamber SPME/HPLC, previously filled with 70% methanol and 30% water. The best recoveries, evaluated at two fortification levels (0.2 and 0.5 mg kg(-1)) in fruit juices, were obtained using PDMS/DVB and CW/TPR fibers, and ranged from 25 to 82% (monolinuron, diuron and diethofencarb), with relative standard deviations (RSDs) from 1 to 17%. All the limits of quantification (LOQs) were in the range of 0.005-0.05 microg ml(-1) and, in any case, equal to, or lower than, maximum residue limits (MRLs) established by Italian and Spanish legislations. The mass spectrometry analyses were carried out using an electrospray ionization (ESI) source operating in the positive mode both for single quadrupole and for QIT mass analysers, operating in selected ion monitoring (SIM) and in multiple reaction monitoring (MRM) modes, respectively. The proposed new method can be applied to the determination of selected pesticides in real samples of fruit juices.

  11. Comparison of Ultrasound-Assisted Headspace Solid-Phase Microextraction and Hydrodistillation for the Identification of Major Constituents in Two Species of Hypericum.

    Science.gov (United States)

    Ghiasvand, Alireza; Shadabi, Shahriar; Hajipour, Somayeh; Nasirian, Afagh; Borzouei, Mohammad; Hassani-Moghadam, Esfandyar; Hashemi, Payman

    2016-02-01

    Ultrasound-assisted headspace solid-phase microextraction (UA-HS-SPME) and hydrodistillation (HD) methods, coupled to gas chromatography-mass spectrometry (GC-MS), were used for the extraction and analysis of volatile compounds from Hypericum perforatum and Hypericum scabrum collected from two different sites in Iran. In the UA-HS-SPME method, various experimental parameters such as the type of fiber coating, sonication time, extraction time, extraction temperature and desorption time were investigated. The highest extraction efficiency was achieved by a 100-µm polydimethylsiloxane (PDMS) fiber. Consequently, 36 compounds were identified in H. perforatum and H. scabrum samples, using the UA-HS-SPME-GC-MS method, of which 14 were the same in both species. On the other hand, 57 compounds of these species were identified by the HD-GC-MS method, of which 21 were the same. The predominant constituents identified using the UA-HS-SPME method in H. perforatum included β-caryophyllene, α-pinene, γ-cadinene, α-selinene, germacrene-D, limonene and myrcene, and in H. scabrum were α-pinene, nonane, β-pinene and limonene. The common constituents identified by the HD-GC-MS method for H. perforatum involved germacrene-D, limonene, β-caryophyllene, α-pinene, β-pinene and germacrene-B, and for H. scabrum were α-pinene, β-pinene, germacrene-D, nonane, limonene and γ-cadinene. The results about the main constituents of the examined species correspond to the findings of other researchers. Additionally, comparing UA-HS-SPME-GC-MS and HD-GC-MS methods showed that the UA-HS-SPME-GC-MS method is much faster and simpler, and it requires much less sample size and lower temperature. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  12. Solid phase microextraction Arrow for the sampling of volatile amines in wastewater and atmosphere.

    Science.gov (United States)

    Helin, Aku; Rönkkö, Tuukka; Parshintsev, Jevgeni; Hartonen, Kari; Schilling, Beat; Läubli, Thomas; Riekkola, Marja-Liisa

    2015-12-24

    A new method is introduced for the sampling of volatile low molecular weight alkylamines in ambient air and wastewater by utilizing a novel SPME Arrow system, which contains a larger volume of sorbent compared to a standard SPME fiber. Parameters affecting the extraction, such as coating material, need for preconcentration, sample volume, pH, stirring rate, salt addition, extraction time and temperature were carefully optimized. In addition, analysis conditions, including desorption temperature and time as well as gas chromatographic parameters, were optimized. Compared to conventional SPME fiber, the SPME Arrow had better robustness and sensitivity. Average intermediate reproducibility of the method expressed as relative standard deviation was 12% for dimethylamine and 14% for trimethylamine, and their limit of quantification 10μg/L and 0.13μg/L respectively. Working range was from limits of quantification to 500μg/L for dimethylamine and to 130μg/L for trimethylamine. Several alkylamines were qualitatively analyzed in real samples, while target compounds dimethyl- and trimethylamines were quantified. The concentrations in influent and effluent wastewater samples were almost the same (∼80μg/L for dimethylamine, 120μg/L for trimethylamine) meaning that amines pass the water purification process unchanged or they are produced at the same rate as they are removed. For the air samples, preconcentration with phosphoric acid coated denuder was required and the concentration of trimethylamine was found to be around 1ng/m(3). The developed method was compared with optimized method based on conventional SPME and advantages and disadvantages of both approaches are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Headspace versus direct immersion solid phase microextraction in complex matrixes: investigation of analyte behavior in multicomponent mixtures.

    Science.gov (United States)

    Gionfriddo, Emanuela; Souza-Silva, Érica A; Pawliszyn, Janusz

    2015-08-18

    This work aims to investigate the behavior of analytes in complex mixtures and matrixes with the use of solid-phase microextraction (SPME). Various factors that influence analyte uptake such as coating chemistry, extraction mode, the physicochemical properties of analytes, and matrix complexity were considered. At first, an aqueous system containing analytes bearing different hydrophobicities, molecular weights, and chemical functionalities was investigated by using commercially available liquid and solid porous coatings. The differences in the mass transfer mechanisms resulted in a more pronounced occurrence of coating saturation in headspace mode. Contrariwise, direct immersion extraction minimizes the occurrence of artifacts related to coating saturation and provides enhanced extraction of polar compounds. In addition, matrix-compatible PDMS-modified solid coatings, characterized by a new morphology that avoids coating fouling, were compared to their nonmodified analogues. The obtained results indicate that PDMS-modified coatings reduce artifacts associated with coating saturation, even in headspace mode. This factor, coupled to their matrix compatibility, make the use of direct SPME very practical as a quantification approach and the best choice for metabolomics studies where wide coverage is intended. To further understand the influence on analyte uptake on a system where additional interactions occur due to matrix components, ex vivo and in vivo sampling conditions were simulated using a starch matrix model, with the aim of mimicking plant-derived materials. Our results corroborate the fact that matrix handling can affect analyte/matrix equilibria, with consequent release of high concentrations of previously bound hydrophobic compounds, potentially leading to coating saturation. Direct immersion SPME limited the occurrence of the artifacts, which confirms the suitability of SPME for in vivo applications. These findings shed light into the implementation of in

  14. Magnetic solid-phase extraction or dispersive liquid-liquid microextraction for pyrethroid determination in environmental samples.

    Science.gov (United States)

    Pastor-Belda, Marta; Navarro-Jiménez, Tania; Garrido, Isabel; Viñas, Pilar; Campillo, Natalia; Fenoll, José; Hernández-Córdoba, Manuel

    2018-03-30

    The determination of 15 pyrethroids in soil and water samples was carried out by gas chromatography with mass spectrometry. Compounds were extracted from the soil samples (4 g) using solid-liquid extraction and then salting-out assisted liquid-liquid extraction. The acetonitrile phase obtained (0.8 mL) was used as dispersant solvent, to which 75 μL of chloroform was added as extractant solvent, submitting the mixture to dispersive liquid-liquid microextraction. For the analysis of water samples (40 mL), magnetic solid phase extraction was performed using nanocomposites of magnetic nanoparticles and multiwalled carbon nanotubes as sorbent material (10 mg). The mixture was shaken for 45 min at room temperature before separation with a magnet and desorption with 3 mL of acetone using ultrasounds for 5 min. The solvent was evaporated and reconstituted with 100 μL acetonitrile before injection. Matrix-matched calibration is recommended for quantification of soil samples, while water samples can be quantified by standards calibration. The limits of detection were in the range of 0.03-0.5 ng g -1 (soil) and 0.09-0.24 ng mL -1 (water), depending on the analyte. The environmental samples analyzed did not contain the studied pyrethroids, at least above the corresponding limits of detection. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  15. Volatiles profiling in medicinal licorice roots using steam distillation and solid-phase microextraction (SPME) coupled to chemometrics.

    Science.gov (United States)

    Farag, Mohamed A; Wessjohann, Ludger A

    2012-11-01

    Licorice (Glycyrrhiza glabra L.) is a plant of considerable commercial importance in traditional medicine and for the flavor and sweets industry. Although Glycyrrhiza species are very competitive targets for phytochemical studies, very little is known about the volatiles composition within that genus, although such knowledge can be suspected to be relevant for understanding the olfactory and taste properties. To provide insight into Glycyrrhiza species aroma composition and for its use in food and pharmaceutical industry, volatile constituents from G. glabra, G. inflata, and G. echinata roots were profiled using steam distillation and solid-phase microextraction. Two phenols, thymol and carvacrol, were found exclusively in essential oil and headspace samples of G. glabra, and with highest amounts for samples that originated from Egypt. In G. echinata oil, (2E, 4E)-decadienal (21%) and β-caryophyllene oxide (24%) were found as main constituents, whereas 1α, 10α-epoxyamorpha-4-ene (13%) and β-dihydroionone (8%) predominated G. inflata. Principal component and hierarchical cluster analyses clearly separated G. echinata and G. inflata from G. glabra; with phenolics and aliphatic aldehydes contributing mostly for species segregation. Licorice (Glycyrrhiza glabra) has large economic, nutritional, and medicinal values. The data presented in this article help in licorice quality control analysis to identify G. glabra from its closely allied species. The presence of thymol and carvacrol exclusively in G. glabra suggests that these volatiles could serve as chemotaxonomic markers and also might be considered as potentially relevant for taste. © 2012 Institute of Food Technologists®

  16. Analysis of Mars Analogue Soil Samples Using Solid-Phase Microextraction, Organic Solvent Extraction and Gas Chromatography/Mass Spectrometry

    Science.gov (United States)

    Orzechowska, G. E.; Kidd, R. D.; Foing, B. H.; Kanik, I.; Stoker, C.; Ehrenfreund, P.

    2011-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are robust and abundant molecules in extraterrestrial environments. They are found ubiquitously in the interstellar medium and have been identified in extracts of meteorites collected on Earth. PAHs are important target molecules for planetary exploration missions that investigate the organic inventory of planets, moons and small bodies. This study is part of an interdisciplinary preparation phase to search for organic molecules and life on Mars. We have investigated PAH compounds in desert soils to determine their composition, distribution and stability. Soil samples (Mars analogue soils) were collected at desert areas of Utah in the vicinity of the Mars Desert Research Station (MDRS), in the Arequipa region in Peru and from the Jutland region of Denmark. The aim of this study was to optimize the solid-phase microextraction (SPME) method for fast screening and determination of PAHs in soil samples. This method minimizes sample handling and preserves the chemical integrity of the sample. Complementary liquid extraction was used to obtain information on five- and six-ring PAH compounds. The measured concentrations of PAHs are, in general, very low, ranging from 1 to 60 ng g(sup -1). The texture of soils is mostly sandy loam with few samples being 100% silt. Collected soils are moderately basic with pH values of 8-9 except for the Salten Skov soil, which is slightly acidic. Although the diverse and variable microbial populations of the samples at the sample sites might have affected the levels and variety of PAHs detected, SPME appears to be a rapid, viable field sampling technique with implications for use on planetary missions.

  17. Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high-performance liquid chromatography.

    Science.gov (United States)

    Wang, Zhibing; He, Mengyu; Jiang, Chunzhu; Zhang, Fengqing; Du, Shanshan; Feng, Wennan; Zhang, Hanqi

    2015-12-01

    Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High-performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid-phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid-phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion-pairing agent (NH4 PF6 ), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3-13.4 μg/kg. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Determination of four sulfonylurea herbicides in tea by matrix solid-phase dispersion cleanup followed by dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Liang, Pei; Wang, Jinjin; Liu, Guojiao; Guan, Jinyan

    2014-09-01

    Matrix solid-phase dispersion combined with dispersive liquid-liquid microextraction has been developed as a new sample pretreatment method for the determination of four sulfonylurea herbicides (chlorsulfuron, bensulfuron-methyl, chlorimuron-ethyl, and pyrazosulfuron) in tea by high-performance liquid chromatography with diode array detection. The extraction and cleanup by matrix solid-phase dispersion was carried out by using CN-silica as dispersant and carbon nanotubes as cleanup sorbent eluted with acidified dichloromethane. The eluent of matrix solid-phase dispersion was evaporated and redissolved in 0.5 mL methanol, and used as the dispersive solvent of the following dispersive liquid-liquid microextraction procedure for further purification and enrichment of the target analytes before high-performance liquid chromatography analysis. Under the optimum conditions, the method yielded a linear calibration curve in the concentration range from 5.0 to 10 000 ng/g for target analytes with a correlation coefficients (r(2)) ranging from 0.9959 to 0.9998. The limits of detection for the analytes were in the range of 1.31-2.81 ng/g. Recoveries of the four sulfonylurea herbicides at two fortification levels were between 72.8 and 110.6% with relative standard deviations lower than 6.95%. The method was successfully applied to the analysis of four sulfonylurea herbicides in several tea samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Determination of N,N-dimethyltryptamine in beverages consumed in religious practices by headspace solid-phase microextraction followed by gas chromatography ion trap mass spectrometry.

    Science.gov (United States)

    Gaujac, Alain; Dempster, Nicola; Navickiene, Sandro; Brandt, Simon D; de Andrade, Jailson Bittencourt

    2013-03-15

    A novel analytical approach combining solid-phase microextraction (SPME)/gas chromatography ion trap mass spectrometry (GC-IT-MS) was developed for the detection and quantification N,N-dimethyltryptamine (DMT), a powerful psychoactive indole alkaloid present in a variety of South American indigenous beverages, such as ayahuasca and vinho da jurema. These particular plant products, often used within a religious context, are increasingly consumed throughout the world following an expansion of religious groups and the availability of plant material over the Internet and high street shops. The method described in the present study included the use of SPME in headspace mode combined GC-IT-MS and included the optimization of the SPME procedure using multivariate techniques. The method was performed with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber in headspace mode (70 min at 60 °C) which resulted in good precision (RSD<8.6%) and accuracy values (71-109%). Detection and quantification limits obtained for DMT were 0.78 and 9.5 mg L(-1), respectively and good linearity (1.56-300 mg L(-1), r(2)=0.9975) was also observed. In addition, the proposed method showed good robustness and allowed for the minimization of sample manipulation. Five jurema beverage samples were prepared in the laboratory in order to study the impact of temperature, pH and ethanol on the ability to extract DMT into solution. The developed method was then applied to the analysis of twelve real ayahuasca and vinho da jurema samples, obtained from Brazilian religious groups, which revealed DMT concentration levels between 0.10 and 1.81 g L(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Validation of an analytical method for analysis of cannabinoids in hair by headspace solid-phase microextraction and gas chromatography-ion trap tandem mass spectrometry.

    Science.gov (United States)

    Emídio, Elissandro Soares; Prata, Vanessa de Menezes; Dórea, Haroldo Silveira

    2010-06-18

    The development of an analytical method for the determination of Delta(9)-tetrahydrocannabinol (THC), cannabidiol (CBD) and cannabinol (CBN) in samples of human hair is described. Samples were subjected to a procedure based on the combination of headspace solid-phase microextraction (HS-SPME) with gas chromatography linked with mass spectrometry operating in tandem mode (GC-MS/MS). A 10 mg aliquot of sample was firstly decontaminated using petroleum ether, deionized water and dichloromethane (2 mL of each solvent), for 10 min under sonication, and then digested in alkaline solution (1 mol L(-1) NaOH). The method variables evaluated were pH, mass of hair, fiber type, extraction temperature, desorption time, ionic strength, pre-equilibrium time and extraction time. Parameters concerning operation of the tandem mode MS/MS were also assessed and optimized. Validation of the method demonstrated excellent linearity in the range 0.1-8.0 ng mg(-1), with regression coefficients better than 0.994. Precision was determined using two different concentrations (upper and lower limits of the linear range), and RSD values were between 6.6 and 16.4%. Absolute recoveries (measured in triplicate) were in the range 1.1-8.7%, and limits of detection and quantification were 0.007-0.031 ng mg(-1) and 0.012-0.062 ng mg(-1), respectively. The LOQ for THC (0.062 ng mg(-1)) was below the cut-off value (LOQ Toxicologie Analytique (SFTA). The optimized SPME method was applied in analysis of hair samples from Cannabis drug users, showing that CBN and CBD were present in all samples analyzed. 2010 Elsevier B.V. All rights reserved.

  1. Automated determination of aliphatic primary amines in wastewater by simultaneous derivatization and headspace solid-phase microextraction followed by gas chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Llop, Anna; Pocurull, Eva; Borrull, Francesc

    2010-01-22

    This paper presents a fully automated method for determining ten primary amines in wastewater at ng/L levels. The method is based on simultaneous derivatization with pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to ion trap tandem mass spectrometry (GC-IT-MS-MS). The influence of main factors on the efficiency of derivatization and of HS-SPME is described in detail and optimized by a central composite design. For all species, the highest enrichment factors were achieved using a 85 microm polyacrylate (PA) fiber exposed in the headspace of stirred water samples (750 rpm) at pH 12, containing 360 g/L of NaCl, at 40 degrees C for 15 min. Under optimized conditions, the proposed method achieved detection limits ranging from 10 to 100 ng/L (except for cyclohexylamine). The optimized method was then used to determine the presence of primary amines in various types of wastewater samples, such as influent and effluent wastewater from municipal and industrial wastewater treatment plants (WWTPs) and a potable water treatment plant. Although the analysis of these samples revealed the presence of up to 1500 microg/L of certain primary amines in influent industrial wastewater, the concentration of these compounds in the effluent and in municipal and potable water was substantially lower, at low microg/L levels. The new derivatization-HS-SPME-GC-IT-MS-MS method is suitable for the fast, reliable and inexpensive determination of primary amines in wastewater in an automated procedure. Copyright 2009 Elsevier B.V. All rights reserved.

  2. A powerful methodological approach combining headspace solid phase microextraction, mass spectrometry and multivariate analysis for profiling the volatile metabolomic pattern of beer starting raw materials.

    Science.gov (United States)

    Gonçalves, João L; Figueira, José A; Rodrigues, Fátima P; Ornelas, Laura P; Branco, Ricardo N; Silva, Catarina L; Câmara, José S

    2014-10-01

    The volatile metabolomic patterns from different raw materials commonly used in beer production, namely barley, corn and hop-derived products - such as hop pellets, hop essential oil from Saaz variety and tetra-hydro isomerized hop extract (tetra hop), were established using a suitable analytical procedure based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography-quadrupole mass spectrometry detection (GC-qMS). Some SPME extraction parameters were optimized. The best results, in terms of maximum signal recorded and number of isolated metabolites, were obtained with a 50/30 μm DVB/CAR/PDMS coating fiber at 40 °C for 30 min. A set of 152 volatile metabolites comprising ketones (27), sesquiterpenes (26), monoterpenes (19), aliphatic esters (19), higher alcohols (15), aldehydes (11), furan compounds (11), aliphatic fatty acids (9), aliphatic hydrocarbons (8), sulphur compounds (5) and nitrogen compounds (2) were positively identified. Each raw material showed a specific volatile metabolomic profile. Monoterpenes in hop essential oil and corn, sesquiterpenes in hop pellets, ketones in tetra hop and aldehydes and sulphur compounds in barley were the predominant chemical families in the targeted beer raw materials. β-Myrcene was the most dominant volatile metabolite in hop essential oil, hop pellets and corn samples while, in barley, the predominant volatile metabolites were dimethyl sulphide and 3-methylbutanal and, in tetra hop, 6-methyl-2-pentanone and 4-methyl-2-pentanone. Principal component analysis (PCA) showed natural sample grouping among beer raw materials. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Volatile Hydrocarbon Analysis in Blood by Headspace Solid-Phase Microextraction: The Interpretation of VHC Patterns in Fire-Related Incidents.

    Science.gov (United States)

    Waters, Brian; Hara, Kenji; Ikematsu, Natsuki; Takayama, Mio; Kashiwagi, Masayuki; Matsusue, Aya; Kubo, Shin-Ichi

    2017-05-01

    A headspace solid-phase microextraction (HS-SPME) technique was used to quantitate the concentration of volatile hydrocarbons from the blood of cadavers by cryogenic gas chromatography-mass spectroscopy. A total of 24 compounds including aromatic and aliphatic volatile hydrocarbons were analyzed by this method. The analytes in the headspace of 0.1 g of blood mixed with 1.0 mL of distilled water plus 1 µL of an internal standard solution were adsorbed onto a 100-µm polydimethylsiloxane fiber at 0°C for 15 min, and measured using a GC-MS full scan method. The limit of quantitation for the analytes ranged from 6.8 to 10 ng per 1 g of blood. This method was applied to actual autopsy cases to quantitate the level of volatile hydrocarbons (VHCs) in the blood of cadavers who died in fire-related incidents. The patterns of the VHCs revealed the presence or absence of accelerants. Petroleum-based fuels such as gasoline and kerosene were differentiated. The detection of C8-C13 aliphatic hydrocarbons indicated the presence of kerosene; the detection of C3 alkylbenzenes in the absence of C8-C13 aliphatic hydrocarbons was indicative of gasoline; and elevated levels of styrene or benzene in the absence of C3/C4 alkylbenzenes and aliphatic hydrocarbons indicated a normal construction fire. This sensitive HS-SPME method could help aid the investigation of fire-related deaths by providing a simple pattern to use for the interpretation of VHCs in human blood. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  4. Nanostructured conducting molecularly imprinted polymer for selective extraction of salicylate from urine and serum samples by electrochemically controlled solid-phase micro-extraction

    International Nuclear Information System (INIS)

    Ameli, Akram; Alizadeh, Naader

    2011-01-01

    Highlights: ► Overoxidized polypyrrole templated with salicylate has been utilized as conducting molecular imprinted polymer for EC-SPME. ► This first study reported on conducting molecular imprinted polymer was used to EC-SPME of salicylate. ► Proposed method, is particularly effective in sample clean-up and selective monitoring of salicylate in physiological samples. - Abstract: Overoxidized polypyrrole (OPPy) films templated with salicylate (SA) have been utilized as conducting molecular imprinted polymers (CMIPs) for potential-induced selective solid-phase micro-extraction processes. Various important fabrication factors for controlling the performance of the OPPy films have been investigated using fluorescence spectrometry. Several key parameters such as applied potential for uptake, release, pH of uptake and release solution were varied to achieve the optimum micro-extraction procedure. The film template with SA exhibited excellent selectivity over some interference. The calibration graphs were linear in the ranges of 5 × 10 −8 to 5 × 10 −4 and 1.2 × 10 −6 to 5 × 10 −4 mol mL −1 and the detection limit was 4 × 10 −8 mol L −1 . The OPPy film as the solid-phase micro-extraction absorbent has been applied for the selective clean-up and quantification of trace amounts of SA from physiological samples. The results of scanning electron microscopy (SEM) have confirmed the nano-structure morphologies of the films.

  5. Ultra trace analysis of PAHs by designing simple injection of large amounts of analytes through the sample reconcentration on SPME fiber after magnetic solid phase extraction.

    Science.gov (United States)

    Khodaee, Nader; Mehdinia, Ali; Esfandiarnejad, Reyhaneh; Jabbari, Ali

    2016-01-15

    A simple solventless injection method was introduced based on the using of a solid-phase microextraction (SPME) fiber for injection of large amounts of the analytes extracted by the magnetic solid phase extraction (MSPE) procedure. The resulted extract from MSPE procedure was loaded on a G-coated SPME fiber, and then the fiber was injected into the gas chromatography (GC) injection port. This method combines the advantages of exhaustive extraction property of MSPE and the solvent-less injection of SPME to improve the sensitivity of the analysis. In addition, the analytes were re-concentrated prior to inject into the gas chromatography (GC) inlet because of the organic solvent removing from the remaining extract of MSPE technique. Injection of the large amounts of analytes was made possible by using the introduced procedure. Fourteen polycyclic aromatic hydrocarbons (PAHs) with different volatility were used as model compounds to investigate the method performance for volatile and semi-volatile compounds. The introduced method resulted in the higher enhancement factors (5097-59376), lower detection limits (0.29-3.3pgmL(-1)), and higher sensitivity for the semi-volatile compounds compared with the conventional direct injection method. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Zinc oxide/polypyrrole nanocomposite as a novel solid phase microextraction coating for extraction of aliphatic hydrocarbons from water and soil samples

    Energy Technology Data Exchange (ETDEWEB)

    Amanzadeh, Hatam; Yamini, Yadollah [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175 Tehran (Iran, Islamic Republic of); Moradi, Morteza [Department of Semiconductors, Materials and Energy Research Center, Karaj (Iran, Islamic Republic of)

    2015-07-16

    Highlights: • ZnO/polypyrrole (ZNO/PPY) nanocomposite coating was fabricated on stainless steel. • Nanocomposite coating morphology was evaluated using scanning electron microscopy. • It was applied for HS-SPME of aliphatic hydrocarbons in water and soil samples. • Separation and determination of the hydrocarbons were performed by GC-FID. • The method is suitable for routine analysis of n-alkanes in various environmental samples. - Abstract: In this work, ZnO/PPy nanocomposite coating was fabricated on stainless steel and evaluated as a novel headspace solid phase microextraction (HS-SPME) fiber coating for extraction of ultra-trace amounts of environmental pollutants; namely, aliphatic hydrocarbons in water and soil samples. The ZnO/PPy nanocomposite were prepared by a two-step process including the electrochemical deposition of PPy on the surface of stainless steel in the first step, and the synthesis of ZnO nanorods by hydrothermal process in the pores of PPy matrix in the second step. Porous structure together with ZnO nanorods with the average diameter of 70 nm were observed on the surface by using scanning electron microscopy (SEM). The effective parameters on HS-SPME of hydrocarbons (i.e., extraction temperature, extraction time, desorption temperature, desorption time, salt concentration, and stirring rate) were investigated and optimized by one-variable-at-a-time method. Under optimized conditions (extraction temperature, 65 ± 1 °C; extraction time, 15 min; desorption temperature, 250 °C; desorption time, 3 min; salt concentration, 10% w/v; and stirring rate, 1200 rpm), the limits of detection (LODs) were found in the range of 0.08–0.5 μg L{sup −1}, whereas the repeatability and fiber-to-fiber reproducibility were in the range 5.4–7.6% and 8.6–10.4%, respectively. Also, the accuracies obtained for the spiked n-alkanes were in the range of 85–108%; indicating the absence of matrix effects in the proposed HS-SPME method. The results

  7. Solid-phase microextraction

    DEFF Research Database (Denmark)

    Nilsson, Torben

    and organophosphate pesticides and triazine herbicides together with their metabolites in aqueous samples. SPME combined with gas chromatography proved to be a precise, accurate and sensitive technique for water analysis. Also SPME combined with high performance liquid chromatography was tested, and a method...

  8. Analysis of polysulfides in drinking water distribution systems using headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Kristiana, Ina; Heitz, Anna; Joll, Cynthia; Sathasivan, Arumugam

    2010-09-17

    Sulfide and polysulfides are strong nucleophiles and reducing agents that participate in many environmentally significant processes such as the formation of sulfide minerals and volatile organic sulfur compounds. Their presence in drinking water distribution systems are of particular concern and need to be assessed, since these species consume disinfectants and dissolved oxygen, react with metal ions to produce insoluble metal sulfides, and cause taste and odour problems. The analysis of sulfide and polysulfides in drinking water distribution systems is challenging due to their low concentrations, thermal instability and their susceptibility to undergo oxidation and disproportionation reactions. This paper reports on the development and optimisation of a rapid, simple, and sensitive method for the determination of sulfide and polysulfides in drinking water distribution systems. The method uses methyl iodide to derivatize sulfide and polysulfides into their corresponding dimethyl(poly)sulfides, which are then extracted using solid-phase microextraction in the headspace mode and analysed by gas chromatography-mass spectrometry. Good sensitivity was achieved for the analysis of dimethyl(poly)sulfides, with detection limits ranging from 50 to 240 ng L(-1). The method also demonstrated good precision (repeatability: 3-7%) and good linearity over two orders of magnitude. Matrix effects from raw drinking water containing organic carbon (3.8 mg L(-1)) and from sediment material from a drinking water distribution system were shown to have no interferences in the analysis of dimethyl(poly)sulfides. The method provides a rapid, robust, and reliable mean to analyse trace levels of sulfides and polysulfides in aqueous systems. The new method described here is more accessible and user-friendly than methods based on closed-loop stripping analysis, which have been traditionally used for the analysis of these compounds. The optimised method was used to analyse samples collected

  9. Modelling of adsorption kinetics and calibration curves of gaseous volatile organic compounds with adsorptive solid-phase microextraction fibre: toluene and acetone for indoor air applications.

    Science.gov (United States)

    Mocho, Pierre; Nicolle, Jérôme; Desauziers, Valérie

    2008-09-01

    Solid-phase microextraction (SPME) with adsorptive Carboxen/PDMS fibre is a powerful sampling device for volatile organic compounds (VOCs) at trace levels in air. However, owing to competitive adsorption, quantification remains a challenging task. In this area, a theoretical model, based on Fick's laws and an extended Langmuir equation, is proposed to deal with the adsorption kinetics of acetone/toluene mixture on SPME fibre under various static extraction conditions. The semipredictive model is first used to determine the axial diffusion coefficients of analytes in the sampling device. The model is then tested with a complex VOC mixture, showing good agreement with experimental data.

  10. Use of solid-phase microextraction for the detection of acetic acid by ion-trap gas chromatography-mass spectrometry and application to indoor levels in museums.

    Science.gov (United States)

    Godoi, Ana F L; Van Vaeck, Luc; Van Grieken, René

    2005-03-04

    A simple and efficient method using solid-phase microextraction (SPME) and gas chromatography-ion trap mass spectrometry (GC-ITMS) was developed for the analysis of acetic acid in air. The choice of the SPME fibre revealed to be critical as well as the sampling and desorption time. A dilution vessel was used for calibration. The precision of the method was found to be 4.7% relative standard deviation (RSD) and the detection limit 5.7 microg m(-3). The SPME-GC-MS technique was applied to the analysis of acetic acid in museum atmospheres.

  11. Poly(Dimethylsiloxane)-Poly(Vinyl Alcohol) Coated Solid Phase Micro extraction Fiber for Chloropyrifos Analysis

    International Nuclear Information System (INIS)

    Wan Aini Wan Ibrahim; Nor Fairul Zukry Ahmad Rasdy; Norfazilah Muhamad

    2016-01-01

    Traditional liquid - liquid extraction of pesticides consumes large volumes of organic solvent which are hazardous to the operator and is not environment friendly. Solid phase micro extraction (SPME) is a solvent less extraction method which is safer to the operator and is environmental friendly. A sol-gel hybrid fibre coating material, poly(dimethylsiloxane)-poly(vinyl alcohol) (PDMS-PVA) was synthesized and used in head space solid phase micro extraction (HS-SPME) of chloropyrifos. The thickness of the synthesised PDMS-PVA fiber coating was 13.5 μm and it is thermally stable up to 400 degree Celsius. The PDMS-PVA sol-gel hybrid fiber was also stable to two organic solvents tested; acetonitrile and dichloromethane (1 hour dipping) and showed no significant changes in extraction performance for chloropyrifos. Extracted chloropyrifos was analysed using gas chromatography electron capture detector (GC-ECD). Optimum SPME parameters affecting the PDMS-PVA HS-SPME performance namely extraction time (15 min), extraction temperature (50 degree Celsius), desorption time (5 min), desorption temperature (260 degree Celsius) and stirring rate (120 rpm) were used for extraction. It was found that HSSPME using PDMS-PVA sol-gel fiber gave significantly better extraction performance of chloropyrifos compared to commercial 100 μm PDMS fiber. The PDMS-PVA fiber showed excellent operational performances such as temperature stability (up to 380 degree Celsius), coating lifetime (up to 170 times use) and organic solvent stability. The PDMS-PVA-HS-SPME method showed excellent recovery for chloropyrifos from tomatoes (98.0 %, 5.9 % RSD) at 0.01 μg/ g spiked level (5 times lower than maximum residue limit set by European Union). (author)

  12. Simple method for the determination of personal care product ingredients in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by GC-MS.

    Science.gov (United States)

    Cabrera-Peralta, Jerónimo; Peña-Alvarez, Araceli

    2018-02-19

    A simple method for the simultaneous determination of personal care product ingredients: galaxolide, tonalide, oxybenzone, 4-methylbenzyliden camphor, padimate-o, 2-ethylhexyl methoxycinnamate, octocrylene, triclosan, and methyl triclosan in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by gas chromatography with mass spectrometry was developed. Lettuce was directly extracted by ultrasound-assisted extraction with methanol, this extract was combined with water, extracted by solid-phase microextraction in immersion mode, and analyzed by gas chromatography with mass spectrometry. Good linear relationships (25-250 ng/g, R 2  > 0.9702) and low detection limits (1.0-25 ng/g) were obtained for analytes along with acceptable precision for almost all analytes (RSDs < 20%). The validated method was applied for the determination of personal care product ingredients in commercial lettuce and lettuces grown in soil and irrigated with the analytes, identifying the target analytes in leaves and roots of the latter. This procedure is a miniaturized and environmentally friendly proposal which can be a useful tool for quality analysis in lettuce. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Simultaneous Determination of Parathion, Malathion, Diazinon, and Pirimiphos Methyl in Dried Medicinal Plants Using Solid-Phase Microextraction Fibre Coated with Single-Walled Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Reza Ahmadkhaniha

    2012-01-01

    Full Text Available A reliable and sensitive headspace solid-phase microextraction gas chromatography-mass spectrometry method for simultaneous determination of different organophosphorus pesticides in dried medicinal plant samples is described. The analytes were extracted by single-walled carbon nanotubes as a new solid-phase microextraction adsorbent. The developed method showed good performance. For diazinon and pirimiphos methyl calibration, curves were linear (r2≥0.993 over the concentration ranges from 1.5 to 300 ng g−1, and the limit of detection at signal-to-noise ratio of 3 was 0.3 ng g−1. For parathion and malathion, the linear range and limit of detection were 2.5–300 (r2≥0.991 and 0.5 ng g−1, respectively. In addition, a comparative study between the single-walled carbon nanotubes and a commercial polydimethylsiloxane fibre for the determination of target analytes was carried out. Single-walled carbon nanotubes fibre showed higher extraction capacity, better thermal stability (over 350∘C, and longer lifespan (over 250 times than the commercial polydimethylsiloxane fibre. The developed method was successfully applied to determine target organophosphorus pesticides in real samples.

  14. Nanostructured conducting molecularly imprinted polymer for selective extraction of salicylate from urine and serum samples by electrochemically controlled solid-phase micro-extraction

    Energy Technology Data Exchange (ETDEWEB)

    Ameli, Akram [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Alizadeh, Naader, E-mail: alizaden@modares.ac.ir [Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2011-11-30

    Highlights: Black-Right-Pointing-Pointer Overoxidized polypyrrole templated with salicylate has been utilized as conducting molecular imprinted polymer for EC-SPME. Black-Right-Pointing-Pointer This first study reported on conducting molecular imprinted polymer was used to EC-SPME of salicylate. Black-Right-Pointing-Pointer Proposed method, is particularly effective in sample clean-up and selective monitoring of salicylate in physiological samples. - Abstract: Overoxidized polypyrrole (OPPy) films templated with salicylate (SA) have been utilized as conducting molecular imprinted polymers (CMIPs) for potential-induced selective solid-phase micro-extraction processes. Various important fabrication factors for controlling the performance of the OPPy films have been investigated using fluorescence spectrometry. Several key parameters such as applied potential for uptake, release, pH of uptake and release solution were varied to achieve the optimum micro-extraction procedure. The film template with SA exhibited excellent selectivity over some interference. The calibration graphs were linear in the ranges of 5 Multiplication-Sign 10{sup -8} to 5 Multiplication-Sign 10{sup -4} and 1.2 Multiplication-Sign 10{sup -6} to 5 Multiplication-Sign 10{sup -4} mol mL{sup -1} and the detection limit was 4 Multiplication-Sign 10{sup -8} mol L{sup -1}. The OPPy film as the solid-phase micro-extraction absorbent has been applied for the selective clean-up and quantification of trace amounts of SA from physiological samples. The results of scanning electron microscopy (SEM) have confirmed the nano-structure morphologies of the films.

  15. Solid-phase extraction combined with dispersive liquid-liquid microextraction for the determination of pyrethroid pesticides in wheat and maize samples.

    Science.gov (United States)

    Zhu, Xiaodan; Jia, Chunhong; Zheng, Zuntao; Feng, Xiaoyuan; He, Yue; Zhao, Ercheng

    2016-12-01

    A rapid, selective and sensitive sample preparation method based on solid-phase extraction combined with the dispersive liquid-liquid microextration was developed for the determination of pyrethroid pesticides in wheat and maize samples. Initially, the samples were extracted with acetonitrile and water solution followed phase separation with the salt addition. The following sample preparation involves a solid-phase extraction and dispersive liquid-liquid microextraction step, which effectively provide cleanup and enrichment effects. The main experimental factors affecting the performance both of solid-phase extraction and dispersive liquid-liquid microextration were investigated. The validation results indicated the suitability of the proposed method for routine analyze of pyrethroid pesticides in wheat and maize samples. The fortified recoveries at three levels ranged between 76.4 and 109.8% with relative standard deviations of less than 10.7%. The limit of quantification of the proposed method was below 0.0125 mg/kg for the pyrethoroid pesticides. The proposed method was successfully used for the rapid determination of pyrethroid residues in real wheat and maize samples from crop field in Beijing, China. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Solid phase microextraction as a reliable alternative to conventional extraction techniques to evaluate the pattern of hydrolytically released components in Vitis vinifera L. grapes.

    Science.gov (United States)

    Perestrelo, Rosa; Caldeira, Michael; Câmara, José S

    2012-06-15

    In present research, headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-qMS), was evaluated as a reliable and improved alternative to the commonly used liquid-liquid extraction (LLE) technique for the establishment of the pattern of hydrolytically released components of 7 Vitis vinifera L. grape varieties, commonly used to produce the world-famous Madeira wine. Since there is no data available on their glycosidic fractions, at a first step, two hydrolyse procedures, acid and enzymatic, were carried out using Boal grapes as matrix. Several parameters susceptible of influencing the hydrolytic process were studied. The best results, expressed as GC peak area, number of identified components and reproducibility, were obtained using ProZym M with b-glucosidase activity at 35°C for 42h. For the extraction of hydrolytically released components, HS-SPME technique was evaluated as a reliable and improved alternative to the conventional extraction technique, LLE (ethyl acetate). HS-SPME using DVB/CAR/PDMS as coating fiber displayed an extraction capacity two fold higher than LLE (ethyl acetate). The hydrolyzed fraction was mainly characterized by the occurrence of aliphatic and aromatic alcohols, followed by acids, esters, carbonyl compounds, terpenoids, and volatile phenols. Concerning to terpenoids its contribution to the total hydrolyzed fraction is highest for Malvasia Cândida (23%) and Malvasia Roxa (13%), and their presence according previous studies, even at low concentration, is important from a sensorial point of view (can impart floral notes to the wines), due to their low odor threshold (μg/L). According to the obtained data by principal component analysis (PCA), the sensorial properties of Madeira wines produced by Malvasia Cândida and Malvasia Roxa could be improved by hydrolysis procedure, since their hydrolyzed fraction is mainly characterized by terpenoids (e.g. linalool, geraniol) which are responsible

  17. Headspace solid-phase microextraction-gas chromatographic-time-of-flight mass spectrometric methodology for geographical origin verification of coffee

    International Nuclear Information System (INIS)

    Risticevic, Sanja; Carasek, Eduardo; Pawliszyn, Janusz

    2008-01-01

    Increasing consumer awareness of food safety issues requires the development of highly sophisticated techniques for the authentication of food commodities. The food products targeted for falsification are either products of high commercial value or those produced in large quantities. For this reason, the present investigation is directed towards the characterization of coffee samples according to the geographical origin. The conducted research involves the development of a rapid headspace solid-phase microextraction (HS-SPME)-gas chromatography-time-of-flight mass spectrometry (GC-TOFMS) method that is utilized for the verification of geographical origin traceability of coffee samples. As opposed to the utilization of traditional univariate optimization methods, the current study employs the application of multivariate experimental designs to the optimization of extraction-influencing parameters. Hence, the two-level full factorial first-order design aided in the identification of two influential variables: extraction time and sample temperature. The optimum set of conditions for the two variables was 12 min and 55 deg. C, respectively, as directed by utilization of Doehlert matrix and response surface methodology. The high-throughput automated SPME procedure was completed by implementing a single divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) 50/30 μm metal fiber with excellent durability properties ensuring the completion of overall sequence of coffee samples. The utilization of high-speed TOFMS instrument ensured the completion of one GC-MS run of a complex coffee sample in 7.9 min and the complete list of benefits provided by ChromaTOF software including fully automated background subtraction, baseline correction, peak find and mass spectral deconvolution algorithms was exploited during the data evaluation procedure. The combination of the retention index (RI) system using C 8 -C 40 alkanes and the mass spectral library search was utilized for the

  18. Determination of volatile organic compounds in water by headspace solid-phase microextraction gas chromatography coupled to tandem mass spectrometry with triple quadrupole analyzer

    Energy Technology Data Exchange (ETDEWEB)

    Cervera, M.I. [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain); Beltran, J., E-mail: joaquim.beltran@uji.es [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain); Lopez, F.J.; Hernandez, F. [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain)

    2011-10-17

    Highlights: {yields} Employing a statistical optimization improves results reducing experiments. {yields} Use of MS (QqQ) allows high sensitivity determination and improves identification capabilities. {yields} Using Q/q intensity ratios is a powerful tool to ensure compound identification. {yields} HS SPME GC-MS/MS method allows determination of VOCs in complex matrix water samples. - Abstract: In the present work, a rapid method with little sample handling has been developed for determination of 23 selected volatile organic compounds in environmental and wastewater samples. The method is based on headspace solid-phase microextraction (SPME) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) determination using triple quadrupole analyzer (QqQ) in electron ionization mode. The best conditions for extraction were optimised with a factorial design taking into account the interaction between different parameters and not only individual effects of variables. In the optimized procedure, 4 mL of water sample were extracted using a 10 mL vial and adding 0.4 g NaCl (final NaCl content of 10%). An SPME extraction with carboxen/polydimethylsiloxane 75 {mu}m fiber for 30 min at 50 deg. C (with 5 min of previous equilibration time) with magnetic stirring was applied. Chromatographic determination was carried out by GC-MS/MS working in Selected Reaction Monitoring (SRM) mode. For most analytes, two MS/MS transitions were acquired, although for a few compounds it was difficult to obtain characteristic abundant fragments. In those cases, a pseudo selected reaction monitoring (pseudo-SRM) with three ions was used instead. The intensity ratio between quantitation (Q) and confirmation (q) signals was used as a confirmatory parameter. The method was validated by means of recovery experiments (n = 6) spiking mineral water samples at three concentration levels (0.1, 5 and 50 {mu}g L{sup -1}). Recoveries between 70% and 120% were generally obtained with

  19. Preparation and evaluation of a novel molecularly imprinted polymer coating for selective extraction of indomethacin from biological samples by electrochemically controlled in-tube solid phase microextraction

    Energy Technology Data Exchange (ETDEWEB)

    Asiabi, Hamid [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Yamini, Yadollah, E-mail: yyamini@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Seidi, Shahram; Ghahramanifard, Fazel [Department of Analytical Chemistry, Faculty of Chemistry, K.N. Toosi University of Technology, Tehran (Iran, Islamic Republic of)

    2016-03-24

    In the present work, an automated on-line electrochemically controlled in-tube solid-phase microextraction (EC-in-tube SPME) coupled with HPLC-UV was developed for the selective extraction and preconcentration of indomethacin as a model analyte in biological samples. Applying an electrical potential can improve the extraction efficiency and provide more convenient manipulation of different properties of the extraction system including selectivity, clean-up, rate, and efficiency. For more enhancement of the selectivity and applicability of this method, a novel molecularly imprinted polymer coated tube was prepared and applied for extraction of indomethacin. For this purpose, nanostructured copolymer coating consisting of polypyrrole doped with ethylene glycol dimethacrylate was prepared on the inner surface of a stainless-steel tube by electrochemical synthesis. The characteristics and application of the tubes were investigated. Electron microscopy provided a cross linked porous surface and the average thickness of the MIP coating was 45 μm. Compared with the non-imprinted polymer coated tubes, the special selectivity for indomethacin was discovered with the molecularly imprinted coated tube. Moreover, stable and reproducible responses were obtained without being considerably influenced by interferences commonly existing in biological samples. Under the optimal conditions, the limits of detection were in the range of 0.07–2.0 μg L{sup −1} in different matrices. This method showed good linearity for indomethacin in the range of 0.1–200 μg L{sup −1}, with coefficients of determination better than 0.996. The inter- and intra-assay precisions (RSD%, n = 3) were respectively in the range of 3.5–8.4% and 2.3–7.6% at three concentration levels of 7, 70 and 150 μg L{sup −1}. The results showed that the proposed method can be successfully applied for selective analysis of indomethacin in biological samples. - Graphical abstract: An automated on

  20. In situ growth and phenyl functionalization of titania nanoparticles coating for solid-phase microextraction of ultraviolet filters in environmental water samples followed by high performance liquid chromatography-UV detection.

    Science.gov (United States)

    Li, Li; Guo, Ruibin; Li, Yi; Guo, Mei; Wang, Xuemei; Du, Xinzhen

    2015-03-31

    Based on TiO2-nanoparticles coating fabricated by a one-step anodization method on titanium wire substrate, a novel phenyl functionalized solid-phase microextraction (SPME) fiber coating was prepared by simple and rapid in situ chemical assembling technique between the fiber surface titanol groups and trichlorophenylsilane reaction. The as-fabricated fiber exhibited good extraction capability for some UV filters and was employed to determine the ultraviolet (UV) filters in combination with high performance liquid chromatography-UV detection (HPLC-UV). The main parameters affecting extraction performance were investigated and optimized. Under the optimized conditions, the developed method was applied to detect several UV filters at trace concentration levels with only 8 mL of sample volume. They were determined in the range from 0.005 to 25 μg L(-1) with detection limits (S/N=3) from 0.1 to 50 ng L(-1). The relative standard deviations (RSDs) for single fiber repeatability varied from 4.6 to 6.5% (n=5) and fiber-to-fiber reproducibility (n=5) ranged from 5.5 to 9.1%. The linear ranges spanned two-four magnitudes with correlation coefficients above 0.9990. Five real water samples including four Yellow River water samples and one rain water sample were determined sensitively with good recoveries ranging from 86.2 to 105.5%. The functionalized fiber coating performed good reproducible manner, high mechanical strength, good stability and long service life. Moreover, this study proposed an efficient sample pretreatment method for the determination of UV filters from environmental water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Determination of styrene content in Gorgonzola PDO cheese by headspace solid phase micro-extraction (HS-SPME) and gas-chromatography mass-spectrometry (GC-MS).

    Science.gov (United States)

    Chiesa, L M; Panseri, S; Soncin, S; Vallone, L; Dragoni, I

    2010-06-01

    Control of the composition of products that are intended for use as packaging material is essential, particularly when these products come into direct contact with food. It is well known that plastics are not inert and that their residual monomers, starting substances, and additives are able to migrate into the food they contact. Among plastics, styrene is a common compound found in many plastic containers that can also be produced by the oxidation of Penicillium roqueforti used in gorgonzola Protected Denomination of Origin cheese manufacturing. Therefore, solid-phase microextraction combined with gas chromatography/mass spectrometry was applied in the present work to determine the styrene content in packaged and unpackaged gorgonzola cheese samples to understand styrene migration phenomena from plastic containers.

  2. Determination of bisphenol-type contaminants from food packaging materials in aqueous foods by solid-phase microextraction-high-performance liquid chromatography.

    Science.gov (United States)

    Nerín, C; Philo, M R; Salafranca, J; Castle, L

    2002-07-19

    A fast screening method consisting of off-line solid-phase microextraction coupled to HPLC and fluorescence detection, suitable for the analysis of several bisphenol derivatives and their degradation products in aqueous solution, has been developed. Detection limits of 0.7 ng ml(-1) for 2,2-bis[4-(glycidyloxy)phenyl]propane, 0.9 ng ml(-1) for bisphenol A bis(3-chloro-2-hydroxypropyl)ether, 1.1 ng ml(-1) for 2,2-bis(4-hydroxyphenyl)propane and 2.4 ng ml(-1) for bisphenol F diglycidyl ether have been achieved working in the linear range 10-500 ng ml(-1). The good analytical features achieved make the proposed method an interesting option for the direct determination of these compounds in aqueous canned food such as peas, tuna, olives, maize, artichokes or palm hearts. Both the optimization process and the results, including the analysis of real samples, are given and discussed.

  3. Development of an in vitro thin-film solid-phase microextraction method to determine the bioavailability of xenoestrogens in soil.

    Science.gov (United States)

    Engler, Katherine Neafsey; Lemley, Ann T

    2013-09-01

    Biosolids applied to agricultural fields, parks, and other areas represent significant sources of estrogen-like endocrine disrupting compound (EEDC) inputs to soil. It is important to determine the bioavailability of EEDCs in soil to inform risk assessment concerning their environmental presence; Eisenia fetida (earthworms) are typically used in traditional in vivo bioavailability experiments. The development of an in vitro bioavailability method will decrease time, expense, and use of solvents in future analyses. A thin-film solid-phase microextraction (TF-SPME) method for determining the bioavailability of several EEDCs detected in biosolids was developed and optimized. It was found that the TF-SPME method could be used to calculate equilibrium porewater concentrations of diethylhexyl phthalate, bisphenol A, benzophenone, and triclosan at environmentally relevant concentrations in artificial soil within 88 min. The potential and limitations of using TF-SPME-generated porewater concentrations to predict E. fetida tissue concentrations are discussed. Copyright © 2013 SETAC.

  4. Speciation of mercury compounds by gas chromatography with atomic emission detection. Simultaneous optimization of a headspace solid-phase microextraction and derivatization procedure by use of chemometric techniques

    Energy Technology Data Exchange (ETDEWEB)

    Carro, A.M.; Neira, I.; Rodil, R.; Lorenzo, R. A. [Univ. Santiago de Compostela (Spain). Dpto. Quimica Analitica, Nutricion y Bromatologia

    2003-06-01

    A method is proposed for the extraction and determination of organomercury compounds and Hg(II) in seawater samples by headspace solid-phase microextraction (HS-SPME) combined with capillary gas chromatography-microwave-induced plasma atomic emission spectrometry. The mercury species were derivatized with sodium tetraphenylborate, sorbed on a polydimethylsiloxane-coated fused-silica fibre, and desorbed in the injection port of the GC, in splitless mode. Experimental design methodology was used to evaluate the effect of six HS-SPME-derivatization variables: sample volume, NaBPh{sub 4} volume, pH, sorption time, extraction-derivatization temperature, and rate of stirring. Use of a multicriterion decision-making approach, with the desirability function, enabled determination of the optimum working conditions of the procedure for simultaneous analysis of three mercury species. (orig.)

  5. Determination of steroids, caffeine and methylparaben in water using solid phase microextraction-comprehensive two dimensional gas chromatography-time of flight mass spectrometry.

    Science.gov (United States)

    Lima Gomes, Paulo C F; Barnes, Brian B; Santos-Neto, Álvaro J; Lancas, Fernando M; Snow, Nicholas H

    2013-07-19

    Analysis of several emerging contaminants (steroids, caffeine and methylparaben) in water using automated solid-phase microextraction with comprehensive two dimensional gas chromatography coupled to time of flight mass spectrometry (SPME-GCxGC-ToF/MS) is presented. Experimental design was used to determine the best SPME extraction conditions and the steroids were not derivatized prior to injection. SPME-GCxGC-ToF/MS provided linear ranges from 0.6 to 1200μgL(-1) and limits of detection and quantitation from 0.02 to 100μgL(-1). A series of river water samples obtained locally were subjected to analysis. SPME-GCxGC-ToF/MS is readily automated, straightforward and competitive with other methods for low level analysis of emerging contaminants. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Identification of volatile organic compounds in leaves, roots and gum of Astragalus compactus Lam. using solid phase microextraction followed by GC-MS analysis.

    Science.gov (United States)

    Movafeghi, A; Djozan, Dj; Razeghi, J A; Baheri, T

    2010-05-01

    A solid phase microextraction sampling method using pencil-lead fibre coupled with gas chromatography-mass spectrometry was used to monitor the organic volatile compounds of the roots, leaves and gum of Astragalus compactus. Under optimised conditions, a range of volatile compounds were recognised in different parts of A. compactus. Based on the results obtained, the nature and level of the volatiles vary in distinct parts of the plant. In comparison with other Astragalus species investigated, only one volatile organochlorine compound, tetradecane,1-chloro, was identified in roots. Intriguingly, the toxic chlorinated component was not detectable in the gum samples. These findings highlight the higher quality of the gum of A. compactus compared to the gums of some other Astragalus species, which are reported to be contaminated with chlorinated components.

  7. Stir bar sorptive extraction-gas chromatography-mass spectrometry analysis of tetramethylene disulfotetramine in food: Method development and comparison to solid-phase microextraction.

    Science.gov (United States)

    De Jager, Lowri S; Perfetti, Gracia A; Diachenko, Gregory W

    2009-03-09

    A stir bar sorptive extraction-gas chromatography-mass spectrometry (SBSE-GC-MS) method for the determination of tetramethylene disulfotetramine is presented. The limits of detection (LOD) of the optimized method was 0.2ngg(-1) for extractions from water and 0.3-2.1ngg(-1) for extractions from foods. Recovery was highly matrix dependent (36-130%) and quantification required standard addition calibrations. Standard addition calibration lines had high linearity (R(2)>0.97) and replicate extractions had good reproducibility (R.S.D.=4.4-9.8%). A comparison of the SBSE method and a previously developed headspace (HS)-solid-phase microextraction (SPME) method was performed. Generally, SBSE provided higher sensitivity with decreased analysis time.

  8. Evaluation of multiple solid-phase microextraction as a technique to remove the matrix effect in packaging analysis for determination of volatile organic compounds.

    Science.gov (United States)

    Ezquerro, Oscar; Pons, Begoña; Tena, María Teresa

    2003-12-12

    Multiple solid-phase microextraction (SPME) is an useful technique for the direct quantification of solid samples removing any matrix effect. The volatile organic compounds formed in the extrusion-coating process of multilayer packaging materials have already been quantified by multiple HS-SPME coupled to gas chromatography (GC)-mass spectrometry (MS) using volatile organic compound (VOC) solutions in hexadecane for calibration. In this article, water is proposed as solvent to prepare the calibration solutions because it provides a shorter calibration time, better linearity, better reproducibility, and lower detection limits than hexadecane. Besides, the extraction of VOCs from aqueous solutions is exhaustive and avoids the extrapolations needed to calculate the total peak areas, as they can be calculated as the sum of the individual areas of each extraction. Finally, it is checked whether the two solvents provide the same mean values for the total peak areas.

  9. [Analysis of volatile components in Qingshanlvshui tea using solid-phase microextraction/accelerated solvent extraction-gas chromatography-mass spectrometry].

    Science.gov (United States)

    Zhan, Jiafen; Lu, Sheming; Meng, Zhaoyu; Xiang, Nengjun; Cao, Qiu'e; Miao, Mingming

    2008-05-01

    The volatile components of Qingshanlvshui Tea were extracted using solid phase micro-extraction (SPME) and accelerated solvent extraction (ASE), and then were identified by gas chromatography-mass spectrometry (GC-MS). It showed that ninety-one compounds were identified, including forty-nine by SPME, fifty-six by ASE, and fourteen by both of them. The main constituents were beta-myrcene, 3,5,5-trimethyl-1,5-heptadiene, L-limonene, alpha-ocimene, beta-ocimene, beta-pinene, 2-methylbenzaldehyde, 5-(hydroxymethyl)-2-furfural. Both SPME and ASE have their advantages. SPME is excellent at simplicity, rapidity, solvent-free, high enrichment, low detection limit, environment friendly etc. ASE has characteristics of time and solvent saving, automation, simplicity, as well as high efficiency.

  10. Determination of 5-hydroxymethylfurfural in honey, using headspace-solid-phase microextraction coupled with a polyoxometalate-coated piezoelectric quartz crystal.

    Science.gov (United States)

    Veríssimo, Marta I S; Gamelas, José A F; Evtuguin, Dmitry V; Gomes, M Teresa S R

    2017-04-01

    High concentrations of 5-hydroxymethylfurfural (HMF) in honey provide an indication of overheating under inappropriate storage conditions or aging. Conventional methods for determining HMF are cumbersome and require expensive equipment or hazardous reagents. Hence the aim of this study was to propose a new analytical tool for HMF determination in honey, using a low cost acoustic wave sensor. Volatile organic compounds (VOCs) of honey samples were extracted, using the solid phase microextraction (SPME) technique, and HMF was quantified, using a piezoelectric quartz crystal with gold electrodes coated with a layer of decamolybdodivanado phosphoric acid, sensitive to HMF. The reliability of the proposed method was confirmed after comparing the results of HMF quantification with those obtained by the conventional spectrophotometric White method, and no statistical differences were found (α=0.05). Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Dispersive solid phase micro-extraction of mercury(II from environmental water and vegetable samples with ionic liquid modified graphene oxide nanoparticles

    Directory of Open Access Journals (Sweden)

    Nasrollahpour Atefeh

    2017-01-01

    Full Text Available A new dispersive solid phase micro-extraction (dispersive-SPME method for separation and preconcentration of mercury(II using ionic liquid modified magnetic reduced graphene oxide (IL-MrGO nanoparticles, prior to the measurement by cold vapour atomic absorption spectrometry (CV-AAS has been developed. The IL-MrGO composite was characterized by Brunauer– Emmett–Teller method (BET for adsorption-desorption measurement, thermogravimetric analysis (TGA, powder X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS. The method is based on the sorption of mercury( II on IL-MrGO nanoparticles due to electrostatic interaction and complex formation of ionic liquid part of IL-MrGO with mercury(II. The effect of experimental parameters for preconcentration of mercury(II, such as solution type, concentration and volume of the eluent, pH, time of the sorption and desorption, amount of the sorbent and coexisting ion concentration have been optimized. Under the optimized conditions, a linear response was obtained in the concentration range of 0.08–10 ng mL-1 with a determination coefficient of 0.9995. The limit of detection (LOD of the method at a signal to noise ratio of 3 was 0.01 ng mL-1. Intra-day and inter-day precisions were obtained equal to 3.4 and 4.5 %, respectively. The dispersive solid phase micro-extraction of mercury(II on IL-MrGO nanoparticles coupled with cold vapour atomic absorption spectrometry was successfully used for extraction and determination of mercury(II in water and vegetable samples.

  12. Optimization of total vaporization solid-phase microextraction (TV-SPME) for the determination of lipid profiles of Phormia regina, a forensically important blow fly species.

    Science.gov (United States)

    Kranz, William; Carroll, Clinton; Dixon, Darren; Picard, Christine; Goodpaster, John

    2017-11-01

    A new method has been developed for the determination of fatty acids, sterols, and other lipids which naturally occur within pupae of the blow fly Phormia regina. The method relies upon liquid extraction in non-polar solvent, followed by derivatization using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) w/ 1% trimethylchlorsilane (TMCS) carried out inside the sample vial. The analysis is facilitated by total vaporization solid-phase microextraction (TV-SPME), with gas chromatography-mass spectrometry (GC-MS) serving as the instrumentation for analysis. The TV-SPME delivery technique is approximately a factor of five more sensitive than traditional liquid injection, which may alleviate the need for rotary evaporation, reconstitution, collection of high performance liquid chromatography fractions, and many of the other pre-concentration steps that are commonplace in the current literature. Furthermore, the ability to derivatize the liquid extract in a single easy step while increasing sensitivity represents an improvement over current derivatization methods. The most common lipids identified in fly pupae were various saturated and unsaturated fatty acids ranging from lauric acid (12:0) to arachinoic acid (20:4), as well as cholesterol. The concentrations of myristic acid (14:0), palmitelaidic acid (16:2), and palmitoleic acid (16:1) were the most reliable indicators of the age of the pupae. Graphical abstract Blow fly pupae were extracted prior to emerging as adults. The extracts were analyzed via total vaporization solid-phase microextraction (TV-SPME), revealing a complex mixture of lipids that could be associated with the age of the insect. This information may assist in determining a post-mortum interval (PMI) in a death investigation.

  13. Analysis of luwak coffee volatile by using solid phase microextraction and gas chromatography (Analisa senyawa volatil kopi luwak dengan menggunakan mikroekstrasi fase padat dan kromatolgi gas.

    Directory of Open Access Journals (Sweden)

    Ariza Budi Tunjung Sari

    2012-08-01

    Full Text Available The approach to authenticate Luwak coffee is made through analysis of volatile compounds of luwak coffee. Luwak coffee bean from type of arabica obtained from Andungsari Plantation in Bondowoso district, East Java Province Indonesia, was wet processed and sundried prior to roasting step. As many as 120 g green bean was roasted at 170-220°C for 8-12 minutes until reached light brown colour (Agtron scale 65 and was ground prior to extraction. Volatile compounds of roasted Luwak arabica coffee bean were extracted by using solid phase microextraction (SPME at 60°C for 30 minutes. The extracted analyte was subsequently transferred into GC-FID system by splitless injection at 260°C with five minutes sampling time, continued with separation through 50% phenyl 50% dimethylpolysiloxane capillary column and oven temperature programmed from 60°C to 180°C with rate of 5°C/min. Resulted chromatogram shows major peaks mainly in Rt 8.360-9.981, and Rt 9.705-14.778, and minor peaks identified before Rt 10 and after Rt 24. Varied sample quantity ranged within 0.5-2.5 g produced chromatograms which were not significantly different (p=0.08. This research also observed the use of γ-picoline (4-methylpyridine as internal standard. It was showed that γ-picoline appeared at Rt 8.6~ without overlaying other peaks originated from sample. Concentration of γ-picoline at 0.05 μL/g, resulted separable peaks. These findings showed that the use of solid phase microextraction and GC-FID is capable to be apply for identification and quantification of Luwak coffee

  14. Solid-phase extraction assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet to determine sildenafil and its analogues in dietary supplements.

    Science.gov (United States)

    Li, Jing; Roh, Si Hun; Shaodong, Jia; Hong, Ji Yeon; Lee, Dong-Kyu; Shin, Byong-Kyu; Park, Jeong Hill; Lee, Jeongmi; Kwon, Sung Won

    2017-08-01

    A novel analytical method for the simultaneous determination of the concentration of sildenafil and its five analogues in dietary supplements using solid-phase extraction assisted reversed-phase dispersive liquid-liquid microextraction based on solidification of floating organic droplet combined with ion-pairing liquid chromatography with an ultraviolet detector was developed. Parameters that affect extraction efficiency were systematically investigated, including the type of solid-phase extraction cartridge, pH of the extraction environment, and the type and volume of extraction and dispersive solvent. The method linearity was in the range of 5.0-100 ng/mL for sildenafil, homosildenafil, udenafil, benzylsildenafil, and thiosildenafil and 10-100 ng/mL for acetildenafil. The coefficients of determination were ≥0.996 for all regression curves. The sensitivity values expressed as limit of detection were between 2.5 and 7.5 ng/mL. Furthermore, intraday and interday precisions expressed as relative standard deviations were less than 5.7 and 9.9%, respectively. The proposed method was successfully applied to the analysis of sildenafil and its five analogues in complex dietary supplements. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Phytotoxic volatiles in the roots and shoots of Artemisia tridentata as detected by headspace solid-phase microextraction and gas chromatographic-mass spectrometry analysis.

    Science.gov (United States)

    Jassbi, Amir Reza; Zamanizadehnajari, Simin; Baldwin, Ian Thomas

    2010-12-01

    In the vicinity of big sagebrush (Artemisia tridentata), the growth of Nicotiana attenuata is negatively affected, in part due to the alleopathic effect of methyl jasmonate (MeJA) which is produced in large quantities by the aerial parts of sagebrush. Preliminary experiments suggested that growth-inhibiting substances were being emitted from the sagebrush roots. To identify the allelochemical secondary metabolites, we tested different root extracts in seedling growth bioassays with the naturally co-occurring native tobacco, Nicotiana attenuata, in a two-chamber Petri dish assay, optimized for tests of volatiles. Fractions rich in volatile compounds were particularly phytotoxic. We analyzed the volatiles emitted from the roots of intact Artemisia tridentata plants grown in soil, sand, and hydroponic cultures by using dynamic headspace extraction, headspace solvent-microextraction (HSME) and headspace solid-phase microextraction (HSPME), and GC-MS. Camphor, 1,8-cineol, nerol, and neryl isovalerate were phytotoxic and released as the major constituents. In addition to the phytotoxic monoterpenes, himachalenes, longifolene, caryophyllene, and acetylenic spiroethers, were found as characteristic components in the root's volatiles. The allelopathic potential of these root volatiles was compared with that of methyl jasmonate (MeJA), one of the most active compounds emitted from above-ground parts of the plant.

  16. On-line electrochemically controlled in-tube solid phase microextraction of inorganic selenium followed by hydride generation atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Asiabi, Hamid [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Yamini, Yadollah, E-mail: yyamini@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Seidi, Shahram [Department of Analytical Chemistry, Faculty of Chemistry, K.N. Toosi University of Technology, Tehran (Iran, Islamic Republic of); Shamsayei, Maryam; Safari, Meysam; Rezaei, Fatemeh [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2016-05-30

    In this work, for the first time, a rapid, simple and sensitive microextraction procedure is demonstrated for the matrix separation, preconcentration and determination of inorganic selenium species in water samples using an electrochemically controlled in-tube solid phase microextraction (EC-in-tube SPME) followed by hydride generation atomic absorption spectrometry (HG-AAS). In this approach, in which EC-in-tube SPME and HG-AAS system were combined, the total analysis time, was decreased and the accuracy, repeatability and sensitivity were increased. In addition, to increases extraction efficiency, a novel nanostructured composite coating consisting of polypyrrole (PPy) doped with ethyleneglycol dimethacrylate (EGDMA) was prepared on the inner surface of a stainless-steel tube by a facile electrodeposition method. To evaluate the offered setup and the new PPy-EGDMA coating, it was used to extract inorganic selenium species in water samples. Extraction of inorganic selenium species was carried out by applying a positive potential through the inner surface of coated in-tube under flow conditions. Under the optimized conditions, selenium was detected in amounts as small as 4.0 parts per trillion. The method showed good linearity in the range of 0.012–200 ng mL{sup −1}, with coefficients of determination better than 0.9996. The intra- and inter-assay precisions (RSD%, n = 5) were in the range of 2.0–2.5% and 2.7–3.2%, respectively. The validated method was successfully applied for the analysis of inorganic selenium species in some water samples and satisfactory results were obtained. - Graphical abstract: An electrochemically controlled in-tube solid phase microextraction followed by hydride generation atomic absorption spectrometry was developed for extraction and determination ultra-trace amounts of Se in aqueous solutions. - Highlights: • A nanostructured composite coating consisting of PPy doped with EGDMA was prepared. • The coating was

  17. Chlorophenol's ultra-trace analysis in environmental samples by chitosan-zinc oxide nanorod composite as a novel coating for solid phase micro-extraction combined with high performance liquid chromatography.

    Science.gov (United States)

    Alizadeh, Reza

    2016-01-01

    In this study, a simple, novel, and efficient preconcentration method has been developed for the determination of some chlorophenols (4-chlorophenol, 2,5-dichlorophenol, 2,3-dichlorophenol, and 2,4,6-trichlorophenol) using a direct solid phase microextraction (D-SPME) based on chitosan-ZnO nanorod composite combined with high performance liquid chromatography (HPLC). A one step-novel hydrothermal method was demonstrated on the fabrication of ZnO nanorods arrayed on the fused silica fiber in the chitosan hydrogel solution (CZNC) as a new coating of SPME fiber. The coating was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) instruments. The CZNC coating has combined the merits of both ZnO nanorods and chitosan hydrogel; it has several improvements such as increased extraction efficiency of chlorophenols and longer life time (over 80 cycles of D-SPME-HPLC operation). Experimental design method was used for optimization of extraction conditions and determination of four chlorophenols in water samples by SPME-HPLC-UV method. The calibration curves were linear from 5 to 1000 µg L(-1) for analytes, and the limits of detection were between 0.1 and 2 µg L(-1). Single fiber repeatability and fiber-to-fiber reproducibility were in the range of 5.8-10.2% and 8.8-14.5%, respectively. The spiked recoveries at 50 µg L(-1) for environmental water sample were in the range of 93-102%. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Solid-Phase Extraction of Sulfur Mustard Metabolites Using an Activated Carbon Fiber Sorbent.

    Science.gov (United States)

    Lee, Jin Young; Lee, Yong Han

    2016-01-01

    A novel solid-phase extraction method using activated carbon fiber (ACF) was developed and validated. ACF has a vast network of pores of varying sizes and microporous structures that result in rapid adsorption and selective extraction of sulfur mustard metabolites according to the pH of eluting solvents. ACF could not only selectively extract thiodiglycol and 1-methylsulfinyl-2-[2-(methylthio)-ethylsulfonyl]ethane eluting a 9:1 ratio of dichloromethane to acetone, and 1,1'-sulfonylbis[2-(methylsulfinyl)ethane] and 1,1'-sulfonylbis- [2-S-(N-acetylcysteinyl)ethane] eluting 3% hydrogen chloride in methanol, but could also eliminate most interference without loss of analytes during the loading and washing steps. A sample preparation method has been optimized for the extraction of sulfur mustard metabolites from human urine using an ACF sorbent. The newly developed extraction method was applied to the trace analysis of metabolites of sulfur mustard in human urine matrices in a confidence-building exercise for the analysis of biomedical samples provided by the Organisation for the Prohibition of Chemical Weapons. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  19. Analysis of heterocyclic amines in hair by on-line in-tube solid-phase microextraction coupled with liquid chromatography−tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kataoka, Hiroyuki, E-mail: hkataoka@shujitsu.ac.jp; Inoue, Tsutomu; Saito, Keita; Kato, Hisato; Masuda, Kazufumi

    2013-07-05

    Graphical abstract: Mutagenic and carcinogenic heterocyclic amines are accumulated in the hair of smoker. -- Highlights: •On-line in-tube solid-phase microextraction of heterocyclic amines was optimized. •Fourteen heterocyclic amines were simultaneously determined by LC–MS/MS. •Pico gram levels of heterocyclic amines could be easily analyzed within 15 min. •Heterocyclic amines could be quantitatively analyzed from several milligrams of hair. •The method is useful for the assessment of long-term exposure to heterocyclic amines. -- Abstract: Mutagenic and carcinogenic heterocyclic amines (HCAs) are formed during heating of various proteinaceous foods, but human exposure to HCAs has not yet been elucidated in detail. To assess long-term exposure to HCAs, we developed a simple and sensitive method for measuring HCAs in hair by automated on-line in-tube solid-phase microextraction (SPME) coupled with liquid chromatography–tandem mass spectrometry (LC–MS/MS). Using a Zorbax Eclipse XDB-C8 column, 16 HCAs were analyzed within 15 min. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 μL sample at a flow rate of 200 μL min{sup −1} using a Supel-Q PLOT capillary column as an extraction device. The extracted HCAs were easily desorbed from the column by passage of the mobile phase, with no carryover observed. This in-tube SPME LC–MS/MS method showed good linearity for HCAs in the range of 10–2000 pg mL{sup −1}, with correlation coefficients above 0.9989 (n = 18), using stable isotope-labeled HCA internal standards. The detection limits (S/N = 3) of 14 HCAs except for MeAαC and Glu-P-1 were 0.10–0.79 pg mL{sup −1}. This method was successfully utilized to analyze 14 HCAs in hair samples without any interference peaks, with quantitative limits (S/N = 10) of about 0.17–1.32 pg mg{sup −1} hair. Using this method, we evaluated the exposure to HCAs in cigarette smoke and the suitability of using hair HCAs as exposure biomarkers.

  20. Analysis of heterocyclic amines in hair by on-line in-tube solid-phase microextraction coupled with liquid chromatography−tandem mass spectrometry

    International Nuclear Information System (INIS)

    Kataoka, Hiroyuki; Inoue, Tsutomu; Saito, Keita; Kato, Hisato; Masuda, Kazufumi

    2013-01-01

    Graphical abstract: Mutagenic and carcinogenic heterocyclic amines are accumulated in the hair of smoker. -- Highlights: •On-line in-tube solid-phase microextraction of heterocyclic amines was optimized. •Fourteen heterocyclic amines were simultaneously determined by LC–MS/MS. •Pico gram levels of heterocyclic amines could be easily analyzed within 15 min. •Heterocyclic amines could be quantitatively analyzed from several milligrams of hair. •The method is useful for the assessment of long-term exposure to heterocyclic amines. -- Abstract: Mutagenic and carcinogenic heterocyclic amines (HCAs) are formed during heating of various proteinaceous foods, but human exposure to HCAs has not yet been elucidated in detail. To assess long-term exposure to HCAs, we developed a simple and sensitive method for measuring HCAs in hair by automated on-line in-tube solid-phase microextraction (SPME) coupled with liquid chromatography–tandem mass spectrometry (LC–MS/MS). Using a Zorbax Eclipse XDB-C8 column, 16 HCAs were analyzed within 15 min. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 μL sample at a flow rate of 200 μL min −1 using a Supel-Q PLOT capillary column as an extraction device. The extracted HCAs were easily desorbed from the column by passage of the mobile phase, with no carryover observed. This in-tube SPME LC–MS/MS method showed good linearity for HCAs in the range of 10–2000 pg mL −1 , with correlation coefficients above 0.9989 (n = 18), using stable isotope-labeled HCA internal standards. The detection limits (S/N = 3) of 14 HCAs except for MeAαC and Glu-P-1 were 0.10–0.79 pg mL −1 . This method was successfully utilized to analyze 14 HCAs in hair samples without any interference peaks, with quantitative limits (S/N = 10) of about 0.17–1.32 pg mg −1 hair. Using this method, we evaluated the exposure to HCAs in cigarette smoke and the suitability of using hair HCAs as exposure biomarkers

  1. Molecularly imprinted sol-gel nanofibers based solid phase microextraction coupled on-line with high performance liquid chromatography for selective determination of acesulfame.

    Science.gov (United States)

    Moein, Mohammad Mahdi; Javanbakht, Mehran; Karimi, Mohammad; Akbari-Adergani, Behrouz

    2015-03-01

    Sol-gel based molecularly imprinted polymer (MIP) nanofiber was successfully fabricated by electrospinning technique on the surface of a stainless steel bar. The manufactured tool was applied for on-line selective solid phase microextraction (SPME) and determination of acesulfame (ACF) as an artificial sweetener with high performance liquid chromatography (HPLC). The selective ability of method for the extraction of ACF was investigated in the presence of some selected sweeteners such as saccharine (SCH), aspartame (ASP) and caffeine (CAF). Electrospinning of MIP sol-gel solution on the stainless steel bar provided an unbreakable sorbent with high thermal, mechanical, and chemical stability. Moreover, application of the MIP-SPME tool revealed a unique approach for the selective microextraction of the analyte in beverage samples. In this work, 3-(triethoxysilyl)-propylamine (TMSPA) was chosen as a precursor due to its ability to imprint the analyte by hydrogen bonding, Van der Walls, and dipole-dipole interactions. Nylon 6 was also added as a backbone and support for the precursor in which sol could greatly growth during the sol-gel process and makes the solution electrospinable. Various effective parameters in the extraction efficiency of the MIP-SPME tool such as loading time, flow rate, desorption time, selectivity, and the sample volume were evaluated. The linearity for the ACF in beverage sample was in the range of 0.78-100.5 ng mL(-1). Limit of detection (LOD) and quantification (LOQ) were 0.23 and 0.78 ng mL(-1) respectively. The RSD values (n=5) were all below 3.5%at the 20 ng mL(-1) level. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Use of solid-phase microextraction (SPME) for the determination of methadone and EDDP in human hair by GC-MS.

    Science.gov (United States)

    Lucas, A C; Bermejo, A M; Tabernero, M J; Fernández, P; Strano-Rossi, S

    2000-01-10

    Solid-phase microextraction (SPME) is a new extraction technique with many advantages: small sample volume, simplicity, quickness and solvent-free. It is mainly applied to environmental analysis, but is also useful for the extraction of drugs from biological samples. In this paper the use of SPME is proposed for the determination of methadone and its main metabolite EDDP in hair by GC-MS. The hair samples were washed, cut into 1-mm segments, and incubated with Pronase E for 12 h. A 100-micron polydimethylsiloxane (PDMS) film fibre was submerged for 30 min in a diluted solution of the hydrolysis liquid (1:4 with borax buffer) containing methadone-d3 and EDDP-d3 as internal standards. Once the microextraction was concluded the fibre was directly inserted into the CG injection port. Linearity was found for methadone and EDDP in the range studied, 1.0-50 ng/mg hair, with correlation coefficients higher than 0.99. Interassay relative standard deviation (R.S.D) was determined to be less than 13.30% for methadone and less than 8.94% for EDDP, at 3.0 and 30.0 ng/mg. Analytical recoveries were close to 100% for both compounds on spiked samples. The method was applied to the analysis of real hair samples from eight patients of a methadone maintenance programme. The concentration of methadone in hair ranged from 2.45 to 78.10 ng/mg, and for EDDP from 0.98 to 7.76 ng/mg of hair.

  3. A Simple Method for the Simultaneous Determination of Pharmaceuticals and Personal Care Products in River Sediment by Ultrasound-Assisted Extraction Followed by Solid-Phase Microextraction Coupled with Gas Chromatography-Mass Spectrometry.

    Science.gov (United States)

    Díaz, Alejandro; Peña-Alvarez, Araceli

    2017-10-01

    A simple method was developed using ultrasound-assisted extraction (UAE) combined with solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of eight different pharmaceuticals and personal care products (PPCPs) (ibuprofen, 2-benzyl-4-chlorophenol, naproxen, triclosan, ketoprofen, diclofenac, bisphenol A and estrone) in river sediment. UAE conditions were optimized involving extraction variables such as extraction solvent, extraction time, sample amount, extraction temperature, pH and salt addition. A 100 mg of sediment was extracted by optimized UAE process using 7 mL deionized water (pH 3) + 1% methanol as solvent, room temperature and 1 min extraction at 70% of amplitude. A 5 mL of supernatant was subsequently extracted by SPME; the extracted analytes were derivatized on fiber in head-space mode with N-methyl-N-(tertbutyldimethylsilyl) trifluoroacetamide and then analyzed by GC-MS. The developed method was evaluated by testing: precision (CV 0.98), recoveries (56-108%), limits of detection (simple and environmentally friendly, and provides straightforward analyses of these trace organic pollutants in sediment samples. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  4. Identification of odor signature chemicals in cocaine using solid-phase microextraction-gas chromatography and detector-dog response to isolated compounds spiked on U.S. paper currency.

    Science.gov (United States)

    Furton, Kenneth G; Hong, Yi-Cheng; Hsu, Ya-Li; Luo, Tianying; Rose, Stefan; Walton, John

    2002-03-01

    Solid-phase microextraction (SPME) combined with gas chromatography (GC) is optimized and applied to the analysis of street-cocaine samples followed by the field-testing of isolated chemicals using certified detector dogs. SPME proves to be a very sensitive and rapid method for isolating odor chemicals from street-cocaine samples. SPME-GC and activated charcoal strip (ACS)-SPME-GC signature profile methods are developed for the detection and quantitation of cocaine-odor chemicals, including the optimization of controllable variables such as fiber chemistry, extraction time, and desorption time. The volatile odor chemicals in representative illicit cocaine samples are identified and quantitated by the ACS-SPME-GC signature profile method and direct injection. Field tests with drug detector dogs show methyl benzoate to be the dominant signature odor chemical along with cocaine on U.S. currency at a threshold level of approximately 1-10 microg when spiked or when 10 ng/s methyl benzoate is diffused from polymer bottles, which is required in order to initiate an alert. No other substance studied initiated consistent responses by the drug dogs. The results indicate that the microgram levels of cocaine that have been reported on circulated U.S. currency are insufficient to signal an alert from law-enforcement trained drug detector dogs.

  5. Combination of solid-phase extraction-hollow fiber for ultra-preconcentration of some triazole pesticides followed by gas chromatography-flame ionization detection.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Khoshmaram, Leila; Mogaddam, Mohammad Reza Afshar

    2012-01-01

    In this study, an extraction and preconcentration technique using solid-phase extraction (SPE) along with hollow fiber (HF) has been developed as an ultra-preconcentration technique for some triazole pesticides in aqueous samples. Triazole pesticides were employed as model compounds to assess the method and were monitored by gas chromatography-flame ionization detection (GC-FID). Initially, an aqueous solution of target analytes was passed through an RP-8 SPE cartridge and then the adsorbed analytes were eluted with μL amounts of toluene. The collected elute was slowly introduced into an HF that had one end blocked. This allowed precipitation inside the lumen and pores of the HF. Finally, the obtained HF was mounted on a home-made solid-phase microextraction syringe and entered into the GC injection port for thermal desorption-GC analysis. The effect of various experimental parameters including injection port temperature, desorption time, state of HF, washing solvent, elution solvent and its volume, sample volume, etc. were investigated for finding the optimum conditions. The calibration graphs were linear in the ranges of 2-1000 ng/mL (penconazole and hexaconazole), 5-1000 ng/mL (tebuconazole), 15-1000 ng/mL (triticonazole) and the detection limits (LODs) ranged from 0.6 to 4.5 ng/mL. The enhancement factors were in the range of 870-950. The relative standard deviations (RSD%) for five repeated experiments (C=250 ng/mL of each pesticide) varied from 4.5 to 8.7%. The relative recoveries obtained for analytes in grape juice samples, spiked with different levels of each pesticide, were in the range of 87-119%. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Headspace-solid phase microextraction approach for dimethylsulphoniopropionate quantification in Solanum lycopersicum plants subjected to water stress

    Directory of Open Access Journals (Sweden)

    Stefano Catola

    2016-08-01

    Full Text Available Dimethylsulphoniopropionate (DMSP and dimethyl sulphide (DMS are compounds found mainly in marine phytoplankton and in some halophytic plants. DMS is a globally important biogenic volatile in regulating of global sulphur cycle and planetary albedo, whereas DMSP is involved in the maintenance of plant-environment homeostasis. Plants emit minute amounts of DMS compared to marine phytoplankton and there is a need for hypersensitive analytic techniques to enable its quantification in plants. Solid Phase Micro Extraction from Head Space (HS-SPME is a simple, rapid, solvent-free and cost-effective extraction mode, which can be easily hyphenated with GC-MS for the analysis of volatile organic compounds (VOCs. Using tomato (Solanum lycopersicum plants subjected to water stress as a model system, we standardized a sensitive and accurate protocol for detecting and quantifying DMSP pool sizes, and potential DMS emissions, in cryoextracted leaves. The method relies on the determination of DMS free and from DMSP pools before and after the alkaline hydrolysis via HS-SPME-GC-MS. We found a significant (2.5 time increase of DMSP content in water-stressed leaves reflecting clear stress to the photosynthetic apparatus. We hypothesize that increased DMSP, and in turn DMS, in water-stressed leaves are produced by carbon sources other than direct photosynthesis, and function to protect plants either osmotically or as antioxidants. Finally, our results suggest that SPME is a powerful and suitable technique for the detection and quantification of biogenic gases in trace amounts.

  7. Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples.

    Science.gov (United States)

    De Toffoli, Ana L; Fumes, Bruno H; Lanças, Fernando M

    2018-02-22

    On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2-4.0 µg L -1 ) and low detection limits (1.1-2.9 ng L -1 ). The high extraction efficiency was determined with enrichment factors ranging from 1.2-2.9 for the lowest level, 1.3-4.9 intermediate level and 1.2-3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.

  8. Magnetic silica nanomaterials for solid-phase extraction combined with dispersive liquid-liquid microextraction of ultra-trace quantities of plasticizers

    International Nuclear Information System (INIS)

    Yamini, Yadollah; Faraji, Mohammad; Adeli, Mahnaz

    2015-01-01

    We are presenting surface modified magnetic silica nanoparticles (m-Si-NPs) for use in solid-phase extraction combined with dispersive liquid-liquid microextraction (DLLME). The m-Si-NPs were surface-functionalized with octadecyl groups to give a material for the extraction of the plasticizers dibutyl phthalate, di(2-ethylhexyl) adipate and di(2-ethylhexyl) phthalate from water samples. The functionalized m-Si-NPs were characterized by scanning electron microscopy, FTIR spectroscopy, thermal gravimetric analysis, and vibrating sample magnetometry. The results showed that the m-Si-NPs were well functionalized with octadecyl groups. The effects of various experimental variables on the extraction efficiencies were investigated. The analytes were quantified by GC/FID. Under optimal conditions, the calibration plots are linear in the range from 0.01 to 100 μg∙L -1 , and very high enrichment factors (mean value ∼20,000) were obtained. As a result of the high enrichment factors, the detection limits are as low as 2–3 ng∙L -1 . The method was successfully employed to the extraction of the plasticizers from (spiked) water samples, and recoveries are in the order of 93.9 to 106.7 %. The method is low cost, fast, and very sensitive (author)

  9. Determination of 3-chloropropane-1,2-diol in liquid hydrolyzed vegetable proteins and soy sauce by solid-phase microextraction and gas chromatography/mass spectrometry.

    Science.gov (United States)

    Huang, Minjia; Jiang, Guibin; He, Bin; Liu, Jingfu; Zhou, Qingxiang; Fu, Wusheng; Wu, Yongning

    2005-11-01

    Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography/mass spectrometry (GC/MS) method was developed to determine 3-chloropropane-1,2-diol (3-MCPD) in hydrolyzed vegetable protein and Chinese soy sauce. The 3-MCPD was firstly derivativized with phenylboronic acid in aqueous solution at 90 degrees C for 10 min, then extracted by HS-SPME and finally detected with GC/MS, parameters related to both the derivative reaction and the HS-SPME process were optimized. The proposed method has a linear range of 0.0194-394 microg g(-1), a detection limit of 3.87 ng g(-1) (S/N = 3), and a precision of RSD = 7.5% (n = 5). Seventeen real samples, including four HVPs and thirteen soy sauce samples, were analyzed to examine the feasibility of the proposed procedure; with a concentration of 3-MCPD and acceptable recoveries at 0.71 microg g(-1) spiked levels were obtained. Being simpler, faster and more environmentally benign than the existing methods, this method is accurate and suitable for routine analysis.

  10. Determination of different recreational drugs in sweat by headspace solid-phase microextraction gas chromatography mass spectrometry (HS-SPME GC/MS): Application to drugged drivers.

    Science.gov (United States)

    Gentili, Stefano; Mortali, Claudia; Mastrobattista, Luisa; Berretta, Paolo; Zaami, Simona

    2016-09-10

    A procedure based on headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography/mass spectrometry (GC/MS) has been developed for the determination of most commonly used drugs of abuse in sweat of drivers stopped during roadside controls. DrugWipe 5A sweat screening device was used to collect sweat by a specific pad rubbed gently over forehead skin surface. The procedure involved an acid hydrolysis, a HS-SPME extraction for drugs of abuse but Δ(9)-tetrahydrocannabinol, which was directly extracted in alkaline medium HS-SPME conditions, a GC separation of analytes by a capillary column and MS detection by electron impact ionisation. The method was linear from the limit of quantification (LOQ) to 50ng drug per pad (r(2)≥0.99), with an intra- and inter-assay precision and accuracy always less than 15% and an analytical recovery between 95.1% and 102.8%, depending on the considered analyte. Using the validated method, sweat from 60 apparently intoxicated drivers were found positive to one or more drugs of abuse, showing sweat patches testing as a viable economic and simple alternative to conventional (blood and/or urine) and non conventional (oral fluid) testing of drugs of abuse in drugged drivers. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Solvent-free sample preparation by headspace solid-phase microextraction applied to the tracing of n-butyl nitrite abuse.

    Science.gov (United States)

    Tytgat, J; Daenens, P

    1996-01-01

    The most common alkyl nitrites encountered in forensic toxicology are iso-butyl, n-butyl and iso-pentyl(amyl) nitrites. All have become popular as an aphrodisiac, especially among the homosexual population. Alkyl nitrites are a volatile and unstable group of compounds, which hydrolyse in aqueous matrices to the alcohol and nitrite ion. Here we describe a fast, clean and sensitive procedure for the detection of hydrolysed n-butyl nitrite in whole human blood using a new, solvent-free sampling technique, the headspace solid-phase micro-extraction (HSPME), combined with GC/FID analysis. Sample preparation was investigated using two different stationary phases (100 microns polydimethylsiloxane and 85 microns polyacrylate), coating a fused silica fibre. The effect of different sampling times at fixed temperatures was also studied. Our results demonstrate that the HSPME/GC/FID procedure allows tracing of n-butyl nitrite abuse and detects hydrolysed n-butyl nitrite, i.e., released n-butanol, in whole blood at the 1 ng/mL level.

  12. Evaluation of Superparamagnetic Silica Nanoparticles for Extraction of Triazines in Magnetic in-Tube Solid Phase Microextraction Coupled to Capillary Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    R. A. González-Fuenzalida

    2014-04-01

    Full Text Available The use of magnetic nanomaterials for analytical applications has increased in the recent years. In particular, magnetic nanomaterials have shown great potential as adsorbent phase in several extraction procedures due to the significant advantages over the conventional methods. In the present work, the influence of magnetic forces over the extraction efficiency of triazines using superparamagnetic silica nanoparticles (NPs in magnetic in tube solid phase microextraction (Magnetic-IT-SPME coupled to CapLC has been evaluated. Atrazine, terbutylazine and simazine has been selected as target analytes. The superparamagnetic silica nanomaterial (SiO2-Fe3O4 deposited onto the surface of a capillary column gave rise to a magnetic extraction phase for IT-SPME that provided a enhancemment of the extraction efficiency for triazines. This improvement is based on two phenomena, the superparamegnetic behavior of Fe3O4 NPs and the diamagnetic repulsions that take place in a microfluidic device such a capillary column. A systematic study of analytes adsorption and desorption was conducted as function of the magnetic field and the relationship with triazines magnetic susceptibility. The positive influence of magnetism on the extraction procedure was demonstrated. The analytical characteristics of the optimized procedure were established and the method was applied to the determination of the target analytes in water samples with satisfactory results. When coupling Magnetic-IT-SPME with CapLC, improved adsorption efficiencies (60%–63% were achieved compared with conventional adsorption materials (0.8%–3%.

  13. Validated modeling for German white wine varietal authentication based on headspace solid-phase microextraction online coupled with gas chromatography mass spectrometry fingerprinting.

    Science.gov (United States)

    Springer, A E; Riedl, J; Esslinger, S; Roth, T; Glomb, M A; Fauhl-Hassek, C

    2014-07-16

    An untargeted analytical approach combined with chemometrics using the volatiles of German white wine was investigated regarding the usefulness for verifying botanical origin. A total of 198 wine samples of Riesling, Müller-Thurgau, Silvaner, Pinot Gris, and Pinot Blanc were examined applying headspace solid-phase microextraction online coupled with gas chromatography mass spectrometry. The resultant three-dimensional raw data were processed by available metabolomics software. After data treatment, a partial least-squares discriminant analysis (PLS-DA) model was validated. External samples were correctly classified for 97% Silvaner, 93% Riesling, 91% Pinot Gris/Blanc, and 80% Müller-Thurgau. This model was related to monoterpenoids, C13-norisoprenoids, and esters. Further, 100% prediction for a two-class model of Riesling versus Pinot Gris/Blanc was confirmed by 74 additional samples measured independently. Hence, the strategy applied was, in particular, reliable and relevant for white wine varietal classification. In addition, the superior classification performance of the Riesling class was revealed.

  14. Identification of halogenated photoproducts generated after ultraviolet-irradiation of parabens and benzoates in water containing chlorine by solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Alvarez-Rivera, Gerardo; Llompart, Maria; Garcia-Jares, Carmen; Lores, Marta

    2014-07-04

    This work presents a new solid-phase microextraction (SPME)-based approach to investigate the formation of halogenated by-products generated by the UV-induced photodegradation of parabens and their congener benzoates in water containing chlorine. Degradation of parent species, and further identification of their transformation by-products were monitored by gas chromatography coupled to mass spectrometry (GC/MS). In order to improve detectability, SPME was applied as a preconcentration step after UV-irradiation of target preservatives. Experiments performed with dechlorinated water, ultrapure water, and tap water showed that under UV-light, the presence of even low levels of free chlorine, increases the photodegradation rate of target preservatives, enhancing the formation of halogenated photoproducts. Monobrominated, dibrominated and bromochlorinated hydroxybenzoates were identified, and the transformation of benzoates into halogenated parabens was also confirmed. Bromination is expected to occur when free chlorine is present, due to the presence of traces of bromide in water samples. Five halogenated phenols (mainly brominated) were detected as breakdown photoproducts from both families of target preservatives. On the basis of the appearance of the aforementioned by-products, a tentative transformation pathway, consistent with the photoformation-photodecay kinetics of the by-products, is proposed herein for the first time. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Studying Plant–Insect Interactions with Solid Phase Microextraction: Screening for Airborne Volatile Emissions Response of Soybeans to the Soybean Aphid, Aphis glycines Matsumura (Hemiptera: Aphididae

    Directory of Open Access Journals (Sweden)

    Lingshuang Cai

    2015-05-01

    Full Text Available Insects trigger plants to release volatile compounds that mediate the interaction with both pest and beneficial insects. Soybean aphids (Aphis glycines induces soybean (Glycine max leaves to produce volatiles that attract predators of the aphid. In this research, we describe the use of solid-phase microextraction (SPME for extraction of volatiles from A. glycines-infested plant. Objectives were to (1 determine if SPME can be used to collect soybean plant volatiles and to (2 use headspace SPME-GC-MS approach to screen compounds associated with A. glycines-infested soybeans, grown in the laboratory and in the field, to identify previously known and potentially novel chemical markers of infestation. A total of 62 plant volatiles were identified, representing 10 chemical classes. 39 compounds had not been found in previous studies of soybean volatile emissions. 3-hexen-1-ol, dimethyl nonatriene, indole, caryophyllene, benzaldehyde, linalool, methyl salicylate (MeSA, benzene ethanol, and farnesene were considered herbivore-induced plant volatiles (HIPVs. For reproductive field-grown soybeans, three compounds were emitted in greater abundance from leaves infested with A. glycines, cis-3-hexen-1-ol acetate, MeSA and farnesene. In summary, SPME can detect the emission of HIPVs from plants infested with insect herbivores.

  16. Biocompatible in-tube solid phase microextraction coupled with liquid chromatography-fluorescence detection for determination of interferon α in plasma samples.

    Science.gov (United States)

    Chaves, Andréa R; Silva, Bruno J G; Lanças, Fernando M; Queiroz, Maria Eugênia C

    2011-05-27

    The present work demonstrates the successful application of automated biocompatible in-tube solid-phase microextraction coupled with liquid chromatography (in-tube SPME/LC) for determination of interferon alpha(2a) (IFN α(2a)) in plasma samples for therapeutic drug monitoring. A restricted access material (RAM, protein-coated silica) was employed for preparation of a lab-made biocompatible in-tube SPME capillary that enables the direct injection of biological fluids as well as the simultaneous exclusion of macromolecules by chemical diffusion barrier and drug pre-concentration. The in-tube SPME variables, such as sample volume, draw/eject volume, number of draw-eject cycles, and desorption mode were optimized, to improve the sensitivity of the proposed method. The IFN α(2a) analyses in plasma sample were carried out within 25min (sample preparation and LC analyses). The response of the proposed method was linear over a dynamic range, from 0.06 to 3.0MIUmL(-1), with correlation coefficient equal to 0.998. The interday precision of the method presented coefficient of variation lower than 8%. The proposed automated method has adequate analytical sensitivity and selectivity for determination of IFN α(2a) in plasma samples for therapeutic drug monitoring. Copyright © 2010 Elsevier B.V. All rights reserved.

  17. Solid-phase extraction followed by dispersive liquid-liquid microextraction for the sensitive determination of ecstasy compounds and amphetamines in biological samples

    Directory of Open Access Journals (Sweden)

    H. A. Mashayekhi

    2014-09-01

    Full Text Available A novel approach for the determination of ecstasy and amphetamines (3,4-methylenedioxymethylamphetamine (MDMA, Ecstasy, 3,4-methylenedioxyamphetamine (MDA, 3,4-methylenedioxyethylamphetamine (MDEA and 3,4-methylenedioxypropylamphetamine (MDPA in biological samples is presented. The analytes were extracted from the matrix and transferred to a small volume of a high density, water insoluble solvent using solid-phase extraction (SPE followed by dispersive liquid-liquid microextraction (DLLME. This combination not only resulted in a high enrichment factor, but also it could be used in complex matrices (biological samples. Some important extraction parameters, such as sample solution flow rate, sample pH, type and volume of extraction and disperser solvents as well as the salt addition, were studied and optimized. Under the optimized conditions, the calibration graphs were linear in the range of 0.5-500 µg L-1 and 1.0-500 µg L-1 with detection limits in the range of 0.1-0.3 µg L-1 and 0.2-0.7 µg L-1 in urine and plasma samples, respectively. The results showed that SPE-DLLME is a suitable method for the determination of ecstasy components and amphetamines in biological and water samples. DOI: http://dx.doi.org/10.4314/bcse.v28i3.3

  18. First results on headspace-solid phase microextraction-gas chromatography/mass spectrometry of volatile organic compounds emitted by wax objects in museums.

    Science.gov (United States)

    Lattuati-Derieux, A; Thao, S; Langlois, J; Regert, M

    2008-04-11

    Sampling volatile organic compounds (VOCs) emitted by a large variety of materials is nowadays a very useful technique for analytical purpose. In the field of cultural heritage, it can be applied to identify some constituents of museum artefacts off-gassing VOCs without sampling on the object itself. In this study, we focused on objects made of wax. First volatiles emitted by a reference beeswax were trapped and identified by headspace-solid phase microextraction (HS-SPME)-gas chromatography and mass spectrometry (GC/MS). This allowed to identify numerous volatile biomarkers, namely saturated n-alkanes from C(10) to C(21), saturated n-carboxylic acids containing 6-12 carbon atoms, benzene and cinnamic derivatives that may be considered as volatile biomarkers of beeswax. The SPME strategy was then performed at the Orsay museum (Paris) in a showcase containing a wax sculpture "Le Mineur de la Loire" by J.-J. Carriès. The use of beeswax in this sculpture was unequivocally confirmed by the VOCs concentrated in the showcase, together with a set of characteristic molecular compounds identified by HT-GC/MS. HS-SPME-GC/MS thus appears to be a powerful in situ and non-invasive analytical technique that allows to identify natural substances in the field of cultural heritage without any sampling of solid matter from the object. The results obtained are promising for orientating the strategy of preventive conservation related to works of art characterised by important emission of VOCs.

  19. A new and efficient Solid Phase Microextraction approach for analysis of high fat content food samples using a matrix-compatible coating.

    Science.gov (United States)

    De Grazia, Selenia; Gionfriddo, Emanuela; Pawliszyn, Janusz

    2017-05-15

    The current work presents the optimization of a protocol enabling direct extraction of avocado samples by a new Solid Phase Microextraction matrix compatible coating. In order to further extend the coating life time, pre-desorption and post-desorption washing steps were optimized for solvent type, time, and degree of agitation employed. Using optimized conditions, lifetime profiles of the coating related to extraction of a group of analytes bearing different physical-chemical properties were obtained. Over 80 successive extractions were carried out to establish coating efficiency using PDMS/DVB 65µm commercial coating in comparison with the PDMS/DVB/PDMS. The PDMS/DVB coating was more prone to irreversible matrix attachment on its surface, with consequent reduction of its extractive performance after 80 consecutive extractions. Conversely, the PDMS/DVB/PDMS coating showed enhanced inertness towards matrix fouling due to its outer smooth PDMS layer. This work represents the first step towards the development of robust SPME methods for quantification of contaminants in avocado as well as other fatty-based matrices, with minimal sample pre-treatment prior to extraction. In addition, an evaluation of matrix components attachment on the coating surface and related artifacts created by desorption of the coating at high temperatures in the GC-injector port, has been performed by GCxGC-ToF/MS. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Poly(ionic liquids)-coated stainless-steel wires packed into a polyether ether ketone tube for in-tube solid-phase microextraction.

    Science.gov (United States)

    Feng, Juanjuan; Wang, Xiuqin; Tian, Yu; Luo, Chuannan; Sun, Min

    2017-12-01

    An in-tube solid-phase microextraction device was developed by packing poly(ionic liquids)-coated stainless-steel wires into a polyether ether ketone tube. An anion-exchange process was performed to enhance the extraction performance. Surface properties of poly(ionic liquids)-coated stainless-steel wires were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. The extraction device was connected to high-performance liquid chromatography equipment to build an online enrichment and analysis system. Ten polycyclic aromatic hydrocarbons were used as model analytes, and important conditions including extraction time and desorption time were optimized. The enrichment factors from 268 to 2497, linear range of 0.03-20 μg/L, detection limits of 0.010-0.020 μg/L, extraction and preparation repeatability with relative standard deviation less than 1.8 and 19%, respectively were given by the established online analysis method. It has been used to detect polycyclic aromatic hydrocarbons in environmental samples, with the relative recovery (5, 10 μg/L) in the range of 85.1-118.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Solid-Phase Extraction Followed by Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Drop for the Determination of Parabens.

    Science.gov (United States)

    Hashemi, Beshare; Shamsipur, Mojtaba; Fattahi, Nazir

    2015-09-01

    A dispersive liquid-liquid microextraction based on solidification of floating organic drop method combined with solid-phase extraction (500-mg C18 sorbent) was developed for preconcentration and determination of some parabens. The experimental parameters influencing the extraction efficiency such as the type of extraction and disperser solvents, as well as their volumes, breakthrough volume, flow rate and salt addition were studied and optimized. The optimum experimental conditions found included: sample volume, 100 mL; KCl concentration, 1% (w/v); extraction solvent (1-undecanol) volume, 20 µL and disperser solvent (acetone) volume, 250 µL. Under the optimum experimental conditions, calibration graphs were linear in the range of 1-200 µg L(-1) with limits of detection ranged from 0.3 to 1.7 µg L(-1). The relative standard deviations were in the range of 1.2-3.1% (n = 5). The enrichment factors and absolute recoveries of parabens in different matrices were 245-1886 and 9.0-69.8%, respectively. The method was applied to the simultaneous determination of parabens in different matrices. The relative recoveries from water, shampoo and mouth rinse samples, which have been spiked at different levels of parabens, were 87.83-112.25%, 82.80-108.40% and 90.10-97.60%, respectively. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  2. CODEX-compliant eleven organophosphorus pesticides screening in multiple commodities using headspace-solid phase microextraction-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Sang, Zi-Ye; Wang, Yu-Ting; Tsoi, Yeuk-Ki; Leung, Kelvin Sze-Yin

    2013-01-15

    A headspace-solid phase microextraction-gas chromatography-mass spectrometric (HS-SPME-GC-MS, hereafter abbreviated as "SPME") method was developed for dedicated organophosphorus (OP) pesticides assessment in multiple vegetable and fruit commodities. Specific extraction variables were optimised to achieve harmonised extraction performance of eleven OPs in a great span of seven characteristic commodities cataloged in Codex Alimentarius Commission. Comprehensive validation study confirmed analytical robustness of the SPME treatment in turnip, green cabbage, French beans, eggplant, apple, nectarine and grapes. Based on range-specific evaluation, extraction of individual OPs was characterised by sub-ppb level sensitivity and a wide 0.01-2.5 mg L(-1) dynamic range. Effective sample clean-up afforded precise quantification (0.5-10.9% R.S.D.) within a 70-120% recovery range at the MRL levels specified for individual commodities. Compared to conventional methods currently used, the SPME treatment developed here is quick, accurate, and relatively environmental friendly; it represents an attractive, practical way to deliver international standards in OP screening routines. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. Analysis of Odorants in Marking Fluid of Siberian Tiger (Panthera tigris altaica) Using Simultaneous Sensory and Chemical Analysis with Headspace Solid-Phase Microextraction and Multidimensional Gas Chromatography-Mass Spectrometry-Olfactometry

    OpenAIRE

    Simone B. Soso; Jacek A. Koziel

    2016-01-01

    Scent-marking is the most effective method of communication in the presence or absence of a signaler. These complex mixtures result in a multifaceted interaction triggered by the sense of smell. The objective was to identify volatile organic compound (VOC) composition and odors emitted by total marking fluid (MF) associated with Siberian tigers (Panthera tigris altaica). Siberian tiger, an endangered species, was chosen because its MF had never been analyzed. Solid phase microextraction (SPME...

  4. Solid phase microextraction (SPME) for extraction of volatile oxidation products from complex food systems – Pros and cons

    DEFF Research Database (Denmark)

    Jacobsen, Charlotte; Horn, Anna Frisenfeldt; Lu, Henna Fung Sieng

    efficiency obtained with the SPME method can be affected by different factors such as fiber type, stirring of sample versus not stirring, extraction temperature and time. These factors can easily be controlled and optimized to obtain the highest possible extraction efficiency. However, extraction efficiency...... can also be affected by uncontrollable factors such as batch to batch variation between fibers of the same type and presence of compounds in the sample matrix, which competes with the compounds of interest for adsorption to the SPME fiber. The latter factor is particularly a problem when SPME is used...... for analysis of lipid oxidation during storage of complex food matrices. Examples on how uncontrollable factors have affected results obtained with the SPME method in the authors’ lab will be given and the appropriateness of the SPME method for the analysis of volatile oxidation products in selected food...

  5. Is Solid Phase Microextraction (SPME) an appropriate method for extraction of volatile oxidation products from complex food systems

    DEFF Research Database (Denmark)

    Jacobsen, Charlotte; Horn, Anna Frisenfeldt; Lu, Henna Fung Sieng

    efficiency obtained with the SPME method can be affected by different factors such as fiber type, stirring of sample versus not stirring, extraction temperature and time. These factors can easily be controlled and optimized to obtain the highest possible extraction efficiency. However, extraction efficiency...... can also be affected by uncontrollable factors such as batch to batch variation between fibers of the same type and presence of compounds in the sample matrix, which competes with the compounds of interest for adsorption to the SPME fiber. The latter factor is particularly a problem when SPME is used...... for analysis of lipid oxidation during storage of complex food matrices. Examples on how uncontrollable factors have affected results obtained with the SPME method in the authors’ lab will be given and the appropriateness of the SPME method for the analysis of volatile oxidation products in selected food...

  6. Ionic liquid-based matrix solid-phase dispersion coupled with homogeneous liquid-liquid microextraction of synthetic dyes in condiments.

    Science.gov (United States)

    Wang, Zhibing; Zhang, Liyuan; Li, Na; Lei, Lei; Shao, Mingyuan; Yang, Xiao; Song, Ying; Yu, Aimin; Zhang, Hanqi; Qiu, Fangping

    2014-06-27

    The ionic liquid-based matrix solid-phase dispersion homogeneous liquid-liquid microextraction (IL-based MSPD-HLLME) was developed and applied to the extraction of four banned dyes, including chrysoidin, safranine O, auramine O and rhodamine B, in condiment samples. High performance liquid chromatography was applied to the separation and determination of the analytes. The solid sample was directly treated by MSPD using ionic liquid as dispersant and the eluate obtained in MSPD was treated by HLLME. Some experimental parameters, including type of dispersant, ratio of sample to dispersant, type and volume of ionic liquid, type and volume of elution solvent, pH value and ionic strength of the elution solvent, amount of ion-pairing agent (NH4PF6) and extraction time, were investigated and optimized. The linearities for determining the analytes were in the range of 60-2000μgkg(-1) for chrysoidin, 40-2000μgkg(-1) for safranine O and 20-1000μgkg(-1) for auramine O and rhodamine B, with the correlation coefficients ranging from 0.9964 to 0.9991. The limits of detection for the analytes were between 6.7 and 26.8μgkg(-1) and the limits of quantification were between 15.99 and 58.48μgkg(-1). When the present method was applied to the analysis of spiked condiment samples, the recoveries of the analytes ranged from 90.69 to 113.52% and relative standard deviations were lower than 8.2%. The present method combined the advantages of MSPD and HLLME, and could be applied for the determination of synthetic dyes in condiment samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Use of solid-phase microextraction coupled to gas chromatography-mass spectrometry for determination of urinary volatile organic compounds in autistic children compared with healthy controls.

    Science.gov (United States)

    Cozzolino, Rosaria; De Magistris, Laura; Saggese, Paola; Stocchero, Matteo; Martignetti, Antonella; Di Stasio, Michele; Malorni, Antonio; Marotta, Rosa; Boscaino, Floriana; Malorni, Livia

    2014-07-01

    Autism spectrum disorders (ASDs) are a group of neurodevelopmental disorders which have a severe life-long effect on behavior and social functioning, and which are associated with metabolic abnormalities. Their diagnosis is on the basis of behavioral and developmental signs usually detected before three years of age, and there is no reliable biological marker. The objective of this study was to establish the volatile urinary metabolomic profiles of 24 autistic children and 21 healthy children (control group) to investigate volatile organic compounds (VOCs) as potential biomarkers for ASDs. Solid-phase microextraction (SPME) using DVB/CAR/PDMS sorbent coupled with gas chromatography-mass spectrometry was used to obtain the metabolomic information patterns. Urine samples were analyzed under both acid and alkaline pH, to profile a range of urinary components with different physicochemical properties. Multivariate statistics techniques were applied to bioanalytical data to visualize clusters of cases and to detect the VOCs able to differentiate autistic patients from healthy children. In particular, orthogonal projections to latent structures discriminant analysis (OPLS-DA) achieved very good separation between autistic and control groups under both acidic and alkaline pH, identifying discriminating metabolites. Among these, 3-methyl-cyclopentanone, 3-methyl-butanal, 2-methyl-butanal, and hexane under acid conditions, and 2-methyl-pyrazine, 2,3-dimethyl-pyrazine, and isoxazolo under alkaline pH had statistically higher levels in urine samples from autistic children than from the control group. Further investigation with a higher number of patients should be performed to outline the metabolic origins of these variables, define a possible association with ASDs, and verify the usefulness of these variables for early-stage diagnosis.

  8. Identification and quantification of seven volatile n-nitrosamines in cosmetics using gas chromatography/chemical ionization-mass spectrometry coupled with head space-solid phase microextraction.

    Science.gov (United States)

    Choi, Na Rae; Kim, Yong Pyo; Ji, Won Hyun; Hwang, Geum-Sook; Ahn, Yun Gyong

    2016-01-01

    An analytical method was developed for the identification and quantification of seven volatile n-nitrosamines (n-nitrosodimethylamine [NDMA], n-nitrosoethylmethylamine [NMEA], n-nitrosodiethylamine [NDEA], n-nitrosodipropylamine [NDPA], n-nitrosodibutylamine [NDBA], n-nitrosopiperidine [NPIP], and n-nitrosopyrrolidine [NPYR]) in water insoluble cream type cosmetics. It was found that the head space-solid phase microextraction (HS-SPME) was suitable for extraction, clean up, and pre-concentration of n-nitrosamines in the cream type samples so its optimal conditions were investigated. Identification and quantification of n-nitrosamines using single quadrupole gas chromatography/mass spectrometry (GC/MS) in chemical ionization (CI) mode were carried out with accurate mass measurements. Their accurate masses of protonated molecular ions were obtained within 10 mDa of the theoretical masses when sufficiently high signal was acquired from the unique calibration method using mass and isotope accuracy. For the method validation of quantification, spiking experiments were carried out to determine the linearity, recovery, and method detection limit (MDL) using three deuterated internal standards. The average recovery was 79% within 20% relative standard deviation (RSD) at the concentration of 50 ng/g. MDLs ranged from 0.46 ng/g to 36.54 ng/g, which was satisfactory for the directive limit of 50 ng/g proposed by the European Commission (EC). As a result, it was concluded that the method could be provided for the accurate mass screening, confirmation, and quantification of n-nitrosamines when applied to cosmetic inspection. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Direct quantitation of volatile organic compounds in packaging materials by headspace solid-phase microextraction-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Ezquerro, Scar; Pons, Begoña; Tena, María Teresa

    2003-01-24

    The quantification of volatile organic compounds (VOCs) in flexible multilayer packaging materials using headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) was studied. The analytes imclude 22 compounds such as aldehydes. ketones, carboxylic acids and hydrocarbons formed by thermooxidative degradation of polyethylene during the extrusion coating process in the manufacture of the packaging, and many of them are involved in the unpleasant and undesirable odour of these materials. External standard calibration using a solution of the analytes in an appropriate solvent was the first approach studied. Aqueous solutions of the analytes provided low reproducibility and the reduction of aldehydes to alcohols under the HS-SPME conditions. Hexadecane was chosen as the solvent since its polarity is similar to that of polyethylene and its volatility is lower than that of the analytes. However, hexadecane should be added to the sample before the analysis as it modifies the absorption capacity of the fibre. A 75-microm Carboxen-poly(dimethylsiloxane) fibre was used to extract the VOCs from the headspace above the packaging in a 15-ml sealed vial at 100 degrees C after 5 min of preincubation. The influence of the extraction time on the amount extracted was studied for a standard solution of the analytes in hexadecane, together with the influence of the volume of the standard solution and the amount of the sample placed in the vial. Standard addition and multiple HS-SPME were also studied as calibration methods and the results obtained in the quantitative analysis of a packaging material were compared.

  10. Dispersive micro-solid phase extraction combined with dispersive liquid-liquid microextraction for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Chen, Shizhong; Zhu, Shengping; Lu, Dengbo

    2018-01-01

    A method was developed for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after preconcentration/separation using dispersive micro-solid phase extraction (DMSPE) and dispersive liquid-liquid micro-extraction (DLLME). In DMSPE, titanium dioxide nanofibers were used for preconcentration and separation of analytes. The upper aqueous phase and elution solution from DMSPE were used for further preconcentration and separation of Sb(III) and Sb(V) by DLLME without any pre-oxidation or pre-reduction operation, respectively. The extracts from DLLME were used for ETV-ICP-MS determination with APDC as a chemical modifier. Under optimal conditions, the detection limits of this method were 0.019 and 0.025 pg mL- 1 with relative standard deviations of 5.7% and 6.9% for Sb(III) and Sb(V) (c = 1.0 ng mL- 1, n = 9), respectively. This method was applied for speciation analysis of Sb and its distribution in the tea leaves and the tea infusion, including total, suspended, soluble, organic and inorganic Sb as well as Sb(III) and Sb(V). The results showed that the contents of Sb are 62.7, 12.9 and 47.3 ng g- 1 in the tea leaves, tea residue and tea soup, respectively; those of soluble, organic, inorganic, Sb(III) and Sb(V) are 0.41, 0.11, 0.29, 0.21 and 0.07 ng mL- 1 in the tea soup, respectively. A certified reference material of tea leaves (GBW 07605) was analyzed by this method with satisfactory results.

  11. A salting out system for improving the efficiency of the headspace solid-phase microextraction of short and medium chain free fatty acids.

    Science.gov (United States)

    Fiorini, Dennis; Pacetti, Deborah; Gabbianelli, Rosita; Gabrielli, Serena; Ballini, Roberto

    2015-08-28

    Given the importance of short and medium chain free fatty acids (FFAs) in several fields, this study sought to improve the extraction efficiency of the solid-phase microextraction (SPME) of FFAs by evaluating salting out agents that appear promising for this application. The salts ammonium sulfate ((NH4)2SO4) and sodium dihydrogen phosphate (NaH2PO4) were tried on their own and in combination (3.7/1), in four different total amounts, as salting out agents in the headspace-SPME-gas chromatographic (HS-SPME-GC) analysis of the FFAs from acetic acid (C2) to decanoic acid (C10). Their performance in a model system of an aqueous standard mixture of FFAs at a pH of 3.5 was compared to that of the more commonly used sodium chloride (NaCl) and sodium sulfate (Na2SO4). All of the salts and salt systems evaluated, in proper amount, gave improved results compared to NaCl (saturated), which instead gave interesting results only for the least volatile FFAs C8 and C10. For C2-C6, the salt system that gave the best results compared to NaCl was (NH4)2SO4/NaH2PO4, in the highest of the four amounts evaluated, with factor increases between 1.2 and 4.1-fold, and NaH2PO4, between 1.0 and 4.3-fold. The SPME extraction efficiency given by the mixture (NH4)2SO4/NaH2PO4 was also assessed on biological and food samples, confirming that overall it performed better than NaCl. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. A novel ionic liquid-modified organic-polymer monolith as the sorbent for in-tube solid-phase microextraction of acidic food additives.

    Science.gov (United States)

    Wang, Ting-Ting; Chen, Yi-Hui; Ma, Jun-Feng; Hu, Min-Jie; Li, Ying; Fang, Jiang-Hua; Gao, Hao-Qi

    2014-08-01

    A novel ionic liquid-modified organic-polymer monolithic capillary column was prepared and used for in-tube solid-phase microextraction (SPME) of acidic food additives. The primary amino group of 1-aminopropyl-3-methylimidazolium chloride was reacted with the epoxide group of glycidyl methacrylate. The as-prepared new monomer was then copolymerized in situ with acrylamide and N,N'-methylenebisacrylamide in the presence of polyethylene glycol (PEG)-8000 and PEG-10,000 as porogens. The extraction performance of the developed monolithic sorbent was evaluated for benzoic acid, 3-hydroxybenzoic acid, cinnamic acid, 2,4-dichlorophenoxyacetic acid, and 3-(trifluoromethyl)-cinnamic acid. Such a sorbent, bearing hydrophobic and anion-exchange groups, had high extraction efficiency towards the test compounds. The adsorption capacities for the analytes dissolved in water ranged from 0.18 to 1.74 μg cm(-1). Good linear calibration curves (R(2) > 0.99) were obtained, and the limits of detection (S/N = 3) for the analytes were found to be in the range 1.2-13.5 ng mL(-1). The recoveries of five acidic food additives spiked in Coca-Cola beverage samples ranged from 85.4 % to 98.3 %, with RSD less than 6.9 %. The excellent applicability of the ionic liquid (IL)-modified monolithic column was further tested by the determination of benzoic acid content in Sprite samples, further illustrating its good potential for analyzing food additives in complex samples.

  13. Evaluation of volatile metabolites as markers in Lycopersicon esculentum L. cultivars discrimination by multivariate analysis of headspace solid phase microextraction and mass spectrometry data.

    Science.gov (United States)

    Figueira, José; Câmara, Hugo; Pereira, Jorge; Câmara, José S

    2014-02-15

    To gain insights on the effects of cultivar on the volatile metabolomic expression of different tomato (Lycopersicon esculentum L.) cultivars--Plum, Campari, Grape, Cherry and Regional, cultivated under similar edafoclimatic conditions, and to identify the most discriminate volatile marker metabolites related to the cultivar, the chromatographic profiles resulting from headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-qMS) analysis, combined with multivariate analysis were investigated. The data set composed by the 77 volatile metabolites identified in the target tomato cultivars, 5 of which (2,2,6-trimethylcyclohexanone, 2-methyl-6-methyleneoctan-2-ol, 4-octadecyl-morpholine, (Z)-methyl-3-hexenoate and 3-octanone) are reported for the first time in tomato volatile metabolomic composition, was evaluated by chemometrics. Firstly, principal component analysis was carried out in order to visualise data trends and clusters, and then, linear discriminant analysis in order to detect the set of volatile metabolites able to differentiate groups according to tomato cultivars. The results obtained revealed a perfect discrimination between the different Lycopersicon esculentum L. cultivars considered. The assignment success rate was 100% in classification and 80% in prediction ability by using "leave-one-out" cross-validation procedure. The volatile profile was able to differentiate all five cultivars and revealed complex interactions between them including the participation in the same biosynthetic pathway. The volatile metabolomic platform for tomato samples obtained by HS-SPME/GC-qMS here described, and the interrelationship detected among the volatile metabolites can be used as a roadmap for biotechnological applications, namely to improve tomato aroma and their acceptance in the final consumer, and for traceability studies. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Determination of caffeine, myosmine, and nicotine in chocolate by headspace solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Müller, Christoph; Vetter, Florian; Richter, Elmar; Bracher, Franz

    2014-02-01

    The occurrence of the bioactive components caffeine (xanthine alkaloid), myosmine and nicotine (pyridine alkaloids) in different edibles and plants is well known, but the content of myosmine and nicotine is still ambiguous in milk/dark chocolate. Therefore, a sensitive method for determination of these components was established, a simple separation of the dissolved analytes from the matrix, followed by headspace solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry (HS-SPME-GC-MS/MS). This is the first approach for simultaneous determination of caffeine, myosmine, and nicotine with a convenient SPME technique. Calibration curves were linear for the xanthine alkaloid (250 to 3000 mg/kg) and the pyridine alkaloids (0.000125 to 0.003000 mg/kg). Residuals of the calibration curves were lower than 15%, hence the limits of detection were set as the lowest points of the calibration curves. The limits of detection calculated from linearity data were for caffeine 216 mg/kg, for myosmine 0.000110 mg/kg, and for nicotine 0.000120 mg/kg. Thirty samples of 5 chocolate brands with varying cocoa contents (30% to 99%) were analyzed in triplicate. Caffeine and nicotine were detected in all samples of chocolate, whereas myosmine was not present in any sample. The caffeine content ranged from 420 to 2780 mg/kg (relative standard deviation 0.1 to 11.5%) and nicotine from 0.000230 to 0.001590 mg/kg (RSD 2.0 to 22.1%). © 2014 Institute of Food Technologists®

  15. Ionic liquid based dispersive liquid-liquid microextraction coupled with micro-solid phase extraction of antidepressant drugs from environmental water samples.

    Science.gov (United States)

    Ge, Dandan; Lee, Hian Kee

    2013-11-22

    Ionic liquid-dispersive liquid-liquid microextraction combined with micro-solid phase extraction (IL-DLLME-μ-SPE), and high-performance liquid chromatography (HPLC) was developed for the determination of tricyclic antidepressants (TCAs) in water samples. Two hundred microliters of an organic solvent (as disperser solvent) and 20 μl of 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate were injected into a 5.0 ml sample for sonication-assisted DLLME. After this, a μ-SPE device, containing a novel material zeolite imidazolate framework 4 (ZIF-4), was added into the sample solution and 1 min of vortex-assisted extraction was performed. After 5 min of sonication-assisted desorption, 10 μl of desorption solvent was injected into a HPLC system for analysis. A characteristic property of DLLME-VA-μ-SPE is that any organic solvent and solid sorbent immiscible with water can be used. Special apparatus, or conical-bottom test tubes, and tedious procedures conventionally associated with DLLME such as centrifugation, or refrigeration of solvent are not necessary in the present approach. A novel material, ZIF-4 was employed as μ-SPE sorbent. Under the optimized conditions, the calibration curves were linear in the range of 1-1000 μg/L. The relative standard deviations and the limits of detection were in the range of 1.5% and 7.8% and 0.3 and 1 μg/L, respectively. The relative recoveries of canal water samples, spiked with drugs, were in the range of 94.3% and 114.7%. The results showed that IL-DLLME-μ-SPE was suitable for the determination of TCAs in water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Quantification of 4-hydroxy-2,5-dimethyl-3-furanone in fruit samples using solid phase microextraction coupled with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Chen, Yong; Sidisky, Leonard M

    2011-09-23

    Furaneol is an important aroma compound. It is very difficult to extract furaneol from food matrices and separate it on a gas chromatography column due to its high polarity and instability. A new quantitative method was developed to quantify furaneol in aqueous samples by the use of derivatization/solid phase microextraction (SPME) coupled with gas chromatography/mass spectrometry (GC/MS). The derivatization was carried out by reacting pentafluorobenzyl bromide with furaneol in basic solutions at elevated temperatures. The derivative was stable and less polar so that SPME-GC/MS could be applied for extraction, separation and detection. The automated analytical method had a limit of detection (LOD) of 0.5 ng mL(-1), a limit of quantification (LOQ) of 2 ng mL(-1), a repeatability of 9.5%, and a linear range from 2 to 500 ng mL(-1). The method was applied to analyze fruit samples. And it was found that the concentrations of furaneol in tomato ranged from 95 to 173 μg kg(-1), in strawberries ranged from 1663 to 4852 μg kg(-1). The results were verified with a LC procedure. To facilitate analytical method development, some physico-chemical parameters for furaneol were determined in this work. Its solubility in water was determined as 0.315 g mL(-1) (25°C). Its LogD in water and LogP in 0.1 M phosphate buffer were -0.133 and 0.95 (20 °C), respectively. Its pKa was 8.56 (20 °C). Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Development of new portable miniaturize solid phase microextraction of silver-APDC complex using micropipette tip in-syringe system couple with electrothermal atomic absorption spectrometry.

    Science.gov (United States)

    Naeemullah; Kazi, Tasneem Gul; Afridi, Hassan Imran; Shah, Faheem; Arain, Sadaf Sadia; Arain, Salma Aslam; Panhwar, Abdul Haleem; Arain, Mariam Shahzadi; Samoon, Muhammad Kashif

    2016-02-05

    An innovative and simple miniaturized solid phase microextraction (M-SPME) method, was developed for preconcentration and determination of silver(I) in the fresh and waste water samples. For M-SPME, a micropipette tip packed with activated carbon cloth (ACC) as sorbent, in a syringe system. The size, morphology and elemental composition of ACC before and after adsorption of analyte have been characterized by scanning electron microscopy and energy dispersive spectroscopy. The sample solution treated with a complexing reagent, ammonium pyrrolidine dithiocarbamate (APDC), was drawn into the syringe filled with ACC and dispensed manually for 2 to 10 aspirating/dispensing cycle. Then the Ag- complex sorbed on the ACC in micropipette was quantitatively eluted by drawing and dispensing of different concentrations of acids for 2 to 5 aspirating/dispensing cycles. The extracted Ag ions with modifier were injected directly into the electrothermal atomic absorption spectrometry for analysis. The influence of different variables on the extraction efficiency, including the concentration of ligand, pH, sample volume, eluent type, concentration and volume was investigated. Validity and accuracy of the developed method was checked by the standard addition method. Reliability of the proposed methodology was checked by the relative standard deviation (%RSD), which was found to be <5%. Under the optimized experimental variables, the limits of detection (LOD) and enhancement factors (EF), were obtained to be 0.86 ng L(-1) and 120, respectively. The proposed method was successfully applied for the determination of trace levels of silver ions in fresh and waste water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. A simple and automated method to determine macrocyclic musk fragrances in sewage sludge samples by headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Vallecillos, Laura; Pocurull, Eva; Borrull, Francesc

    2013-11-01

    For the first time, headspace solid-phase microextraction (HS-SPME) has shown to be a powerful technique to extract macrocyclic musk fragrances directly from sewage sludge. It avoids the need to use additional extraction/preconcentration techniques or clean-up procedure and facilitates the automation of the method. Thus, a simple and fully automated method based on HS-SPME and GC-MS has been developed which allows the determination of eight macrocyclic musk fragrances at ngg(-1) (d.w.) levels. The optimal HS-SPME conditions were achieved when a PDMS/DVB 65μm fibre was exposed for 45min in the headspace of 0.25g sewage sludge samples mixed with 0.5mL of water stirred at 750rpm at 80°C. Optimal desorption conditions were found to be 250°C for 3min. Method detection limits were found in the low pgg(-1) range between 10pgg(-1) (d.w.) and 25pgg(-1) (d.w.) depending on the target analytes. In addition, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in sewage sludge with relative standard deviations varying between 1% to 9% and 6% to 15% respectively (n=5, 1000pgg(-1) d.w.). The applicability of the method was tested with sewage sludge from three urban sewage treatment plants (STPs). The analysis revealed the presence of the macrocyclic musks studied in several samples, with concentrations ranging between below MQL (method quantification limit) and 0.89ngg(-1) (d.w.). Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Development of a novel graphene/polyaniline electrodeposited coating for on-line in-tube solid phase microextraction of aldehydes in human exhaled breath condensate.

    Science.gov (United States)

    Li, Yu; Xu, Hui

    2015-05-22

    In this work, we introduced a novel graphene/polyaniline (G/PANI) electrodeposited coating for on-line in-tube solid phase microextraction (IT-SPME) for the first time. The G/PANI coating was prepared on the internal surface of stainless steel tube by a facile in-situ electrodeposition method. The morphology and formation of the composite coating were confirmed by scanning electronic microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Some important experimental parameters that could affect the extraction and separation such as the coating thickness, internal diameter of tube, sampling flow rate as well as sample volume were optimized. The extraction performance of the IT-SPME coating was evaluated systematically. The coating exhibited enhanced mechanical stability, long lifespan, large specific surface area and good biocompatibility compared with polyaniline coating. The on-line IT-SPME method showed higher enrichment efficiency, faster analysis speed and higher automation level than off-line manual mode. Six aldehydes were determined simultaneously with low limits of detection of 0.02-0.04nmolL(-1) and good linearity (R(2)≥0.9920). The method has been applied successfully for the determination of aldehydes in human exhaled breath condensates with good recovery (70-120%) and satisfied reproducibility (relative standard deviation: 1.1-11.9%). This on-line IT-SPME method provides a promising approach for the determination of trace aldehydes with approving sensitivity in human exhaled breath condensates. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Analysis of volatile compounds emitted from fresh Syringa oblata flowers in different florescence by headspace solid-phase microextraction-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Li, Zu-Guang; Lee, Maw-Rong; Shen, De-Long

    2006-08-18

    In this study, a simple and solvent-free method was developed for determination of the volatile compounds from fresh flowers of Syringa oblata using headspace solid-phase microextraction and gas chromatography-mass spectrometry. The SPME parameters were studied, the optimum conditions of a 65mum polydimethylsiloxan/divinylbenezene (PDMS/DVB), extraction temperature of 25 degrees C and extraction time of 30 min were obtained and applied to extraction of the volatile compounds emitted from fresh flowers of S. oblata. The volatile compounds released from fresh flowers of S. oblata were separated and identified by GC-MS. Lilac aldehyde A, lilac aldehyde B, lilac aldehyde C, lilac aldehyde D, lilac alcohol A, lilac alcohol B, lilac alcohol C, lilac alcohol D, alpha-pinene, sabinene, beta-pinene, myrcene, d-limonene, eucalyptol, cis-ocimene, benzaldehyde, terpinolene, linalool, benzene acetaldehyde, alpha-terpineol, p-methoxyanisole, p-anisaldehyde, (Z,E)-alpha-farnesene and (E,E)-alpha-farnesene were the most abundant volatiles released from fresh flowers of S. oblata var. alba. The relative contents of main volatile fragrance were found to be different in emissions from two varieties of S. oblata flowers (white or purple in color). The four isomers of lilac alcohol and four isomer lilac aldehyde were the characteristic components of the scent of fresh flowers of S. oblata. The main volatile fragrance from fresh flowers of S. oblata var. alba in different florescence ((A) flower buds; (B) at the early stage of flower blooming; (C) during the flower blooming; (D) at the end of flower blooming; (E) senescence) were studied in this paper. The results demonstrated that headspace SPME-GC-MS is a simple, rapid and solvent-free method suitable for analysis of volatile compounds emitted from fresh flowers of S. oblata in different florescence.

  1. Extração em fase sólida (SPE e micro extração em fase sólida (SPME de piretróides em água Solid-phase extraction (SPE and solid-phase microextraction of pyrethroids in water

    Directory of Open Access Journals (Sweden)

    Wilma Regina Barrionuevo

    2001-04-01

    Full Text Available The pyrethroids bifenthrin, permethrin, cypermethrin and deltamethrin were extracted by solid phase extraction (SPE and solid phase microextraction (SPME. The analysis were performed on a gas chromatograph with electron capture detection (GC-ECD. Octadecil Silano-C18, Florisil and Silica stationary phases were studied for SPE. Better results were obtained for Florisil which gave recoveries from 80% to 108%. Pyrethroids extraction by SPME showed a linear response and a detection limit of 10 pg ml-1. Although the data showed that the two extraction methods were able to isolate the pesticide residues from water samples, the best results were obtained by using SPME which is more sensitive, faster, cheeper, being a more useful technique for the analysis of pyrethroids in drinking water.

  2. Development of a New Microextraction Fiber Combined to On-Line Sample Stacking Capillary Electrophoresis UV Detection for Acidic Drugs Determination in Real Water Samples

    Directory of Open Access Journals (Sweden)

    Maria Espina-Benitez

    2017-07-01

    Full Text Available A new analytical method coupling a (off-line solid-phase microextraction with an on-line capillary electrophoresis (CE sample enrichment technique was developed for the analysis of ketoprofen, naproxen and clofibric acid from water samples, which are known as contaminants of emerging concern in aquatic environments. New solid-phase microextraction fibers based on physical coupling of chromatographic supports onto epoxy glue coated needle were studied for the off-line preconcentration of these micropollutants. Identification and quantification of such acidic drugs were done by capillary zone electrophoresis (CZE using ultraviolet diode array detection (DAD. Further enhancement of concentration sensitivity detection was achieved by on-line CE “acetonitrile stacking” preconcentration technique. Among the eight chromatographic supports investigated, Porapak Q sorbent showed higher extraction and preconcentration capacities. The screening of parameters that influence the microextraction process was carried out using a two-level fractional factorial. Optimization of the most relevant parameters was then done through a surface response three-factor Box-Behnken design. The limits of detection and limits of quantification for the three drugs ranged between 0.96 and 1.27 µg∙L−1 and 2.91 and 3.86 µg∙L−1, respectively. Recovery yields of approximately 95 to 104% were measured. The developed method is simple, precise, accurate, and allows quantification of residues of these micropollutants in Genil River water samples using inexpensive fibers.

  3. Determination of Methyl tert-Butyl Ether and tert-Butyl Alcohol in Water by Solid-Phase Microextraction/Head Space Analysis in Comparison to EPA Method 5030/8260B

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Keun-Chan; Stringfellow, William T.

    2003-10-02

    Methyl tert-butyl ether (MTBE) is now one of the most common groundwater contaminants in the United States. Groundwater contaminated with MTBE is also likely to be contaminated with tert-butyl alcohol (TBA), because TBA is a component of commercial grade MTBE, TBA can also be used as a fuel oxygenate, and TBA is a biodegradation product of MTBE. In California, MTBE is subject to reporting at concentrations greater than 3 {micro}g/L. TBA is classified as a ''contaminant of current interest'' and has a drinking water action level of 12 {micro}g/L. In this paper, we describe the development and optimization of a simple, automated solid phase microextraction (SPME) method for the analysis of MTBE and TBA in water and demonstrate the applicability of this method for monitoring MTBE and TBA contamination in groundwater, drinking water, and surface water. In this method, the headspace (HS) of a water sample is extracted with a carboxen/polydimethylsiloxane SPME fiber, the MTBE and TBA are desorbed into a gas chromatograph (GC), and detected using mass spectrometry (MS). The method is optimized for the routine analysis of MTBE and TBA with a level of quantitation of 0.3 {micro}g/L and 4 {micro}g/L, respectively, in water. MTBE quantitation was linear for over two orders of concentration (0.3 {micro}g/L -80 {micro}g/L). TBA was found to be linear within the range of 4 {micro}g/L-7,900 {micro}g/L. The lower level of detection for MTBE is 0.03 {micro}g/L using this method. This SPME method using headspace extraction was found to be advantageous over SPME methods requiring immersion of the fiber into the water samples, because it prolonged the life of the fiber by up to 400 sample analyses. This is the first time headspace extraction SPME has been shown to be applicable to the measurement of both MTBE and TBA at concentrations below regulatory action levels. This method was compared with the certified EPA Method 5030/8260B (purge-and-trap/GC/MS) using split

  4. Effectiveness of different solid-phase microextraction fibres for differentiation of selected Madeira island fruits based on their volatile metabolite profile--identification of novel compounds.

    Science.gov (United States)

    Pereira, João; Pereira, Jorge; Câmara, José S

    2011-01-15

    A headspace solid-phase microextraction (HS-SPME) procedure based on five commercialised fibres (85 μm polyacrylate - PA, 100 μm polydimethylsiloxane - PDMS, 65 μm polydimethylsiloxane/divinylbenzene - PDMS/DVB, 70 μm carbowax/divinylbenzene - CW/DVB and 85 μm carboxen/polydimethylsiloxane - CAR/PDMS) is presented for the characterization of the volatile metabolite profile of four selected Madeira island fruit species, lemon (Citrus limon), kiwi (Actinidia deliciosa), papaya (Carica papaya L.) and Chickasaw plum (Prunus angustifolia). The isolation of metabolites was followed by thermal desorption gas chromatography-quadrupole mass spectrometry (GC-qMS) methodology. The performance of the target fibres was evaluated and compared. The SPME fibre coated with CW/DVB afforded the highest extraction efficiency in kiwi and papaya pulps, while in lemon and plum the same was achieved with PMDS/DVB fibre. This procedure allowed for the identification of 80 compounds, 41 in kiwi, 24 in plums, 23 in papaya and 20 in lemon. Considering the best extraction conditions, the most abundant volatiles identified in kiwi were the intense aldehydes and ethyl esters such as (E)-2-hexenal and ethyl butyrate, while in Chicasaw plum predominate 2-hexenal, 2-methyl-4-pentenal, hexanal, (Z)-3-hexenol and cyclohexylene oxide. The major compounds identified in the papaya pulp were benzyl isothiocyanate, linalool oxide, furfural, hydroxypropanone, linalool and acetic acid. Finally, lemon was shown to be the most divergent of the four fruits, being its aroma profile composed almost exclusively by terpens, namely limonene, γ-terpinene, o-cymene and α-terpinolene. Thirty two volatiles were identified for the first time in the fruit or close related species analysed and 14 volatiles are reported as novel volatile metabolites in fruits. This includes 5 new compounds in kiwi (2-cyclohexene-1,4-dione, furyl hydroxymethyl ketone, 4-hydroxydihydro-2(3H)-furanone, 5-acetoxymethyl-2-furaldehyde and

  5. Determination of aflatoxins in food samples by automated on-line in-tube solid-phase microextraction coupled with liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Nonaka, Y; Saito, K; Hanioka, N; Narimatsu, S; Kataoka, H

    2009-05-15

    A simple and sensitive automated method for determination of aflatoxins (B1, B2, G1, and G2) in nuts, cereals, dried fruits, and spices was developed consisting of in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-mass spectrometry (LC-MS). Aflatoxins were separated within 8 min by high-performance liquid chromatography using a Zorbax Eclipse XDB-C8 column with methanol/acetonitrile (60/40, v/v): 5mM ammonium formate (45:55) as the mobile phase. Electrospray ionization conditions in the positive ion mode were optimized for MS detection of aflatoxins. The pseudo-molecular ions [M+H](+) were used to detect aflatoxins in selected ion monitoring (SIM) mode. The optimum in-tube SPME conditions were 25draw/eject cycles of 40 microL of sample using a Supel-Q PLOT capillary column as an extraction device. The extracted aflatoxins were readily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. Using the in-tube SPME LC-MS with SIM method, good linearity of the calibration curve (r>0.9994) was obtained in the concentration range of 0.05-2.0 ng/mL using aflatoxin M1 as an internal standard, and the detection limits (S/N=3) of aflatoxins were 2.1-2.8 pg/mL. The in-tube SPME method showed >23-fold higher sensitivity than the direct injection method (10 microL injection volume). The within-day and between-day precision (relative standard deviations) at the concentration of 1 ng/mL aflatoxin mixture were below 3.3% and 7.7% (n=5), respectively. This method was applied successfully to analysis of food samples without interference peaks. The recoveries of aflatoxins spiked into nuts and cereals were >80%, and the relative standard deviations were Aflatoxins were detected at <10 ng/g in several commercial food samples.

  6. Determination of anabolic steroids in human urine by automated in-tube solid-phase microextraction coupled with liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Saito, Keita; Yagi, Katsuharu; Ishizaki, Atsushi; Kataoka, Hiroyuki

    2010-09-05

    A simple, rapid and sensitive method was developed for determining the presence of seven anabolic steroids (boldenone, nandrolone, testosterone, methyltestosterone, epiandrosterone, androsterone, and atnozolol) in human urine. Glucuronide-conjugates of these compounds were hydrolyzed with beta-glucuronidase. The anabolic steroids were analyzed by on-line in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-mass spectrometry (LC-MS). The steroids were separated within 14 min by high performance liquid chromatography using a Chromolith RP-18e column and 5 mM ammonium formate/methanol (35/65, v/v) as a mobile phase at a flow rate of 1.0 mL/min. Electrospray ionization conditions in the positive ion mode were optimized for the MS detection of these compounds. The optimum in-tube SPME conditions were 20 draw/eject cycles with a sample size of 40 microL using a Supel-Q PLOT capillary column for the extraction. The extracted compounds could be desorbed readily from the capillary column by flow of the mobile phase, and no carryover was observed. Using the in-tube SPME LC-MS with SIM mode detection, good linearity of the calibration curve (r>0.995) was obtained in the concentration range of 0.5-20 ng/mL, except for stanozolol. The detection limits (S/N=3) of anabolic steroids were in the range 9-182 pg/mL and the proposed method showed 20-33-fold higher sensitivity than the direct injection method. The within-day and between-day precisions were below 4.0% and 7.3% (n=5), respectively. This method was applied successfully to the analysis of urine samples without the interference peaks. The recovery rates of anabolic steroids spiked into urine samples were above 85%. This method is useful to analyze the urinary levels of these compounds in anti-doping tests. 2010 Elsevier B.V. All rights reserved.

  7. Optimization of ultrasound-assisted dispersive solid-phase microextraction based on nanoparticles followed by spectrophotometry for the simultaneous determination of dyes using experimental design.

    Science.gov (United States)

    Asfaram, Arash; Ghaedi, Mehrorang; Goudarzi, Alireza

    2016-09-01

    A simple, low cost and ultrasensitive method for the simultaneous preconcentration and determination of trace amount of auramine-O and malachite green in aqueous media following accumulation on novel and lower toxicity nanomaterials by ultrasound-assisted dispersive solid phase micro-extraction (UA-DSPME) procedure combined with spectrophotometric has been described. The Mn doped ZnS nanoparticles loaded on activated carbon were characterized by Field emission scanning electron microscopy (FE-SEM), particle size distribution, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) analyses and subsequently were used as green and efficient material for dyes accumulation. Contribution of experimental variables such as ultrasonic time, ultrasonic temperature, adsorbent mass, vortex time, ionic strength, pH and elution volume were optimized through experimental design, and while the preconcentrated analytes were efficiently eluted by acetone. Preliminary Plackett-Burman design was applied for selection of most significant factors and giving useful information about their main and interaction part of significant variables like ultrasonic time, adsorbent mass, elution volume and pH were obtained by central composite design combined with response surface analysis and optimum experimental conditions was set at pH of 8.0, 1.2mg of adsorbent, 150μL eluent and 3.7min sonication. Under optimized conditions, the average recoveries (five replicates) for two dyes (spiked at 500.0ngmL(-1)) changes in the range of 92.80-97.70% with acceptable RSD% less than 4.0% over a linear range of 3.0-5000.0ngmL(-1) for the AO and MG in water samples with regression coefficients (R(2)) of 0.9975 and 0.9977, respectively. Acceptable limits of detection of 0.91 and 0.61ngmL(-1) for AO and MG, respectively and high accuracy and repeatability are unique advantages of present method to improve the figures of merit for their accurate determination at trace level in complicated

  8. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC-qMSD for evaluation the chemical profile in alcoholic beverages

    International Nuclear Information System (INIS)

    Rodrigues, F.; Caldeira, M.; Camara, J.S.

    2008-01-01

    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC-qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 μm); polyacrylate (PA, 85 μm); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm); carboxen TM /polydimethylsiloxane (CAR/PDMS, 75 μm) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 μm) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC-qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl decanoate (58

  9. Análise de fármacos em material biológico: acoplamento microextração em fase sólida "no tubo" e cromatografia líquida de alta eficiência Analysis of drugs in biological samples: automated "in-tube" solid-phase microextraction and high performance liquid chromatography

    Directory of Open Access Journals (Sweden)

    Maria Eugênia C. Queiroz

    2005-10-01

    Full Text Available A new solid phase microextraction (SPME system, known as in-tube SPME, was recently developed using an open tubular fused-silica capilary column, instead of an SPME fiber, as the SPME device. On-line in-tube SPME is usually used in combination with high performance liquid chromatography. Drugs in biological samples are directly extracted and concentrated in the stationary phase of capillary columns by repeated draw/eject cycles of sample solution, and then directly transferred to the liquid chromatographic column. In-tube SPME is suitable for automation. Automated sample handling procedures not only shorten the total analysis time, but also usually provide better accuracy and precision relative to manual techniques. In-tube SPME has been demonstrated to be a very effective and highly sensitive technique to determine drugs in biological samples for various purposes such as therapeutic drug monitoring, clinical toxicology, bioavailability and pharmacokinetics.

  10. Application of carbon nanotubes modified with a Keggin polyoxometalate as a new sorbent for the hollow-fiber micro-solid-phase extraction of trace naproxen in hair samples with fluorescence spectrophotometry using factorial experimental design.

    Science.gov (United States)

    Naddaf, Ezzat; Ebrahimi, Mahmoud; Es'haghi, Zarrin; Bamoharram, Fatemeh Farrash

    2015-07-01

    A sensitive technique to determinate naproxen in hair samples was developed using hollow-fiber micro-solid-phase combined with fluorescence spectrophotometry. The incorporation of multi-walled carbon nanotubes modified with a Keggin polyoxometalate into a silica matrix prepared by the sol-gel method was reported. In this research, the Keggin carbon nanotubes /silica composite was used in the pores and lumen of a hollow fiber as the hollow-fiber micro-solid-phase extraction device. The device was used for the microextraction of the analyte from hair and water samples under the optimized conditions. An orthogonal array experimental design with an OA24 (4(6) ) matrix was employed to optimize the conditions. The effect of six factors influencing the extraction efficiency was investigated: pH, salt, volume of donor and desorption phase, extraction and desorption time. The effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance was employed for estimating the main significant factors and their contributions in the extraction. Calibration curve plot displayed linearity over a range of 0.2-10 ng/mL with detection limits of 0.072 and 0.08 ng/mL for hair and aqueous samples, respectively. The relative recoveries in the hair and aqueous matrices ranged from 103-95%. The relative standard deviation for fiber-to-fiber repeatability was 3.9%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Facile synthesis of stereoregular carbon fiber precursor polymers by template assisted solid phase polymerization

    Directory of Open Access Journals (Sweden)

    G. Santhana Krishnan

    2012-09-01

    Full Text Available Predominantly isotactic stereoregular polyacrylonitrile copolymers (PAC were prepared by solid phase polymerization techniques using hexagonal crystalline metal salts as template compounds. Stereoregular distributions of the prepared polymer were studied using high resolution 13C nuclear magnetic resonance spectroscopy (13C NMR spectra. The extent of isotacticity was directly determined from the peak intensity of the methine carbon (CH. The triad tacticity from the intensities of methine carbon peaks were examined by statistical methods. It was found that the PAC was predominantly isotactic in stereoregularity, and its sequence distribution obeys Bernoulli statistics. The optimum polymerization conditions ensuring isotactic content over 50% were disclosed experimentally. The chemical composition of PAC was confirmed with 1H NMR data. The obtained polyacrylonitrile copolymers were also characterized for molecular parameters such as viscosity average molecular weight (Mv, number average molecular weight (Mn, weight average molecular weight (Mw and polydispersity index.

  12. New Methyltrimethoxysilane-(3-Mercaptopropyl)- Trimethoxysilane Coated Hollow Fiber-Solid Phase Micro extraction for Hexanal and Heptanal Analysis

    International Nuclear Information System (INIS)

    Siti Munirah Abd Wahib; Mohd Marsin Sanagi

    2016-01-01

    Determination of volatile organic compounds (VOCs) in various matrices is often accomplished using solid phase micro extraction (SPME) as a superior mode of extraction. Alternatively, another configuration of solid phase micro extraction (SPME) namely hollow fiber-solid phase micro extraction (HF-SPME) is a great approach to redress some limitations of the ordinary SPME fibers including fiber breakage, coating stripping and sample carry over. The HF-SPME technique highlights the use of hollow polypropylene (PP) membrane to hold and protect the adsorbent inside its lumen. Unlike the conventional SPME, the inexpensive HF device can be disposed after single use. Introducing extracting phase via sol-gel technology has gained great interest owing to its simple preparation method and promising way to obtain materials with good characteristics. In the present work, a new hybrid silica material based on methyltrimethoxysilane-(3-mercaptopropyl)trimethoxysilane (MTMOS-MPTMOS) was introduced as a new extractant of HF-SPME and the effectiveness of the proposed method was tested for analysis of hexanal and heptanal as the target VOC analytes. Preparation of the HF-SPME MTMOS-MPTMOS was simple in which the hybrid material was synthesized via sol-gel method and was self-polymerized in small segments of HF. Parameters affecting the efficiency of the HF-SPME MTMOS-MPTMOS in extracting both aldehydes were thoroughly investigated and analyzed by gas chromatography-flame ionization detection (GC-FID). It was found that the highest efficiency was achieved as the extraction was conducted in 30 min at a stirring rate of 1000 rpm in a 10 mL of sample solution whereby the back-extraction was performed via vortex for 3 min using 100 μL methanol as desorption solvent. Under the optimal conditions, linearity was observed over a range of 0.020-10.00 μg mL -1 with detection limits of 0.015 μg mL -1 and 0.010 μg mL -1 for hexanal and heptanal, respectively. The applicability of the HF

  13. Solid Phase Extraction of Trace Copper(II Using Modified Nano Polyacrylonitrile Fiber

    Directory of Open Access Journals (Sweden)

    A. Moghimi

    2012-07-01

    Full Text Available A simple method has been developed for the preconcentration of copper(II based on the adsorption of its Modified nano polyacrylonitrile fiber. Modified nano polyacrylonitrile fiber (PANF was prepared by adding of acrylic fibers to mSethanolamine (MMA with different concentration solutions. The stability of a chemically Modified nano polyacrylonitrile fiber especially in concentrated hydrochloric acid which was then used as a recycling and pre-concentration reagent for further uses of modified nano polyacrylonitrile fiber. The application of this Modified nano polyacrylonitrile fiber for sorption of a series of metal ions was performed by using different controlling factors such as the pH of metal ion solution and the equilibration shaking time by the static technique. Cu (II was found to exhibit the highest affinity towards extraction by these Modified nano polyacrylonitrile fiber phases. The pronounced selectivity was also confirmed from the determined distribution coefficient (Kd of all the metal ions, showing the highest value reported for Cu (II to occur by Modified nano polyacrylonitrile fiber. The potential applications ofModified nano polyacrylonitrile fiber for selective extraction of Cu(II to occur from aqueous solution were successfully accomplished as well as pre- concentration of low concentration of Cu(II (60 pg ml-1 from natural tap water with a pre-concentration factor of 100 for Cu(II off-line analysis by flame atomic absorption analysis.

  14. New method for the discovery of adulterated cognacs and brandies based on solid-phase microextraction and gas chromatography - mass spectrometry

    Directory of Open Access Journals (Sweden)

    Darya Mozhayeva

    2014-10-01

    Full Text Available The article represents new method for discovery of adulterated cognacs and brandies based on solidphase microextraction (SPME in combination with gas chromatography – mass spectrometry (GC-MS. The work comprised optimization of SPME parameters (extraction temperature and time, concentration of added salt with subsequent analysis of authentic samples and comparison of the obtained chromatograms using principal component analysis (PCA. According to the obtained results, increase of extraction temperature resulted in an increase of response of the most volatile brandy constituents. To avoid chemical transformations and/or degradation of the samples, the extraction temperature must be limited to 30!C. Increase of the extraction time lead to higher total peak area, but longer extraction times (>10 min for 100 µm polydimethylsiloxane and >2 min for divinylbenzene/Carboxen/polydimethylsiloxane fibers caused displacement of analytes. Salt addition increased total response of analytes, but caused problems with reproducibility. The developed method was successfully applied for discovery of adulterated samples of brandy, cognac, whisky and whiskey sold in Kazakhstan. The obtained data was analyzed applying principal component analysis (PCA. Five adulterated brandy and whisky samples were discovered and confirmed. The developed method is recommended for application in forensic laboratories.

  15. Non-targeted volatile profiles for the classification of the botanical origin of Chinese honey by solid-phase microextraction and gas chromatography-mass spectrometry combined with chemometrics.

    Science.gov (United States)

    Chen, Hui; Jin, Linghe; Fan, Chunlin; Wang, Wenwen

    2017-11-01

    A potential method for the discrimination and prediction of honey samples of various botanical origins was developed based on the non-targeted volatile profiles obtained by solid-phase microextraction with gas chromatography and mass spectrometry combined with chemometrics. The blind analysis of non-targeted volatile profiles was carried out using solid-phase microextraction with gas chromatography and mass spectrometry for 87 authentic honey samples from four botanical origins (acacia, linden, vitex, and rape). The number of variables was reduced from 2734 to 70 by using a series of filters. Based on the optimized 70 variables, 79.12% of the variance was explained by the first four principal components. Partial least squares discriminant analysis, naïve Bayes analysis, and back-propagation artificial neural network were used to develop the classification and prediction models. The 100% accuracy revealed a perfect classification of the botanical origins. In addition, the reliability and practicability of the models were validated by an independent set of additional 20 authentic honey samples. All 20 samples were accurately classified. The confidence measures indicated that the performance of the naïve Bayes model was better than the other two models. Finally, the characteristic volatile compounds of linden honey were tentatively identified. The proposed method is reliable and accurate for the classification of honey of various botanical origins. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Trace determination of five triazole fungicide residues in traditional Chinese medicine samples by dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction and UHPLC-MS/MS.

    Science.gov (United States)

    Ma, Shuping; Yuan, Xucan; Zhao, Pengfei; Sun, Hong; Ye, Xiu; Liang, Ning; Zhao, Longshan

    2017-08-01

    A novel and reliable method for determination of five triazole fungicide residues (triadimenol, tebuconazole, diniconazole, flutriafol, and hexaconazol) in traditional Chinese medicine samples was developed using dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction before ultra-high performance liquid chromatography with tandem mass spectrometry. The clean up of the extract was conducted using dispersive solid-phase extraction by directly adding sorbents into the extraction solution, followed by shaking and centrifugation. After that, a mixture of 400 μL trichloromethane (extraction solvent) and 0.5 mL of the above supernatant was injected rapidly into water for the dispersive liquid-liquid microextraction procedure. The factors affecting the extraction efficiency were optimized. Under the optimum conditions, the calibration curves showed good linearity in the range of 2.0-400 (tebuconazole, diniconazole, and hexaconazole) and 4.0-800 ng/g (triadimenol and flutriafol) with the regression coefficients higher than 0.9958. The limit of detection and limit of quantification for the present method were 0.5-1.1 and 1.8-4.0 ng/g, respectively. The recoveries of the target analytes ranged from 80.2 to 103.2%. The proposed method has been successfully applied to the analysis of five triazole fungicides in traditional Chinese medicine samples, and satisfactory results were obtained. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Dispersive solid-phase extraction followed by vortex-assisted dispersive liquid-liquid microextraction based on the solidification of a floating organic droplet for the determination of benzoylurea insecticides in soil and sewage sludge.

    Science.gov (United States)

    Peng, Guilong; He, Qiang; Mmereki, Daniel; Lu, Ying; Zhong, Zhihui; Liu, Hanyang; Pan, Weiliang; Zhou, Guangming; Chen, Junhua

    2016-04-01

    A novel dispersive solid-phase extraction combined with vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet was developed for the determination of eight benzoylurea insecticides in soil and sewage sludge samples before high-performance liquid chromatography with ultraviolet detection. The analytes were first extracted from the soil and sludge samples into acetone under optimized pretreatment conditions. Clean-up of the extract was conducted by dispersive solid-phase extraction using activated carbon as the sorbent. The vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet procedure was performed by using 1-undecanol with lower density than water as the extraction solvent, and the acetone contained in the solution also acted as dispersive solvent. Under the optimum conditions, the linearity of the method was in the range 2-500 ng/g with correlation coefficients (r) of 0.9993-0.9999. The limits of detection were in the range of 0.08-0.56 ng/g. The relative standard deviations varied from 2.16 to 6.26% (n = 5). The enrichment factors ranged from 104 to 118. The extraction recoveries ranged from 81.05 to 97.82% for all of the analytes. The good performance has demonstrated that the proposed methodology has a strong potential for application in the multiresidue analysis of complex matrices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Novel functionalized polymeric fabric and fiber material as solid support for solid-phase synthesis and biomedical applications

    Science.gov (United States)

    Xiang, Bei

    The aim of the research is to develop novel polymer solid support by modifying or fabricating polymeric fibrous materials for peptide synthesis and biomedical applications. Originally chemical inert isotactic polypropylene (iPP) fabric was utilized and modified to serve as a functional flexible planar solid support for solid phase peptide synthesis. The modification was achieved through thermal initiated radical grafting polymerization using acrylic acid, poly (ethylene glycol) diacrylate as monomers, and benzoyl peroxide as radical initiator. The iPP fabric was successfully functionalized and possessing as high as 0.7mmol/g carboxylic acid groups. Peptide ligand LHPQF was successfully synthesized on the new functional planar support. Specific enzyme immobilization was fulfilled on the functional iPP fabric support. A commercially available ethylene-acrylic acid copolymer was made into ultrafine copolymer fiber bundles which are composed of nanofibers with diameters ranging from 200nm to 800nm. Various mixing ratios of copolymer/matrix materials were utilized to explore the effect on the final nanofiber physical properties including morphology and stability in solvents. The surface carboxylic acid groups were further converted to amino groups before the functional nanofibers can be applied in solid phase peptide synthesis. Two peptide ligands, LHPQF and HWRGWV, were also successfully synthesized on the nanofiber bundles. Streptavidin and human immunoglobulin G specific binding with the corresponding ligand which was anchored on the nanofibers was conducted successfully to illustrate the potential applications of the nanofiber materials in biomedical field. Further study on the dispersion of the ethylene-acrylic acid nanofiber bundles was pursued to take advantage of the super high active surface area of functional nanofibers. To manipulate the polymer nanofibers during synthesis and bio-assays, a technique was developed to controllably assemble and disperse the

  19. Development of a fiber coating based on molecular sol-gel imprinting technology for selective solid-phase micro extraction of caffeine from human serum and determination by gas chromatography/mass spectrometry.

    Science.gov (United States)

    Rajabi Khorrami, Afshin; Rashidpur, Amene

    2012-05-21

    In this work, a molecular sol-gel imprinting approach has been introduced to produce a fiber coating for selective direct immersion solid-phase microextraction (SPME) of caffeine. The polymerization mixture was composed of vinyl trimethoxysilane and methacrylic acid as vinyl sol-gel precursor and functional monomer, respectively. Caffeine was used as template molecule during polymerization process. The prepared fibers could be coupled directly to gas chromatography/mass spectrometry (GC/MS) and used for trace analysis of caffeine in a complex sample such as human serum. The parameters influencing SPME such as time, temperature and stirring speed were optimized. The prepared coating showed good selectivity towards caffeine in the presence of some structurally related compounds. Also, it offered high imprinting capability in comparison to bare fiber and non-imprinted coating. Linear range for caffeine detection was 1-80 μg mL(-1) and the limit of detection was 0.1 μg mL(-1). The intra-day and inter-day precisions of the peak areas for five replicates were 10 and 16%, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Solid-phase extraction in combination with dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis: the ultra-trace determination of 10 antibiotics in water samples.

    Science.gov (United States)

    Liang, Ning; Huang, Peiting; Hou, Xiaohong; Li, Zhen; Tao, Lei; Zhao, Longshan

    2016-02-01

    A novel method, solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME), was developed for ultra-preconcentration of 10 antibiotics in different environmental water samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry detection. The optimized results were obtained as follows: after being adjusted to pH 4.0, the water sample was firstly passed through PEP-2 column at 10 mL min(-1), and then methanol was used to elute the target analytes for the following steps. Dichloromethane was selected as extraction solvent, and methanol/acetonitrile (1:1, v/v) as dispersive solvent. Under optimal conditions, the calibration curves were linear in the range of 1-1000 ng mL(-1) (sulfamethoxazole, cefuroxime axetil), 5-1000 ng mL(-1) (tinidazole), 10-1000 ng mL(-1) (chloramphenicol), 2-1000 ng mL(-1) (levofloxacin oxytetracycline, doxycycline, tetracycline, and ciprofloxacin) and 1-400 ng mL(-1) (sulfadiazine) with a good precision. The LOD and LOQ of the method were at very low levels, below 1.67 and 5.57 ng mL(-1), respectively. The relative recoveries of the target analytes were in the range from 64.16% to 99.80% with relative standard deviations between 0.7 and 8.4%. The matrix effect of this method showed a great decrease compared with solid-phase extraction and a significant value of enrichment factor (EF) compared with dispersive liquid-liquid microextraction. The developed method was successfully applied to the extraction and analysis of antibiotics in different water samples with satisfactory results.

  1. Trace determination of antibacterial pharmaceuticals in fishes by microwave-assisted extraction and solid-phase purification combined with dispersive liquid-liquid microextraction followed by ultra-high performance liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Huang, Peiting; Zhao, Pan; Dai, Xinpeng; Hou, Xiaohong; Zhao, Longshan; Liang, Ning

    2016-02-01

    A novel pretreatment method involving microwave-assisted extraction and solid-phase purification combined with dispersive liquid-liquid microextraction (MAE-SPP-DLLME) followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was established for the simultaneous determination of six antibacterial pharmaceuticals including metronidazole, tinidazole, chloramphenicol, thiamphenicol, malachite green and crystal violet. The conditions of MAE were optimized using an orthogonal design and the optimal conditions were found to be 8mL for acetonitrile, 50°C for 5min. Then, neutral alumina column was employed in the solid-phase purification. Finally, the critical parameters affecting DLLME, including selection of extraction and dispersive solvent, adjustment of pH, salt concentration, extraction time, were investigated by single factor study. Under optimum conditions, good linearities (r>0.9991) and satisfied recoveries (Recoveries>87.0%, relative standard deviation (RSD)extraction followed by purification. The established method was sensitive, rapid, accurate and employable to simultaneously determine target analytes in farmed fish, river fish and marine fish. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Bioanalytical method for in vitro metabolism study of repaglinide using 96-blade thin-film solid-phase microextraction and LC-MS/MS.

    Science.gov (United States)

    Simões, Rodrigo Almeida; Bonato, Pierina Sueli; Mirnaghi, Fatemeh S; Bojko, Barbara; Pawliszyn, Janusz

    2015-01-01

    A high-throughput bioanalytical method using 96-blade thin film microextraction (TFME) and LC-MS/MS for the analysis of repaglinide (RPG) and two of its main metabolites was developed and used for an in vitro metabolism study. The target analytes were extracted from human microsomal medium by a 96-blade-TFME system employing the low-cost prototype 'SPME multi-sampler' using C18 coating. Method validation showed recoveries around 90% for all analytes and was linear over the concentration range of 2-1000 ng ml(-1) for RPG and of 2-500 ng ml(-1) for each RPG metabolite. The method was applied to an in vitro metabolism study of RPG employing human liver microsomes and proved to be very useful for this purpose.

  3. MOF-5(Zn)-Fe2O4 nanocomposite based magnetic solid-phase microextraction followed by HPLC-UV for efficient enrichment of colchicine in root of colchicium extracts and plasma samples.

    Science.gov (United States)

    Bahrani, Sonia; Ghaedi, Mehrorang; Dashtian, Kheibar; Ostovan, Abbas; Mansoorkhani, Mohammad Javad Khoshnood; Salehi, Amin

    2017-11-01

    In present work, facile method is developed for determination of colchicine in human plasma sample, autumn and spring root of colchicium extracts by ultrasound assisted dispersive magnetic solid phase microextraction followed by HPLC-UV method (UAD-MSPME-HPLC-UV). Magnetic (Fe 2 O 4 -nanoparticles) metal organic framework-5, (MOF-5(Zn)-Fe 2 O 4 NPs) was synthesized by dispersing MOF-5 and Fe(NO 3 ) 3 .9H 2 O in ethylene glycol (as capping agent) and NaOH (pH adjustment agent) by hydrothermal method. The prepared sorbent was characterized via XRD and SEM analysis and applied as magnetic solid phase in UAD-MSPME-HPLC-UV method. In this method, colchicine molecules were sorbed on MOF-5(Zn)-Fe 2 O 4 NPs sorbent by various mechanisms like ion exchange, hydrogen bonding and electrostatic, ᴨ-ᴨ, hard-hard and dipole-ion interaction followed by exposing sonication waves as incremental mass transfer agent and then the sorbent was separated from the sample matrix by an external magnetic fields. Subsequently, accumulated colchicine were eluted by small volume of desorption organic solvent. Influence of operational variables such as MOF-5(Zn)-Fe 2 O 4 NPs mass, volume of extracting solvent and sonication time on response property (recovery) were studied and optimized by central composite design (CCD) combined with desirability function (DF) approach. Under optimum condition, the method has wide linear calibration rang (0.5-1700ngmL -1 ) with reasonable detection limit (0.13ngmL -1 ) and R 2 =0.9971. Finally, the UAD-MSPME-HPLC-UV method was successfully applied for determination of colchicine autumn and spring root of colchicium extracts and plasma samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Speciation of As(III) and As(V) in water samples by graphite furnace atomic absorption spectrometry after solid phase extraction combined with dispersive liquid-liquid microextraction based on the solidification of floating organic drop.

    Science.gov (United States)

    Shamsipur, Mojtaba; Fattahi, Nazir; Assadi, Yaghoub; Sadeghi, Marzieh; Sharafi, Kiomars

    2014-12-01

    A solid phase extraction (SPE) coupled with dispersive liquid-liquid microextraction based on the solidification of floating organic drop (DLLME-SFO) method, using diethyldithiphosphate (DDTP) as a proper chelating agent, has been developed as an ultra preconcentration technique for the determination of inorganic arsenic in water samples prior to graphite furnace atomic absorption spectrometry (GFAAS). Variables affecting the performance of both steps were thoroughly investigated. Under optimized conditions, 100mL of As(ΙΙΙ) solution was first concentrated using a solid phase sorbent. The extract was collected in 2.0 mL of acetone and 60.0 µL of 1-undecanol was added into the collecting solvent. The mixture was then injected rapidly into 5.0 mL of pure water for further DLLME-SFO. Total inorganic As(III, V) was extracted similarly after reduction of As(V) to As(III) with potassium iodide and sodium thiosulfate and As(V) concentration was calculated by difference. A mixture of Pd(NO3)2 and Mg(NO3)2 was used as a chemical modifier in GFAAS. The analytical characteristics of the method were determined. The calibration graph was linear in the rage of 10-100 ng L(-1) with detection limit of 2.5 ng L(-1). Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 80 ng L(-1) of As(ΙΙΙ) were 6.8% and 7.5%, respectively. The method was successfully applied to speciation of As(III), As(V) and determination of the total amount of As in water samples and in a certified reference material (NIST RSM 1643e). Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Zero valent Fe-reduced graphene oxide quantum dots as a novel magnetic dispersive solid phase microextraction sorbent for extraction of organophosphorus pesticides in real water and fruit juice samples prior to analysis by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Akbarzade, Samaneh; Chamsaz, Mahmoud; Rounaghi, Gholam Hossein; Ghorbani, Mahdi

    2018-01-01

    A selective and sensitive magnetic dispersive solid-phase microextraction (MDSPME) coupled with gas chromatography-mass spectrometry was developed for extraction and determination of organophosphorus pesticides (Sevin, Fenitrothion, Malathion, Parathion, and Diazinon) in fruit juice and real water samples. Zero valent Fe-reduced graphene oxide quantum dots (rGOQDs@ Fe) as a new and effective sorbent were prepared and applied for extraction of organophosphorus pesticides using MDSPME method. In order to study the performance of this new sorbent, the ability of rGOQDs@ Fe was compared with graphene oxide and magnetic graphene oxide nanocomposite by recovery experiments of the organophosphorus pesticides. Several affecting parameters in the microextraction procedure, including pH of donor phase, donor phase volume, stirring rate, extraction time, and desorption conditions such as the type and volume of solvents and desorption time were thoroughly investigated and optimized. Under the optimal conditions, the method showed a wide linear dynamic range with R-square between 0.9959 and 0.9991. The limit of detections, the intraday and interday relative standard deviations (n = 5) were less than 0.07 ngmL -1 , 4.7, and 8.6%, respectively. The method was successfully applied for extraction and determination of organophosphorus pesticides in real water samples (well, river and tap water) and fruit juice samples (apple and grape juice). The obtained relative recoveries were in the range of 82.9%-113.2% with RSD percentages of less than 5.8% for all the real samples.

  6. A new strategy for synthesis of an in-tube molecularly imprinted polymer-solid phase microextraction device: selective off-line extraction of 4-nitrophenol as an example of priority pollutants from environmental water samples.

    Science.gov (United States)

    Zarejousheghani, Mashaalah; Möder, Monika; Borsdorf, Helko

    2013-10-10

    In this study a novel preparation protocol has been developed for the construction of an in-tube molecularly imprinted polymer-solid phase microextraction (MIP-SPME) device. Open tubular capillaries have been molded from a polymer sorbent imprinted for 4-nitrophenol as target molecule. Different parameters like inner diameter and volume of the polymer, porogen volume, swelling and shrinking effects of the polymer tubes, polymerization time, pH of the sample, extraction time, 'salting out' effect and serial connection of the tubes were evaluated and optimized. Particularly, an optimized polymer preparation process and extraction condition enhanced the final extraction recovery of 4-nitrophenol substantially. Using this new MIP-SPME technique with high-performance liquid chromatography-ultraviolet (HPLC-UV) analysis of the extracts, the linear range and the limits of detection and quantification are 0.001-10 mg L(-1), 0.33 μg L(-1) and 1.1 μg L(-1) respectively. At optimized conditions, a mixture of nitrophenols, alkylated and chlorinated phenols spiked into municipal waste water were analyzed to evaluate the matrix effects and cross selectivity of the new MIP capillary tubes. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Headspace solid-phase microextraction and gas chromatographic analysis of low-molecular-weight sulfur volatiles with pulsed flame photometric detection and quantification by a stable isotope dilution assay.

    Science.gov (United States)

    Ullrich, Sebastian; Neef, Sylvia K; Schmarr, Hans-Georg

    2018-02-01

    Low-molecular-weight volatile sulfur compounds such as thiols, sulfides, disulfides as well as thioacetates cause a sulfidic off-flavor in wines even at low concentration levels. The proposed analytical method for quantification of these compounds in wine is based on headspace solid-phase microextraction, followed by gas chromatographic analysis with sulfur-specific detection using a pulsed flame photometric detector. Robust quantification was achieved via a stable isotope dilution assay using commercial and synthesized deuterated isotopic standards. The necessary chromatographic separation of analytes and isotopic standards benefits from the inverse isotope effect realized on an apolar polydimethylsiloxane stationary phase of increased film thickness. Interferences with sulfur-specific detection in wine caused by sulfur dioxide were minimized by addition of propanal. The method provides adequate validation data, with good repeatability and limits of detection and quantification. It suits the requirements of wine quality management, allowing the control of oenological treatments to counteract an eventual formation of excessively high concentration of such malodorous compounds. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Analysis of enantiomeric and non-enantiomeric monoterpenes in plant emissions using portable dynamic air sampling/solid-phase microextraction (PDAS-SPME) and chiral gas chromatography/mass spectrometry

    Science.gov (United States)

    Yassaa, Noureddine; Williams, Jonathan

    A portable dynamic air sampler (PDAS) using a porous polymer solid-phase microextraction (SPME) fibre has been validated for the determination of biogenic enantiomeric and non-enantiomeric monoterpenes in air. These compounds were adsorbed in the field, and then thermally desorbed at 250 °C in a gas chromatograph injector port connected via a β-cyclodextrin capillary separating column to a mass spectrometer. The optimized method has been applied for investigating the emissions of enantiomeric monoterpenes from Pseudotsuga menziesii (Douglas-fir), Rosmarinus officinalis (Rosemary) and Lavandula lanata (Lavender) which were selected as representative of coniferous trees and aromatic plants, respectively. The enantiomers of α-pinene, sabinene, camphene, δ-3-carene, β-pinene, limonene, β-phellandrene, 4-carene and camphor were successfully determined in the emissions from the three plants. While Douglas-fir showed a strong predominance toward (-)-enantiomers, Rosemary and Lavender demonstrated a large variation in enantiomeric distribution of monoterpenes. The simplicity, rapidity and sensitivity of dynamic sampling with porous polymer coated SPME fibres coupled to chiral capillary gas chromatography/mass spectrometry (GC/MS) makes this method potentially useful for in-field investigations of atmosphere-biosphere interactions and studies of optically explicit atmospheric chemistry.

  9. Analysis of Odorants in Marking Fluid of Siberian Tiger (Panthera tigris altaica Using Simultaneous Sensory and Chemical Analysis with Headspace Solid-Phase Microextraction and Multidimensional Gas Chromatography-Mass Spectrometry-Olfactometry

    Directory of Open Access Journals (Sweden)

    Simone B. Soso

    2016-06-01

    Full Text Available Scent-marking is the most effective method of communication in the presence or absence of a signaler. These complex mixtures result in a multifaceted interaction triggered by the sense of smell. The objective was to identify volatile organic compound (VOC composition and odors emitted by total marking fluid (MF associated with Siberian tigers (Panthera tigris altaica. Siberian tiger, an endangered species, was chosen because its MF had never been analyzed. Solid phase microextraction (SPME for headspace volatile collection combined with multidimensional gas chromatography-mass spectrometry-olfactometry for simultaneous chemical and sensory analyses were used. Thirty-two VOCs emitted from MF were identified. 2-acetyl-1-pyrroline, the sole previously identified compound responsible for the “characteristic” odor of P. tigris MF, was identified along with two additional compounds confirmed with standards (urea, furfural and four tentatively identified compounds (3-methylbutanamine, (R-3-methylcyclopentanone, propanedioic acid, and 3-hydroxybutanal as being responsible for the characteristic aroma of Siberian tiger MF. Simultaneous chemical and sensory analyses improved characterization of scent-markings and identified compounds not previously reported in MF of other tiger species. This research will assist animal ecologists, behaviorists, and zookeepers in understanding how scents from specific MF compounds impact tiger and wildlife communication and improve management practices related to animal behavior. Simultaneous chemical and sensory analyses is applicable to unlocking scent-marking information for other species.

  10. Characterization of the Typical Potent Odorants in Chinese Roasted Sesame-like Flavor Type Liquor by Headspace Solid Phase Microextraction-Aroma Extract Dilution Analysis, with Special Emphasis on Sulfur-Containing Odorants.

    Science.gov (United States)

    Sha, Sha; Chen, Shuang; Qian, Michael; Wang, Chengcheng; Xu, Yan

    2017-01-11

    The aroma profile of Chinese roasted sesame-like flavor type liquor was investigated by means of headspace solid phase microextraction-aroma extract dilution analysis (HS-SPME-AEDA). Sixty-three odor-active regions were detected by HS-SPME-AEDA with flavor dilution (FD) factors >5, and 58 of these were further identified. Among them, ethyl hexanoate, 2-furfurylthiol, dimethyl trisulfide, 3-methylbutanal, ethyl butanoate, ethyl 2-methylbutanoate, ethyl pentanoate, and ethyl 4-methylpentanoate appeared with the highest FD factors. In particular, eight sulfur-containing odorants were identified to be potentially important to roasted sesame-like flavor type liquor. The concentration of these odor-active compounds was further quantitated by combination of four different quantitative measurements, and 36 odorants had concentrations higher than their corresponding odor thresholds. On the basis of the odor activity values (OAVs), 2-furfurylthiol (OAV 1182), dimethyl trisulfide (OAV 220), β-damascenone (OAV 116), and methional (OAV 99) could be responsible for the unique aroma of roasted sesame-like flavor type liquor. An aroma recombination model prepared by mixing 36 aroma compounds with OAVs >1 showed a good similarity to the aroma of the original roasted sesame-like flavor type liquor. For the first time, 2-furfurylthiol was determined to be a typical potent odorant in roasted sesame-like flavor type liquor by omission study.

  11. Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira wine.

    Science.gov (United States)

    Perestrelo, Rosa; Petronilho, Sílvia; Câmara, José S; Rocha, Sílvia M

    2010-05-14

    An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r(2)) higher than 0.981. A good precision was attained (R.S.D. wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 microg/L and 88.6%, whereas for sweet wines were 9.16 microg/L and 99.4%, respectively. The higher performance was attained with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 microg/L (medium dry) to 162.5 microg/L (medium sweet). 2010 Elsevier B.V. All rights reserved.

  12. Accurate determination of 3-alkyl-2-methoxypyrazines in wines by gas chromatography quadrupole time-of-flight tandem mass spectrometry following solid-phase extraction and dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Fontana, Ariel; Rodríguez, Isaac; Cela, Rafael

    2017-09-15

    A new reliable method for the determination 3-alkyl-2-methoxypyrazines (MPs) in wine samples based on the sequential combination of solid-phase extraction (SPE), dispersive liquid-liquid microextraction (DLLME) and gas chromatography (GC) quadrupole time-of-flight accurate tandem mass spectrometry (QTOF-MS/MS) is presented. Primary extraction of target analytes was carried out by using a reversed-phase Oasis HLB (200mg) SPE cartridge combined with acetonitrile as elution solvent. Afterwards, the SPE extract was submitted to DLLME concentration using 0.06mL carbon tetrachloride (CCl 4 ) as extractant. Under final working conditions, sample concentration factors above 379 times and limits of quantification (LOQs) between 0.3 and 2.1ngL -1 were achieved. Moreover, the overall extraction efficiency of the method was unaffected by the particular characteristics of each wine; thus, accurate results (relative recoveries from 84 to 108% for samples spiked at concentrations from 5 to 25ngL -1 ) were obtained using matrix-matched standards, without using standard additions over every sample. Highly selective chromatographic records were achieved considering a mass window of 5mDa, centered in the quantification product ion corresponding to each compound. Twelve commercial wines, elaborated with grapes from different varieties and geographical origins, were processed with the optimized method. The 2-isobutyl-3-methoxypyrazine (IBMP) was determined at levels above the LOQs of the method in half of the samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Reliable, rapid and simple method for the analysis of phthalates in sediments by ultrasonic solvent extraction followed by head space-solid phase microextraction gas chromatography mass spectrometry determination.

    Science.gov (United States)

    Fernández-González, V; Moscoso-Pérez, C; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

    2017-01-01

    In this work, a new reliable, simple and fast method for the determination of six PAEs in sediments, based on ultrasonic solvent extraction (USE) followed by head space solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry determination (GC-MS), is proposed. The extraction parameters were studied, and the most favourable conditions were selected. The analytical features of the method were calculated: matrix effect, accuracy (ranged from 90% to 111%), repeatability and intermediate precision (RSD <10%), detection and quantification limits of the method (ranged from 0.001µgg -1 (DOP) to 0.142µgg -1 (DEP)), and satisfactory results were obtained. Major advantages of this approach are low consumption of reagents and solvents, no clean-up or evaporation steps were required and minimum sample manipulation. In addition, cross contamination from glassware, solvents and samples is minimized, thus procedural blanks are keeping to a minimum.. The applicability of the proposed method was demonstrated analysing sediment samples from Galician coast (NW Spain). The proposed method allows the application in routine laboratory conditions and its implementation in environmental monitoring studies under the European Water Framework Directive (WFD) and Marine Strategy Framework Directive (MSFD). Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Headspace sorptive solid phase microextraction (HS-SPME) combined with a spectrophotometry system: A simple glass devise for extraction and simultaneous determination of cyanide and thiocyanate in environmental and biological samples.

    Science.gov (United States)

    Al-Saidi, H M; Al-Harbi, Sami A; Aljuhani, E H; El-Shahawi, M S

    2016-10-01

    A simple, low cost and efficient headspace sorptive solid phase microextraction (HS-SPME) method for determination of cyanide has been developed. The system comprises of a glass tube with two valves and a moveable glass slide fixed at its centre. It includes an acceptor phase polyurethane foam treated mercury (II) dithizonate [Hg(HDz)2-PUF] complex fixed inside by a septum cap in a cylindrical configuration (5.0cm length and 1.0cm diameter). The extraction is based upon the contact of the acceptor phase to the headspace and subsequently measuring the absorbance of the recovered mercury (II) dithizonate from PUFs sorbent. Unlike other HSSE, extraction and back - extractions was carried out in a closed system, thereby improving the analytical performance by preventing the analyte loss. Under the optimized conditions, a linear calibration plot in the range of 1.0-50.0µmolL(-1) was achieved with limits of detection (LOD) and quantification (LOQ) of 0.34, 1.2µmolL(-1) CN(-), respectively. Simultaneous analysis of cyanide and thiocyanate in saliva was also performed with satisfactory recoveries. Copyright © 2016. Published by Elsevier B.V.

  15. Zeolite imidazolate frameworks 8 as sorbent and its application to sonication-assisted emulsification microextraction combined with vortex-assisted porous membrane-protected micro-solid-phase extraction for fast analysis of acidic drugs in environmental water samples.

    Science.gov (United States)

    Ge, Dandan; Lee, Hian Kee

    2012-09-28

    A novel and fast procedure, sonication-assisted emulsification microextraction combined with vortex-assisted porous membrane protected micro-solid-phase extraction (SAEME-VA-μ-SPE), was developed for the gas chromatography-mass spectrometric determination of acidic drugs from environmental water samples. One advantage of the new procedure is that any solvent immiscible with water can be used as extractant solvent of SAEME and any solid sorbent can be used for μ-SPE in the SAEME-VA-μ-SPE process. In the present work, zeolite imidazolate framework 8 (ZIF-8) was employed as extraction sorbent for μ-SPE and 1-octanol as extractant solvent for SAEME. ZIF-8 has very good thermal, chemical and water stability, which make it a suitable material for the extraction of trace analytes from aqueous samples. Under the optimized extraction conditions, the developed method exhibited low limits of detection (0.01-0.04 ng/ml), good linearity (with r² between 0.9965 and 0.9993) from 0.5 to 50 ng/ml and satisfactory repeatability (between 4.1% and 7.6%). In essence SAEME-VA-μ-SPE is a combination of two different and efficient miniaturized techniques. It was demonstrated to be a fast, accurate, and convenient pretreatment procedure for trace analysis of environmental water samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Comparison of two extraction techniques, solid-phase microextraction versus continuous liquid-liquid extraction/solvent-assisted flavor evaporation, for the analysis of flavor compounds in gueuze lambic beer.

    Science.gov (United States)

    Thompson-Witrick, Katherine A; Rouseff, Russell L; Cadawallader, Keith R; Duncan, Susan E; Eigel, William N; Tanko, James M; O'Keefe, Sean F

    2015-03-01

    Lambic is a beer style that undergoes spontaneous fermentation and is traditionally produced in the Payottenland region of Belgium, a valley on the Senne River west of Brussels. This region appears to have the perfect combination of airborne microorganisms required for lambic's spontaneous fermentation. Gueuze lambic is a substyle of lambic that is made by mixing young (approximately 1 year) and old (approximately 2 to 3 years) lambics with subsequent bottle conditioning. We compared 2 extraction techniques, solid-phase microextraction (SPME) and continuous liquid-liquid extraction/solvent-assisted flavor evaporation (CCLE/SAFE), for the isolation of volatile compounds in commercially produced gueuze lambic beer. Fifty-four volatile compounds were identified and could be divided into acids (14), alcohols (12), aldehydes (3), esters (20), phenols (3), and miscellaneous (2). SPME extracted a total of 40 volatile compounds, whereas CLLE/SAFE extracted 36 volatile compounds. CLLE/SAFE extracted a greater number of acids than SPME, whereas SPME was able to isolate a greater number of esters. Neither extraction technique proved to be clearly superior and both extraction methods can be utilized for the isolation of volatile compounds found in gueuze lambic beer. © 2015 Institute of Food Technologists®

  17. Influence of harvest maturity and fruit logistics on pineapple (Ananas comosus [L.] Merr.) volatiles assessed by headspace solid phase microextraction and gas chromatography-mass spectrometry (HS-SPME-GC/MS).

    Science.gov (United States)

    Steingass, Christof B; Grauwet, Tara; Carle, Reinhold

    2014-05-01

    Profiling of volatiles from pineapple fruits was performed at four ripening stages using headspace solid-phase microextraction and gas chromatography-mass spectrometry (HS-SPME-GC/MS). In total, 142 volatiles were detected, of which 132 were identified. Multivariate data analysis was carried out to assess the effect of post-harvest storage on volatiles composition of green-ripe sea-freighted pineapple in comparison to air-freighted fruits harvested at full maturity. The latter fruits were characterised by volatiles described as potent odorants in pineapples, such as δ-octalactone, γ-lactones, 1-(E,Z)-3,5-undecatriene and 1,3,5,8-undecatetraene, as well as various methyl esters. In contrast, post-harvest storage of green-ripe sea-freighted fruits resulted in an increased formation of ethyl esters, acetates, acetoxy esters and alcohols, thus allowing the authentication of sea- and air-freighted pineapples, respectively. Particularly, compounds presumably derived from methyl-branched amino acid catabolism were identified in the fruits at later post-harvest stages. In addition, physicochemical traits were determined to characterise the fruit maturity stages. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Analysis of Odorants in Marking Fluid of Siberian Tiger (Panthera tigris altaica) Using Simultaneous Sensory and Chemical Analysis with Headspace Solid-Phase Microextraction and Multidimensional Gas Chromatography-Mass Spectrometry-Olfactometry.

    Science.gov (United States)

    Soso, Simone B; Koziel, Jacek A

    2016-06-25

    Scent-marking is the most effective method of communication in the presence or absence of a signaler. These complex mixtures result in a multifaceted interaction triggered by the sense of smell. The objective was to identify volatile organic compound (VOC) composition and odors emitted by total marking fluid (MF) associated with Siberian tigers (Panthera tigris altaica). Siberian tiger, an endangered species, was chosen because its MF had never been analyzed. Solid phase microextraction (SPME) for headspace volatile collection combined with multidimensional gas chromatography-mass spectrometry-olfactometry for simultaneous chemical and sensory analyses were used. Thirty-two VOCs emitted from MF were identified. 2-acetyl-1-pyrroline, the sole previously identified compound responsible for the "characteristic" odor of P. tigris MF, was identified along with two additional compounds confirmed with standards (urea, furfural) and four tentatively identified compounds (3-methylbutanamine, (R)-3-methylcyclopentanone, propanedioic acid, and 3-hydroxybutanal) as being responsible for the characteristic aroma of Siberian tiger MF. Simultaneous chemical and sensory analyses improved characterization of scent-markings and identified compounds not previously reported in MF of other tiger species. This research will assist animal ecologists, behaviorists, and zookeepers in understanding how scents from specific MF compounds impact tiger and wildlife communication and improve management practices related to animal behavior. Simultaneous chemical and sensory analyses is applicable to unlocking scent-marking information for other species.

  19. Preparation of 2,4-dichlorophenoxyacetic acid imprinted organic-inorganic hybrid monolithic column and application to selective solid-phase microextraction.

    Science.gov (United States)

    Liu, Xiaofang; Zhu, Quanfei; Chen, Huaixia; Zhou, Liuzi; Dang, Xueping; Huang, Jianlin

    2014-03-01

    An organic-inorganic hybrid molecular imprinting monolith (HMIM) has been prepared, characterized and applied for the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in rice with high-performance liquid chromatography-photodiodes array detector (HPLC-PAD). By optimizing the polymerization conditions, such as the volume ratio of the inorganic alcoholysate and organic part, the 2,4-D-HMIM was synthesized in a micro pipette tip using acrylamide as the functional monomer, ethylene dimethacrylate as the cross-linker and methanol as the porogenic solvent. The morphology of the monolith was studied by scanning electronmicroscopy and Fourier transform infrared spectra. The imprinted factor of the monolith for 2,4-D reached 3.29. A simple, rapid and sensitive method for the determination of 2,4-D in rice using the HMIM microextraction combined with high-performance liquid chromatography-photodiodes array detector was developed. Some parameters affecting the sample pretreatment were investigated, including the type and volume of eluent, the flow rate and volume of sample solution. The assay exhibited a linear dynamic range of 167-4167μg/kg with the correlation coefficient above 0.9972. The detection limit (at S/N=3) was 50μg/kg. The proposed method was successfully applied for the selective determination of 2,4-D in rice. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Enantioselective separation and electrochemical sensing of D- and L-tryptophan at ultratrace level using molecularly imprinted micro-solid phase extraction fiber coupled with complementary molecularly imprinted polymer-fiber sensor.

    Science.gov (United States)

    Prasad, Bhim Bali; Tiwari, Mahavir Prasad; Madhuri, Rashmi; Sharma, Piyush Sindhu

    2011-02-15

    Highly efficient enantioselective separation and quantitative recoveries of D- and L-tryptophan in aqueous and real samples can be achieved, with a monolithic molecularly imprinted polymeric fiber that serves both for micro-solid phase extraction and ultratrace sensing, without any false-positive (non-specific) contribution and cross-reactivity, in the range of 0.15-30.00 ng mL(-1) with detection limit as low as 0.0261 ng mL(-1) (relative standard deviation=0.64%, signal/noise=3). The proposed method combining molecularly imprinted micro-solid phase extraction fiber and a complementary molecularly imprinted polymer-carbon composite fiber sensor is proven to be useful for clinical diagnosis of stress-related diseases caused by acute tryptophan depletion. Copyright © 2010 Elsevier B.V. All rights reserved.

  1. Ionic-liquid-based dispersive liquid-liquid microextraction combined with magnetic solid-phase extraction for the determination of aflatoxins B1, B2, G1, and G2in animal feeds by high-performance liquid chromatography with fluorescence detection.

    Science.gov (United States)

    Zhao, Jiao; Zhu, Yan; Jiao, Yang; Ning, Jinyan; Yang, Yaling

    2016-10-01

    A novel two-step extraction technique combining ionic-liquid-based dispersive liquid-liquid microextraction with magnetic solid-phase extraction was developed for the preconcentration and separation of aflatoxins in animal feedstuffs before high-performance liquid chromatography coupled with fluorescence detection. In this work, ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate was used as the extractant in dispersive liquid-liquid microextraction, and hydrophobic pelargonic acid modified Fe 3 O 4 magnetic nanoparticles as an efficient adsorbent were applied to retrieve the aflatoxins-containing ionic liquid. Notably, the target of magnetic nanoparticles was the ionic liquid rather than the aflatoxins. Because of the rapid mass transfer associated with the dispersive liquid-liquid microextraction and magnetic solid phase steps, fast extraction could be achieved. The main parameters affecting the extraction recoveries of aflatoxins were investigated and optimized. Under the optimum conditions, vortexing at 2500 rpm for 1 min in the dispersive liquid-liquid microextraction and magnetic solid-phase extraction and then desorption by sonication for 2 min with acetonitrile as eluent. The recoveries were 90.3-103.7% with relative standard deviations of 3.2-6.4%. Good linearity was observed with correlation coefficients ranged from 0.9986 to 0.9995. The detection limits were 0.632, 0.087, 0.422 and 0.146 ng/mL for aflatoxins B 1 , B2, G1, and G2, respectively. The results were also compared with the pretreatment method carried out by conventional immunoaffinity columns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. An improved method for the analysis of 2-aminoacetophenone in wine based on headspace solid-phase microextraction and heart-cut multidimensional gas chromatography with selective detection by tandem mass spectrometry.

    Science.gov (United States)

    Schmarr, Hans-Georg; Keiser, Jutta; Krautwald, Susann

    2016-12-16

    Heart-cut multidimensional gas chromatography coupled to selective mass spectrometric detection (H/C MDGC-MS-MS) was shown to be a suitable combination for analysis of the key component for the wine off-flavor named "atypical aging off-flavor" (german: "Untypische Alterungsnote", UTA), 2-aminoacetophenone (2-AAP). Headspace solid phase microextraction (HS-SPME) was applied as an easy to automate sample preparation step suiting routine control situations. During method development two critical aspects were found, of which one is the chemical degradation of the neat substance, leading to signal reduction and a false response behavior. A second aspect is the pH stability of the deuterated isotopologue 1-(2-aminophenyl)-2,2,2-trideuterio-ethanone (2-AAP-d3) used for quantification via a stable isotope dilution assay. Despite an earlier suggestion to increase the extractable amount of 2-AAP and its isotopic standard in the headspace, alkalization of 2-AAP-d3 containing aqueous samples were found to be critical. In such a milieu a deuterium exchange can then cause erroneous quantitative results. The method proposed in our study thus uses native wine pH conditions and proved to be suitable for routine control with respect to the detection of the "atypical aging off-flavor" in wine at concentration levels below its sensory threshold of about 1μgL -1 . Good linearity was obtained in the calibrated range from 0.1-8μgL -1 (y=1,2338x+0,1029, R=0,9985) with limits of detection or quantification being 0.01 and 0.14μg/L, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Analysis of urinary 8-isoprostane as an oxidative stress biomarker by stable isotope dilution using automated online in-tube solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Mizuno, Keisuke; Kataoka, Hiroyuki

    2015-08-10

    We have developed a simple and sensitive method for the determination of the oxidative stress biomarker 8-isoprostane (8-IP) in human urine by automated online in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) using a Zorbax Eclipse XDB-8 column and 0.1% formic acid/methanol (25/75, v/v) as a mobile phase. Electrospray MS/MS for 8-IP was performed on an API 4000 triple quadruple mass spectrometer in negative ion mode. The optimum in-tube SPME conditions were 20 draw/eject cycles with a sample size of 40 μL using a Carboxen 1006 PLOT capillary column for the extraction. The extracted compounds were easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. Total analysis time of this method including online extraction and analysis was about 30 min for each sample. The in-tube SPME LC-MS/MS method showed good linearity in the concentration range of 20-1000 pg/mL with a correlation coefficient r = 0.9999 for 8-IP using a stable isotope-labeled internal standard, 8-IP-d4. The detection limit of 8-IP was 3.3 pg/mL and the proposed method showed 42-fold higher sensitivity than the direct injection method. The intra-day and inter-day precisions (relative standard deviations) were below 5.0% and 8.5% (n = 5), respectively. This method was applied successfully to the analysis of urine samples without pretreatment or interference peaks. The recovery rates of 8-IP spiked into urine samples were above 92%. This method is useful for assessing the effects of oxidative stress and antioxidant intake. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Development of magnetic dispersive solid phase extraction using toner powder as an efficient and economic sorbent in combination with dispersive liquid-liquid microextraction for extraction of some widely used pesticides in fruit juices.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Mohebbi, Ali

    2018-01-12

    In this study, for the first time, a magnetic dispersive solid phase extraction method using an easy-accessible, cheap, and efficient magnetic sorbent (toner powder) combined with dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of some widely used pesticides (diazinon, ametryn, chlorpyrifos, penconazole, oxadiazon, diniconazole, and fenazaquin) from fruit juices prior to their determination by gas chromatography-flame ionization detection. In this method, the magnetic sorbent is mixed with an appropriate dispersive solvent (methanol-water, 80:20, v/v) and then injected into an aqueous sample containing the analytes. By this action the analytes are rapidly adsorbed on the sorbent by binding to its carbon. The sorbent particles are isolated from the aqueous solution in the presence of an external magnetic field. Then an appropriate organic solvent (acetone) is used to desorb the analytes from the sorbent. Finally, the obtained supernatant is mixed with an extraction solvent and injected into deionized water in order to achieve high enrichment factors and sensitivity. Several significant factors affecting the performance of the introduced method were investigated and optimized. Under the optimum experimental conditions, the extraction recoveries of the proposed method for the selected analytes ranged from 49-75%. The relative standard deviations were ≤7% for intra- (n = 6) and inter-day (n = 4) precisions at a concentration of 10 μg L -1 of each analyte. The limits of detection were in the range of 0.15-0.36 μg L -1 . Finally, the applicability of the proposed method was evaluated by analysis of the selected analytes in some fruit juices. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Ion-pair in-tube solid-phase microextraction and capillary liquid chromatography using a titania-based column: application to the specific lauralkonium chloride determination in water.

    Science.gov (United States)

    Prieto-Blanco, M C; Moliner-Martínez, Y; López-Mahía, P; Campíns-Falcó, P

    2012-07-27

    A quick, miniaturized and on-line method has been developed for the determination in water of the predominant homologue of benzalkonium chloride, dodecyl dimethyl benzyl ammonium chloride or lauralkonium chloride (C(12)-BAK). The method is based on the formation of an ion-pair in both in-tube solid-phase microextraction (IT-SPME) and capillary liquid chromatography. The IT-SPME optimization required the study of the length and nature of the stationary phase of capillary and the processed sample volume. Because to the surfactant character of the analyte both, the extracting and replacing solvents, have played a decisive role in the IT-SPME optimized procedure. Conditioning the capillary with the mobile phase which contains the counter ion (acetate), using an organic additive (tetrabutylammonium chloride) added to the sample and a mixture water/methanol as replacing solvent (processed just before the valve is switched to the inject position), allowed to obtain good precision of the retention time and a narrow peak for C(12)-BAK. A reversed-phase capillary based TiO(2) column and a mobile phase containing ammonium acetate at pH 5.0 for controlling the interactions of cationic surfactant with titania surface were proposed. The optimized procedure provided adequate linearity, accuracy and precision at the concentrations interval of 1.5-300 μg L(-1) .The limit of detection (LOD) was 0.5 μg L(-1) using diode array detection (DAD). The applicability of proposed IT-SPME-capillary LC method has been assessed in several water samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Dynamic headspace solid-phase microextraction combined with one-dimensional gas chromatography-mass spectrometry as a powerful tool to differentiate banana cultivars based on their volatile metabolite profile.

    Science.gov (United States)

    Pontes, Marisela; Pereira, Jorge; Câmara, José S

    2012-10-15

    In this study the effect of the cultivar on the volatile profile of five different banana varieties was evaluated and determined by dynamic headspace solid-phase microextraction (dHS-SPME) combined with one-dimensional gas chromatography-mass spectrometry (1D-GC-qMS). This approach allowed the definition of a volatile metabolite profile to each banana variety and can be used as pertinent criteria of differentiation. The investigated banana varieties (Dwarf Cavendish, Prata, Maçã, Ouro and Platano) have certified botanical origin and belong to the Musaceae family, the most common genomic group cultivated in Madeira Island (Portugal). The influence of dHS-SPME experimental factors, namely, fibre coating, extraction time and extraction temperature, on the equilibrium headspace analysis was investigated and optimised using univariate optimisation design. A total of 68 volatile organic metabolites (VOMs) were tentatively identified and used to profile the volatile composition in different banana cultivars, thus emphasising the sensitivity and applicability of SPME for establishment of the volatile metabolomic pattern of plant secondary metabolites. Ethyl esters were found to comprise the largest chemical class accounting 80.9%, 86.5%, 51.2%, 90.1% and 6.1% of total peak area for Dwarf Cavendish, Prata, Ouro, Maçã and Platano volatile fraction, respectively. Gas chromatographic peak areas were submitted to multivariate statistical analysis (principal component and stepwise linear discriminant analysis) in order to visualise clusters within samples and to detect the volatile metabolites able to differentiate banana cultivars. The application of the multivariate analysis on the VOMs data set resulted in predictive abilities of 90% as evaluated by the cross-validation procedure. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. Headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry for the determination of haloanisoles in sparkling (cava and cider) and non-sparkling (wine) alcoholic beverages.

    Science.gov (United States)

    Ruiz-Delgado, Ana; Arrebola-Liébanas, Francisco Javier; Romero-González, Roberto; López-Ruiz, Rosalía; Garrido Frenich, Antonia

    2016-10-01

    A highly sensitive analytical method was developed to determine 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,4,6-tribromoanisole (TBA) and 2,3,4,5,6-pentachloroanisole (PCA) in sparkling alcoholic beverages. The method was based on the use of headspace solid-phase microextraction (HS-SPME) using a polydimethylsiloxane (PDMS) fibre. It was coupled to gas chromatography-triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) for the detection and quantification of the target haloanisoles. The method was fully automated and no sample preparation was needed. The method was validated for alcoholic beverages. The influence of CO 2 on the extraction efficiency was also evaluated for the studied sparkling drinks (cava and cider). All the calibration curves showed good linearity (R 2  > 0.98) within the tested range (1-50 ng l -1 ). Recoveries were evaluated at three different levels (1, 5 and 50 ng l -1 ) and were always between 71% and 119%. Precision was expressed as relative standard deviation (RSD), and was evaluated as intra- and inter-day precisions, with values ≤ 22% in both cases. Limits of quantitation (LOQs) were ≤ 0.91 ng l -1 , which are below the sensory threshold levels for such compounds in humans. The validated method was applied to commercial samples, 10 cavas and 10 ciders, but it was also used for the analysis of nine red wines and four white wines, demonstrating the further applicability of the proposed method to non-sparkling beverages. TCA was detected in most samples at up to 0.45 ng l -1 .

  8. Online analysis of five organic ultraviolet filters in environmental water samples using magnetism-enhanced monolith-based in-tube solid phase microextraction coupled with high-performance liquid chromatography.

    Science.gov (United States)

    Mei, Meng; Huang, Xiaojia

    2017-11-24

    Due to the endocrine disrupting properties, organic UV filters have been a great risk for humans and other organisms. Therefore, development of accurate and effective analytical methods is needed for the determination of UV filters in environmental waters. In this work, a fast, sensitive and environmentally friendly method combining magnetism-enhanced monolith-based in-tube solid phase microextraction with high-performance liquid chromatography with diode array detection (DAD) (ME-MB-IT/SPME-HPLC-DAD) for the online analysis of five organic UV filters in environmental water samples was developed. To extract UV filters effectively, an ionic liquid-based monolithic capillary column doped with magnetic nanoparticles was prepared by in-situ polymerization and used as extraction medium of online ME-MB-IT/SPME-HPLC-DAD system. Several extraction conditions including the intensity of magnetic field, sampling and desorption flow rate, volume of sample and desorption solvent, pH value and ionic strength of sample matrix were optimized thoroughly. Under the optimized conditions, the extraction efficiencies for five organic UV filters were in the range of 44.0-100%. The limits of detection (S/N=3) and limits of quantification (S/N=10) were 0.04-0.26μg/L and 0.12-0.87μg/L, respectively. The precisions indicated by relative standard deviations (RSDs) were less than 10% for both intra- and inter-day variabilities. Finally, the developed method was successfully applied to the determination of UV filters in three environmental water samples and satisfactory results were obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Simultaneous analysis of organochlorine pesticides and polychlorinated biphenyls in air samples by using accelerated solvent extraction (ASE) and solid-phase micro-extraction (SPME) coupled to gas chromatography dual electron capture detection.

    Science.gov (United States)

    Mokbel, Haifaa; Al Dine, Enaam Jamal; Elmoll, Ahmad; Liaud, Céline; Millet, Maurice

    2016-04-01

    An analytical method associating accelerated solvent extraction (ASE) and solid-phase micro-extraction (SPME) in immersion mode combined with gas chromatography dual electrons capture detectors (SPME-GC-2ECD) has been developed and studied for the simultaneous determination of 19 organochlorine pesticides (OCPs) and 22 polychlorinated biphenyls (PCBs) in air samples (active and XAD-2 passive samplers). Samples were extracted with ASE with acetonitrile using the following conditions: temperature, 150 °C; pressure, 1500 psi; static, 15 min; cycles, 3; purge, 300 s; flush, 100 %. Extracts were reduced to 1 mL, and 500 μL of this extract, filled with deionised water, was subject to SPME extraction. Experimental results indicated that the proposed method attained the best extraction efficiency under the optimised conditions: extraction of PCB-OCP mixture using 100-μm PDMS fibre at 80 °C for 40 min with no addition of salt. The performance of the proposed ASE-SPME-GC-2ECD methodology with respect to linearity, limit of quantification and detection was evaluated by spiking of XAD-2 resin with target compounds. The regression coefficient (R (2)) of most compounds was found to be high of 0.99. limits of detection (LODs) are between 0.02 and 4.90 ng m(-3), and limits of quantification (LOQs) are between 0.05 and 9.12 ng m(-3) and between 0.2 and 49 ng/sampler and 0.52 and 91 ng/sampler, respectively, for XAD-2 passive samplers. Finally, a developed procedure was applied to determine selected PCBs and OCPs in the atmosphere.

  10. Quantification of selected volatile organic compounds in human urine by gas chromatography selective reagent ionization time of flight mass spectrometry (GC-SRI-TOF-MS) coupled with head-space solid-phase microextraction (HS-SPME).

    Science.gov (United States)

    Mochalski, Paweł; Unterkofler, Karl

    2016-08-07

    Selective reagent ionization time of flight mass spectrometry with NO(+) as the reagent ion (SRI-TOF-MS(NO(+))) in conjunction with gas chromatography (GC) and head-space solid-phase microextraction (HS-SPME) was used to determine selected volatile organic compounds in human urine. A total of 16 volatiles exhibiting high incidence rates were quantified in the urine of 19 healthy volunteers. Amongst them there were ten ketones (acetone, 2-butanone, 3-methyl-2-butanone, 2-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, and 4-heptanone), three volatile sulphur compounds (dimethyl sulfide, allyl methyl sulfide, and methyl propyl sulfide), and three heterocyclic compounds (furan, 2-methylfuran, 3-methylfuran). The concentrations of the species under study varied between 0.55 nmol L(-1) (0.05 nmol mmol(-1)creatinine) for allyl methyl sulfide and 11.6 μmol L(-1) (1.54 μmol mmol(-1)creatinine) for acetone considering medians. Limits of detection (LODs) ranged from 0.08 nmol L(-1) for allyl methyl sulfide to 1.0 nmol L(-1) for acetone and furan (with RSDs ranging from 5 to 9%). The presented experimental setup assists both real-time and GC analyses of volatile organic compounds, which can be performed consecutively using the same analytical system. Such an approach supports the novel concept of hybrid volatolomics, an approach which combines VOC profiles obtained from two or more body fluids to improve and complement the chemical information on the physiological status of an individual.

  11. Solid phase radioimmunoassays

    International Nuclear Information System (INIS)

    Wide, L.

    1977-01-01

    Solid phase coupled antibodies were introduced to facilitate the separation of bound and free labelled ligand in the competitive inhibition radioimmunoassay. Originally, the solid matrix used was in the form of small particles and since then a number of different matrices have been used such as very fine powder particles, gels, paper and plastic discs, magnetic particles and the inside surface of plastic tubes. The coupling of antibodies may be that of a covalent chemical binding, a strong physical adsorbtion, or an immunological binding to a solid phase coupled antigen. New principles of radioimmunoassay such as the solid phase sandwich techniques and the immunoradiometric assay were developped from the use of solid phase coupled antigens and antibodies. The solid phase sandwich techniques are reagent excess methods with a very wide applicability. Several of the different variants of solid phase techniques are suitable for automation. Advantages and disadvantages of solid phase radioimmunoassays when compared with those using soluble reagents are discussed. (orig.) [de

  12. Optimization of headspace solid-phase microextraction for analysis of {beta}-caryophyllene in a nanoemulsion dosage form prepared with copaiba (Copaifera multijuga Hayne) oil

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Daiane de O; Colombo, Mariana; Kelmann, Regina G. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Av. Ipiranga, 2752, CEP 90610-000 (Brazil); De Souza, Tatiane P. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Universidade Federal do Amazonas, Manaus, Amazonas (Brazil); Bassani, Valquiria L.; Teixeira, Helder F. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Av. Ipiranga, 2752, CEP 90610-000 (Brazil); Veiga, Valdir F. [Departamento de Quimica, Instituto de Ciencias Exatas, UFAM, Av. Gal. Rodrigo Octavio, 6.200 - Japiim, 69.079-000, Manaus - AM (Brazil); Limberger, Renata P. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Av. Ipiranga, 2752, CEP 90610-000 (Brazil); and others

    2012-04-06

    Highlights: Black-Right-Pointing-Pointer A SPME-CG method is proposed for {beta}-caryophyllene assay in nanoemulsions containing copaiba oil. Black-Right-Pointing-Pointer SPME parameters were optimized for efficient {beta}-caryophyllene extraction. Black-Right-Pointing-Pointer The stability-indicating capability and specificity of the method were satisfied. Black-Right-Pointing-Pointer Nanoemulsions partially protected {beta}-caryophyllene under stressing conditions. Black-Right-Pointing-Pointer The proposed method presents linearity, lows LOD and LOQ, good precision, accuracy and robustness. - Abstract: Recent studies have shown the anti-inflammatory activity of Copaiba oils may be addressed to the high content of {beta}-caryophyllene, the most common sesquiterpene detected, especially in the Copaifera multijuga Hayne species. In the present study, nanoemulsions were proposed as a delivery system for copaiba oil in view to treat locally inflamed skin. This article describes the optimization and validation of a stability-indicating SPME-GC method, for {beta}-caryophyllene analysis in the nanoemulsions produced by high pressure homogenization. SPME methods are performed with PDMS (polydimethylsiloxane) fiber (100 {mu}m). Three SPME parameters were evaluated by a three-level-three-factor Box-Behnken factorial design as potentially affecting the technique efficiency. According to the results obtained, the best conditions to extract {beta}-caryophyllene were: (i) sampling temperature of 45 Degree-Sign C, (ii) sampling time of 20 min and (iii) no NaCl addition. Results coming from the forced degradation tests showed a reduction of {beta}-caryophyllene peak area when both caryophyllene methanolic solution and nanoemulsions were exposed to acid hydrolysis, UV-A irradiation, oxidative (H{sub 2}O{sub 2}) and thermolitic (60 Degree-Sign C) conditions. Such reduction occurred in lower extent in the nanoemulsions, suggesting a protective effect of the formulation to {beta

  13. Solid phase microextraction-high performance liquid chromatographic determination of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in the presence of sodium dodecyl sulfate surfactant.

    Science.gov (United States)

    Malik, Ashok Kumar; Rai, Parmod Kumar

    2008-07-01

    A simple and sensitive method has been developed using preconcentration technique solid phase microextraction (SPME) and analytical technique HPLC-UV for the determination of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from the environmental samples. Aqueous solution of anionic surfactant SDS was used for the extraction of both nitramine high explosives, viz., HMX and RDX from soil samples which were subsequently sorbed on SPME fiber. The static desorption was carried out in the desorption chamber of the SPME-HPLC interface in the presence of mobile phase ACN/methanol/water (30:35:35) and the subsequent chromatographic analysis at a flow rate of 0.5 mL/min and detection at 230 nm. For this purpose, a C(18), 5 microm RP analytical column was used as a separation medium in this method. Several parameters relating to SPME, e.g., adsorption/desorption time, concentration of salt, stirring rate, etc., were optimized. The method was linear over the range of 20-400 ng/mL for HMX and RDX standards in the presence of surfactant in aqueous phase, respectively. The correlation coefficient (R(2)) for HMX and RDX are 0.9998 and 0.9982, respectively. With SPME, the detection limits (S/N = 3) in ng/mL are 0.05 and 0.1 for HMX and RDX, respectively in the presence of the SDS surfactant. The developed method has been applied successfully to the analysis of real environmental samples like bore well water, river water, and ground alluvial soil.

  14. Determination of the oxidative stress biomarker urinary 8-hydroxy-2'-deoxyguanosine by automated on-line in-tube solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Kataoka, Hiroyuki; Mizuno, Keisuke; Oda, Eri; Saito, Akihiro

    2016-04-15

    A simple and sensitive method for the determination of 8-hydroxy-2'-deoxyguanosine (8-OHdG), a marker of oxidative DNA damage in human urine, was developed using automated on-line in-tube solid-phase microextraction (SPME) coupled with stable isotope-dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS). Creatinine was also analyzed simultaneously to normalize urine volume by the in-tube SPME LC-MS/MS method, and 8-OHdG and creatinine were separated within 3 min using a Zorbax Eclipse XDB-C8 column. Electrospray MS/MS for these compounds was performed on an API 4000 triple quadruple mass spectrometer in the positive ion mode by multiple reaction monitoring. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 μL of sample at a flow rate of 200 μL/min using a Carboxen 1006 PLOT capillary column as an extraction device. The extracted compounds were easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. The calibration curve for 8-OHdG using its stable isotope-labeled internal standard was linear in the range of 0.05-10 ng/mL, and the detection limit was 8.3 pg/mL. The intra-day and inter-day precision (relative standard deviations) were below 3.1% and 9.6% (n=5), respectively. This method was applied successfully to the analysis of urine samples without any other pretreatment and interference peaks, with good recovery rates above 91% in spiked urine samples. The limits of quantification of 8-OHdG and creatinine in 0.1 mL urine samples were about 0.32 and 0.69 ng/mL (S/N=10), respectively. This method was utilized to assess the effects of smoking, green tea drinking and alcohol drinking on the urinary excretion of 8-OHdG. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Dummy-surface molecularly imprinted polymers as a sorbent of micro-solid-phase extraction combined with dispersive liquid-liquid microextraction for determination of five 2-phenylpropionic acid NSAIDs in aquatic environmental samples.

    Science.gov (United States)

    Guo, Ping; Yuan, Xucan; Zhang, Jingjing; Wang, Binjie; Sun, Xiaoyang; Chen, Xiaohui; Zhao, Longshan

    2018-01-01

    their environmental fate and risk to ecological health. Graphical abstract Dummy-surface molecularly imprinted polymers as a sorbent of micro-solid-phase extraction combined with dispersive liquid-liquid microextraction for determination of five 2-phenylpropionic acid NSAIDs in aquatic environmental samples.

  16. Optimization of headspace experimental factors to determine chlorophenols in water by means of headspace solid-phase microextraction and gas chromatography coupled with mass spectrometry and parallel factor analysis.

    Science.gov (United States)

    Morales, Rocío; Cruz Ortiz, M; Sarabia, Luis A

    2012-11-19

    In this work an analytical procedure based on headspace solid-phase microextraction and gas chromatography coupled with mass spectrometry (HS-SPME-GC/MS) is proposed to determine chlorophenols with prior derivatization step to improve analyte volatility and therefore the decision limit (CCα). After optimization, the analytical procedure was applied to analyze river water samples. The following analytes are studied: 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TrCP), 2,3,4,6-tetrachlorophenol (2,4,6-TeCP) and pentachlorophenol (PCP). A D-optimal design is used to study the parameters affecting the HS-SPME process and the derivatization step. Four experimental factors at two levels and one factor at three levels were considered: (i) equilibrium/extraction temperature, (ii) extraction time, (iii) sample volume, (iv) agitation time and (v) equilibrium time. In addition two interactions between four of them were considered. The D-optimal design enables the reduction of the number of experiments from 48 to 18 while maintaining enough precision in the estimation of the effects. As every analysis took 1h, the design is blocked in 2 days. The second-order property of the PARAFAC (parallel factor analysis) decomposition avoids the need of fitting a new calibration model each time that the experimental conditions change. In consequence, the standardized loadings in the sample mode estimated by a PARAFAC decomposition are the response used in the design because they are proportional to the amount of analyte extracted. It has been found that block effect is significant and that 60°C equilibrium temperature together with 25min extraction time are necessary to achieve the best extraction for the chlorophenols analyzed. The other factors and interactions were not significant. After that, a calibration based in a PARAFAC2 decomposition provided the following values of CCα: 120, 208, 86, 39ngL(-1) for 2,4-DCP, 2,4,6-TrCP, 2,3,4,5-TeCP and PCP respectively for a

  17. Multifunctional Flexible Composites Based on Continuous Carbon Nanotube Fiber

    Science.gov (United States)

    2014-07-28

    different amounts of CNTs [23]. We wrap the graphene fiber with highly aligned CNT film (Fig. 14a). After the hybrid fibers were densified with ethanol ...multifunctional composites fibers [28] and accessing of large polymer chains to enhance fiber mechanical properties [29]. 2.14 Electromechanical...emitters, solid-phase microextraction and catalysis . Different from graphene- based aerogels (GBAs) and membranes (GBMs), GBFs have demonstrated

  18. Extraction of Pesticides from Plants using Solid Phase ...

    African Journals Online (AJOL)

    NICO

    Extraction of Pesticides from Plants using Solid Phase. Microextraction and QuEChERS. Veronica C. Obusenga*, Beauty M. Mookantsaa, Harriet Okatcha,. Ketlhatlogile Mosepeleb and NelsonTortoc. aDepartment of Chemistry. University of Botswana, Private Bag UB 00704, Gaborone, Botswana. bUniversity of Botswana ...

  19. Identificação de compostos voláteis da cúrcuma empregando microextração por fase sólida e cromatografia gasosa acoplada à espectrometria de massas Identification of volatile compounds of turmeric using solid phase microextraction and gas chromatography coupled to mass spectrometry

    Directory of Open Access Journals (Sweden)

    Adriana R. Mata

    2004-03-01

    Full Text Available Compostos voláteis da cúrcuma (Curcuma longa L. cultivada no Brasil foram isolados por microextração por fase sólida. Os rizomas foram cozidos em solução de bicarbonato de sódio 0,1%, fatiados, secos e triturados. Visando estabelecer o sistema ideal para a microextração, fibras de polidimetilsiloxano de 100µm de espessura foram expostas ao headspace de frascos de 10mL. Estudou-se a influência das seguintes variáveis sobre o rendimento dos compostos voláteis obtidos: amostras em pó (0,1 a 1,0g e em solução (40mg/L, diferentes temperaturas (40 a 70ºC e tempos (2 a 20min de partição. O efeito da temperatura (210 a 240ºC e do tempo (3 e 5min de dessorção também foi avaliado. As melhores condições para a partição dos compostos voláteis foram 0,1g do pó, 70ºC e 5min. A temperatura de 220ºC e o tempo de 5 minutos foram os de maior eficiência para a dessorção. A cromatografia gasosa foi conduzida em coluna capilar, detecção por ionização de chama e identificação por espectrometria de massas. A análise dos espectros de massas obtidos para os nove compostos voláteis predominantes indicou a presença de ar-curcúmeno, ar-turmerona, zingibereno, beta-sesquifelandreno, sabineno, 1,8-cineol e 1,4-terpineol.Volatile compounds from turmeric (Curcuma longa L. cultived in Brazil were isolated by solid phase microextraction. The rhizomes were cooked in 0.1% sodium bicarbonate solution, sliced, dried and ground. Polydimethyldiloxanes fibers (100 mm diameter were exposed to the headspace of 10 mL flasks with the aim of establishing an ideal microextraction system. The influence of the following parameters on the volatile substances obtained was studied: powder samples (0.1 to 1.0 g and dissolved samples (40 mg/L, different temperatures (40 to 70ºC and partition periods (2 to 20 min. The effect of temperature (210 to 240ºC and time (3 to 5 min on desorption efficiency was also evaluated. Optimum conditions for the

  20. Hollow fiber liquid-phase microextraction as clean-up step for the determination of organophosphorus pesticides residues in fish tissue by gas chromatography coupled with mass spectrometry.

    Science.gov (United States)

    Sun, Xiaojin; Zhu, Fang; Xi, Jiabin; Lu, Tongbu; Liu, Hong; Tong, Yexiang; Ouyang, Gangfeng

    2011-01-01

    Hollow fiber liquid-phase microextraction (HF-LPME) technique was used as a clean-up procedure for the determination of organophosphorus pesticides (OPPs) in fish tissue. In this study, eight OPPs were first extracted with acetone from fish sample, the organic extract after rotatory evaporation was then redissolved with water-methanol (95:5, v/v) solution, followed by polyvinylidene difluoride (PVDF) HF-LPME. Experimental HF-LPME and other sample preparation conditions were carefully investigated and optimized. Under the optimum conditions, good linearity were observed in the range of 20-500 ng/g, limits of detections (LODs) were in the range of 2.1-4.5 ng/g. The repeatability and recovery of the method also showed satisfactory results. Compared with traditional sample preparation method for the determination of OPPs in fish tissue, the method developed in this study eliminated the solid phase extraction (SPE) step, simplified the sample preparation procedure and lowered the cost of analysis. Copyright © 2011 Elsevier Ltd. All rights reserved.

  1. Solid phase extraction membrane

    Science.gov (United States)

    Carlson, Kurt C [Nashville, TN; Langer, Roger L [Hudson, WI

    2002-11-05

    A wet-laid, porous solid phase extraction sheet material that contains both active particles and binder and that possesses excellent wet strength is described. The binder is present in a relatively small amount while the particles are present in a relatively large amount. The sheet material is sufficiently strong and flexible so as to be pleatable so that, for example, it can be used in a cartridge device.

  2. Solid phase assays

    International Nuclear Information System (INIS)

    Reese, M.G.; Johnson, L.R.; Ransom, D.K.

    1980-01-01

    In a solid phase assay for quantitative determination of biological and other analytes, a sample such as serum is contacted with a receptor for the analyte being assayed, the receptor being supported on a solid support. No tracer for the analyte is added to the sample before contacting with the receptor; instead the tracer is contacted with the receptor after unbound analyte has been removed from the receptor. The assay can be otherwise performed in a conventional manner but can give greater sensitivity. (author)

  3. Solid phase transformations

    CERN Document Server

    Čermák, J

    2008-01-01

    This special-topic book, devoted to ""Solid Phase Transformations"" , covers a broad range of phenomena which are of importance in a number of technological processes. Most commercial alloys undergo thermal treatment after casting, with the aim of imparting desired compositions and/or optimal morphologies to the component phases. In spite of the fact that the topic has lain at the center of physical metallurgy for a long time, there are numerous aspects which are wide open to potential investigative breakthroughs. Materials with new structures also stimulate research in the field, as well as n

  4. Solid-phase spectrophotometry

    International Nuclear Information System (INIS)

    Brykina, G.D.; Marchenko, D.Yu.; Shpigun, O.A.

    1995-01-01

    Solid-phase spectrophotometry (SPS), which is based on the direct measurement of light absorption of an ion exchanger containing a substance of interest, was reviewed. Since 1976, it has been known that aborbance of an ion exchanger is directly proportional to the concentration of a particular ion in solution. A similar dependence can also be followed for other sorbents, as well as for foams, membranes, films, etc., which do not exhibit ion exchange properties. One can use absorption, diffuse reflection, and luminescence spectra parameters as an analytical signal. Thus, SPS of ion exchangers is among the analytical techniques that combine the sorption concentration and surface determination of the substance of interest. This review summarizes the advancements in SPS over the last six years and demonstrates the prospects for its development. Special attention is paid to experimental methods for measuring solid-phase absorption and to the basic procedures of sample preparation, including new ones. These two facets are of great importance for obtaining precise results and extending the capabilities of SPS

  5. Highly porous nanostructured copper foam fiber impregnated with an organic solvent for headspace liquid-phase microextraction.

    Science.gov (United States)

    Saraji, Mohammad; Ghani, Milad; Rezaei, Behzad; Mokhtarianpour, Maryam

    2016-10-21

    A new headspace liquid-phase microextraction technique based on using a copper foam nanostructure substrate followed by gas chromatography-flame ionization detection was developed for the determination of volatile organic compounds in water and wastewater samples. The copper foam with highly porous nanostructured walls was fabricated on the surface of a copper wire by a rapid and facile electrochemical process and used as the extractant solvent holder. Propyl benzoate was immobilized in the pores of the copper foam coating and used for the microextraction of benzene, toluene, ethylbenzene and xylenes. The experimental parameters such as the type of organic solvent, desorption temperature, desorption time, salt concentration, sample temperature, equilibrium time and extraction time, were investigated and optimized. Under the optimum conditions, the method detection limit was between 0.06 and 0.25μgL -1 . The relative standard deviation of the method for the analytes at 4-8μgL -1 concentration level ranged from 7.9 to 11%. The fiber-to-fiber reproducibility for three fibers prepared under the same condition was 9.3-12%. The enrichment factor was in the range of 615-744. Different water samples were analyzed for the evaluation of the method in real sample analysis. Relative recoveries for spiked tap, river and wastewater samples were in the range of 85-94%. Finally, the extraction efficiency of the method was compared with those of headspace single drop microextraction and headspace SPME with the commercial fibers. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Liquid-phase microextraction combined with hollow fiber as a sample preparation technique prior to gas chromatography/mass spectrometry.

    Science.gov (United States)

    Zhao, Limian; Lee, Hian Kee

    2002-06-01

    Two modes of liquid-phase microextraction (LPME) combined with hollow fiber (HF) were developed for gas chromatography/mass spectrometry (GC/MS). Both methodologies, that is, static LPME with HF and dynamic LPME with HF, involved the use of a small volume of organic solvent impregnated in the hollow fiber, which was held by the needle of a conventional GC syringe. In static LPME/HF, the hollow fiber impregnated with solvent was immersed in the aqueous sample, and the extraction processed under stirring; in dynamic LPME/HF, the solvent was repeatedly withdrawn into and discharged from the hollow fiber by a syringe pump. This is believed to be the first reported instance of a semiautomated liquid microextraction procedure. The performance of the two techniques was demonstrated in the analysis of two PAH compounds in an aqueous sample. Static LPME/HF provided approximately 35-fold enrichment in 10 min and good reproducibility (approximately 4%). Dynamic LPME/HF could provide higher enrichment (approximately 75-fold) in 10 min and even better reproducibility (approximately 3%). Both methods allow the direct transfer of extracted analytes to a GC/MS system for analysis.

  7. Double salts of ionic-liquid-based surfactants in microextraction: application of their mixed hemimicelles as novel sorbents in magnetic-assisted micro-dispersive solid-phase extraction for the determination of phenols.

    Science.gov (United States)

    Trujillo-Rodríguez, María J; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

    2015-11-01

    The use of mixed hemimicelles of ionic liquid (IL)-based surfactants in a magnetic-based micro-dispersive solid-phase extraction (m-μdSPE) approach is described. Not only is the symmetric monocationic IL-based surfactant 1,3-didodecylimidazolium bromide (C12C12Im-Br) studied for first time in m-μdSPE, but double-salt (DS) IL (DSIL)-based surfactants are also examined. Nine DSIL-based surfactants were formed by combination of C12C12Im-Br with other IL-based surfactants, including nonsymmetric monocationic and dicationic ILs combined at three different molar fractions. The analytical application was focused on the determination of a group of eight phenols, including bisphenol A, in water samples. The best results were obtained with the DSIL formed by C12C12Im-Br (molar fraction 0.5) and 1-hexadecyl-3-methylimidazolium bromide (C16MIm-Br), after proper optimization of the overall method in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD). The optimum conditions for 100 mL of water samples require a small amount (10 mg) of Fe3O4 magnetic nanoparticles, a low content (5.0 mg of C12C12Im-Br and 3.9 mg of C16MIm-Br) of the selected DSIL, pH 11, a sonication time of 2.5 min, and an equilibration time of 5 min with the aid of NdFeB magnets, followed by elution of phenols, evaporation, and reconstitution with 0.5 mL of acetonitrile. The overall m-μdSPE-HPLC-DAD method is characterized for limits of detection down to 1.3 μg · L(-1), intraday relative standard deviations lower than 13 % (n = 3), and interday relative standard deviations lower than 17 % (n = 9), with a spiking level of 15 μg · L(-1); with enrichment factors between 15.7 and 141, and average relative recoveries of 99.9 %.

  8. Novel materials and methods for solid-phase extraction and liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Ambrose, Diana [Iowa State Univ., Ames, IA (United States)

    1997-06-24

    This report contains a general introduction which discusses solid-phase extraction and solid-phase micro-extraction as sample preparation techniques for high-performance liquid chromatography, which is also evaluated in the study. This report also contains the Conclusions section. Four sections have been removed and processed separately: silicalite as a sorbent for solid-phase extraction; a new, high-capacity carboxylic acid functionalized resin for solid-phase extraction; semi-micro solid-phase extraction of organic compounds from aqueous and biological samples; and the high-performance liquid chromatographic determination of drugs and metabolites in human serum and urine using direct injection and a unique molecular sieve.

  9. Magnetical hollow fiber bar collection of extract in homogenous ionic liquid microextraction of triazine herbicides in water samples.

    Science.gov (United States)

    Wang, Kun; Jiang, Jia; Kang, Mingqin; Li, Dan; Zang, Shuang; Tian, Sizhu; Zhang, Hanqi; Yu, Aimin; Zhang, Ziwei

    2017-04-01

    The homogeneous ionic liquid microextraction combined with magnetical hollow fiber bar collection was developed for extracting triazine herbicides from water samples. These analytes were separated and determined by high performance liquid chromatography. The triazines were quickly extracted into ionic liquid microdroplets dispersed in solution, and then these microdroplets were completely collected with magnetical hollow fiber bars; the pores of which were impregnated with hydrophobic ionic liquid, which makes the phase separation simplified with no need of centrifugation. Some experimental parameters, such as the type of ionic liquid, ultrasonic immersion time of hollow fiber, pH of sample solution, volume of hydrophilic ionic liquid, amount of ion-pairing agent NH 4 PF 6 , NaCl concentration, number of magnetical hollow fiber bar, stirring rate, and collection time were investigated and optimized. When the present method was applied to the analysis of real water samples, the precision and recoveries of six triazine herbicides vary from 0.1 to 9.2% and 73.4 to 118.5%, respectively. The detection limits for terbumeton, ametryn, prometryn, terbutryn, trietazine, and dimethametryn were 0.48, 0.15, 0.15, 0.14, 0.35, and 0.16 μg L -1 , respectively.

  10. Solid-phase peptide synthesis

    DEFF Research Database (Denmark)

    Jensen, Knud Jørgen

    2013-01-01

    This chapter provides an introduction to and overview of peptide chemistry with a focus on solid-phase peptide synthesis. The background, the most common reagents, and some mechanisms are presented. This chapter also points to the different chapters and puts them into perspective....

  11. A novel extraction technique based on carbon nanotubes reinforced hollow fiber solid/liquid microextraction for the measurement of piroxicam and diclofenac combined with high performance liquid chromatography.

    Science.gov (United States)

    Song, Xin-Yue; Shi, Yan-Ping; Chen, Juan

    2012-10-15

    A novel design of carbon nanotubes reinforced hollow fiber solid/liquid phase microextraction (CNTs-HF-SLPME) was developed to determine piroxicam and diclofenac in different real water samples. Functionalized multi-walled carbon nanotubes (MWCNTs) were held in the pores of hollow fiber with sol-gel technology. The pores and lumen of carbon nanotubes reinforced hollow fiber were subsequently filled with a μL volume of organic solvent (1-octanol), and then the whole assembly was used for the extraction of the target analytes in direct immersion sampling mode. The target analytes were extracted from the sample by two extractants, one of which is organic solvent placed inside the pores and lumen of hollow fiber and the other one is CNTs held in the pores of hollow fiber. After extraction, the analytes were desorbed in acetonitrile and analyzed using high performance liquid chromatography. This novel extraction mode showed more excellent extraction performance in comparison with conventional hollow fiber liquid microextraction (without adding CNTs) and carbon nanotubes reinforced hollow fiber solid microextraction (CNTs held in the pores of hollow fiber, but no organic solvents placed inside the lumen of hollow fiber) under the respective optimum conditions. This method provided 47- and 184-fold enrichment factors for piroxicam and diclofenac, respectively, good inter-fiber repeatability and batch-to-batch reproducibility. Linearity was observed in the range of 20-960 μg L(-1) for piroxicam, and 10-2560 μg L(-1) for diclofenac, with correlation coefficients of 0.9985 and 0.9989, respectively. The limits of detection were 4.58 μg L(-1) for piroxicam and 0.40 μg L(-1) for diclofenac. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Determination of polychlorinated biphenyls in water using dynamic hollow fiber liquid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Li, Guanhua; Zhang, Lijun; Zhang, Zhanen

    2008-09-12

    The application of dynamic hollow fiber liquid-phase microextraction (dynamic HF-LPME) and gas chromatography-mass spectrometry (GC-MS) for the determination of trace amounts of polychlorinated biphenyls (PCBs) in water was investigated. The experimental parameters were optimized. Under the optimum conditions, the concentration enrichment factors for PCBs were from 718-fold to 840-fold. The calibration curves were linear over a range of 0.05-90 microg/L, with a correlation coefficient (r(2)) of 0.9957-0.9979. The relative standard deviation (RSD) ranged from 3.4% to 5.8% for intra-day variation and from 4.1% to 7.3% for inter-day variation. The limits of detection (LODs, S/N=3:1) were in the range of 13-41 ng/L. The recoveries for spiked water samples ranged from 85.9% to 92.0%.

  13. Nonequilibrium hollow-fiber liquid-phase microextraction with in situ derivatization for the measurement of triclosan in aqueous samples by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Zhao, Ru-Song; Yuan, Jin-Peng; Li, Hai-Fang; Wang, Xu; Jiang, Ting; Lin, Jin-Ming

    2007-04-01

    Hollow-fiber liquid-phase microextraction (HF-LPME), a relatively new sample preparation technique, has attracted much interest in the field of environmental analysis. In the current study, a novel method based on hollow-fiber liquid-phase microextraction with in situ derivatization and gas chromatography-mass spectrometry for the measurement of triclosan in aqueous samples is described. Hollow-fiber liquid-phase microextraction conditions such as the type of extraction solvent, the stirring rate, the volume of derivatizing reagent, and the extraction time were investigated. When the conditions had been optimized, the linear range was found to be 0.05-100 microg l(-1) for triclosan, and the limit of detection to be 0.02 microg l(-1). Tap water and surface water samples collected from our laboratory and Wohushan reservoir, respectively, were successfully analyzed using the proposed method. The recoveries from the spiked water samples were 83.6 and 114.1%, respectively; and the relative standard deviation (RSD) at the 1.0 microg l(-1) level was 6.9%.

  14. In situ derivatization and hollow fiber membrane microextraction for gas chromatographic determination of haloacetic acids in water.

    Science.gov (United States)

    Varanusupakul, Pakorn; Vora-Adisak, Narongchai; Pulpoka, Bancha

    2007-08-13

    An alternative method for gas chromatographic determination of haloacetic acids (HAAs) in water using direct derivatization followed by hollow fiber membrane liquid-phase microextraction (HF-LPME) has been developed. The method has improved the sample preparation step according to the conventional US EPA Method 552.2 by combining the derivatization and the extraction into one step prior to determination by gas chromatography electron captured detector (GC-ECD). The HAAs were derivatized with acidic methanol into their methyl esters and simultaneously extracted with supported liquid hollow fiber membrane in headspace mode. The derivatization was attempted directly in water sample without sample evaporation. The HF-LPME was performed using 1-octanol as the extracting solvent at 55 degrees C for 60 min with 20% Na2SO4. The linear calibration curves were observed for the concentrations ranging from 1 to 300 microg L(-1) with the correlation coefficients (R2) being greater than 0.99. The method detection limits of most analytes were below 1 microg L(-1) except DCAA and MCAA that were 2 and 18 microg L(-1), respectively. The recoveries from spiked concentration ranged from 97 to 109% with %R.S.D. less than 12%. The method was applied for determination of HAAs in drinking water and tap water samples. The method offers an easy one step high sample throughput sample preparation for gas chromatographic determination of haloacetic acids as well as other contaminants in water.

  15. Salicylic acid determination in estuarine and riverine waters using hollow fiber liquid-phase microextraction and capillary zone electrophoresis.

    Science.gov (United States)

    da Silva, Gilmar Silvério; Lima, Diana L D; Esteves, Valdemar Inocêncio

    2017-06-01

    A low-cost methodology using hollow fiber liquid-phase microextraction (HF-LPME) and capillary zone electrophoresis (CZE) with UV-Vis detector was developed to analyze the salicylic acid (SA) in estuarine and riverine waters. The technique is easy-to-use and rapid, and demands little volume of organic solvent. The extraction was carried out using a polypropylene membrane supporting into octan-1-ol. HF-LPME under optimized conditions (donor solution sample pH 2, acceptor solution pH 14, sample volume 25 mL, fiber length 10 cm, acceptor volume 25 μL, extraction time 3 h and stirring speed 350 rpm) presented high enrichment factor (407 times) and good recovery in real water samples (from 88 to 110%). A limit of detection of 2.6 μg L -1 was achieved using CZE with UV-Vis detector as quantification method. The method was applied to direct quantification of SA in environmental complex estuarine and riverine water matrices.

  16. In situ derivatization and hollow fiber membrane microextraction for gas chromatographic determination of haloacetic acids in water

    International Nuclear Information System (INIS)

    Varanusupakul, Pakorn; Vora-adisak, Narongchai; Pulpoka, Bancha

    2007-01-01

    An alternative method for gas chromatographic determination of haloacetic acids (HAAs) in water using direct derivatization followed by hollow fiber membrane liquid-phase microextraction (HF-LPME) has been developed. The method has improved the sample preparation step according to the conventional US EPA Method 552.2 by combining the derivatization and the extraction into one step prior to determination by gas chromatography electron captured detector (GC-ECD). The HAAs were derivatized with acidic methanol into their methyl esters and simultaneously extracted with supported liquid hollow fiber membrane in headspace mode. The derivatization was attempted directly in water sample without sample evaporation. The HF-LPME was performed using 1-octanol as the extracting solvent at 55 deg. C for 60 min with 20% Na 2 SO 4 . The linear calibration curves were observed for the concentrations ranging from 1 to 300 μg L -1 with the correlation coefficients (R 2 ) being greater than 0.99. The method detection limits of most analytes were below 1 μg L -1 except DCAA and MCAA that were 2 and 18 μg L -1 , respectively. The recoveries from spiked concentration ranged from 97 to 109% with %R.S.D. less than 12%. The method was applied for determination of HAAs in drinking water and tap water samples. The method offers an easy one step high sample throughput sample preparation for gas chromatographic determination of haloacetic acids as well as other contaminants in water

  17. Solid phase syntheses of oligoureas

    Energy Technology Data Exchange (ETDEWEB)

    Burgess, K.; Linthicum, D.S.; Russell, D.H.; Shin, H.; Shitangkoon, A.; Totani, R.; Zhang, A.J.; Ibarzo, J. [Texas A& M Univ., College Station, TX (United States)

    1997-02-19

    Isocyanates 7 were formed from monoprotected diamines 3 or 6, which in turn can be easily prepared from commercially available N-BOC- or N-FMOC-protected amino acid derivatives. Isocyanates 7, formed in situ, could be coupled directly to a solid support functionalized with amine groups or to amino acids anchored on resins using CH{sub 2}Cl{sub 2} as solvent and an 11 h coupling time at 25 {degree}C. Such couplings afforded peptidomimetics with an N-phthaloyl group at the N-terminus. The optimal conditions identified for removal of the N-phthaloyl group were to use 60% hydrazine in DMF for 1-3 h. Several sequences of amino acids coupled to ureas (`peptidic ureas`) and of sequential urea units (`oligoureas`) were prepared via solid phase syntheses and isolated by HPLC. Partition coefficients were measured for two of these peptidomimetics, and their water solubilities were found to be similar to the corresponding peptides. A small library of 160 analogues of the YGGFL-amide sequence was prepared via Houghten`s tea bag methodology. This library was tested for binding to the anti-{beta}-endorphin monoclonal antibody. Overall, this paper describes methodology for solid phase syntheses of oligourea derivatives with side chains corresponding to some of the protein amino acids. The chemistry involved is ideal for high-throughput syntheses and screening operations. 51 refs., 3 figs., 2 tabs.

  18. Simultaneous derivatization and extraction of primary amines in river water with dynamic hollow fiber liquid-phase microextraction followed by gas chromatography-mass spectrometric detection.

    Science.gov (United States)

    Chia, Kan-Jung; Huang, Shang-Da

    2006-01-20

    A one-step derivatization and extraction technique for the determination of primary amines in river water by liquid-phase microextraction (LPME) is presented. In this method the primary amines are derivatized with pentafluorobenzaldehyde (PFBAY) in aqueous solution and extracted by dynamic hollow fiber-protected-LPME (HF-LPME) simultaneously. The effects of solvent selection, sample agitation, extraction time, extraction temperature and salt concentration on the extraction performance are investigated. High enrichments (172-244-fold) and good repeatabilities (RSD less than 7.2%) were obtained. Linearity in this developed method was ranging from 1 to 500 ng/ml, and the correlation coefficients (R2) were between 0.992 and 0.998. Comparisons of sensitivity and precision between dynamic HF-LPME and single-drop liquid-phase microextraction (SDME) were also made.

  19. Determination of polycyclic aromatic hydrocarbons in fresh milk by hollow fiber liquid-phase microextraction-gas chromatography mass spectrometry.

    Science.gov (United States)

    Sanagi, Mohd Marsin; Loh, Saw Hong; Wan Ibrahim, Wan Aini; Hasan, Mohamed Noor; Aboul Enein, Hassan Y

    2013-02-01

    In this work, a two-phase hollow fiber liquid-phase microextraction (HF-LPME) method combined with gas chromatography-mass spectrometry (GC-MS) is developed to provide a rapid, selective and sensitive analytical method to determine polycyclic aromatic hydrocarbons (PAHs) in fresh milk. The standard addition method is used to construct calibration curves and to determine the residue levels for the target analytes, fluorene, phenanthrene, fluoranthene, pyrene and benzo[a]pyrene, thus eliminating sample pre-treatment steps such as pH adjustment. The HF-LPME method shows dynamic linearity from 5 to 500 µg/L for all target analytes with R(2) ranging from 0.9978 to 0.9999. Under optimized conditions, the established detection limits range from 0.07 to 1.4 µg/L based on a signal-to-noise ratio of 3:1. Average relative recoveries for the determination of PAHs studied at 100 µg/L spiking levels are in the range of 85 to 110%. The relative recoveries are slightly higher than those obtained by conventional solvent extraction, which requires saponification steps for fluorene and phenanthrene, which are more volatile and heat sensitive. The HF-LPME method proves to be simple and rapid, and requires minimal amounts of organic solvent that supports green analysis.

  20. The mass transfer dynamics of hollow fiber liquid-phase microextraction and its application for rapid analysis of biological samples.

    Science.gov (United States)

    Cui, Shufen; Ouyang, Gangfeng; Duan, Guijiao; Hou, Jinxing; Luan, Tiangang; Zhang, Xu

    2012-11-30

    Hollow fiber liquid-phase microextraction (HF-LPME) has been demonstrated to potentially become a mainstream sample preparation technique for complex samples. Nevertheless, the need for a relatively long extraction time is considered to be the major disadvantage of this method. Lengthy extractions may cause the loss of the extraction phase and may change the contents of biological samples via the action of enzymes. Therefore, control calibrations for particular biological systems must be made. In this study, a theoretical model of the mass transfer dynamics of two-phase HF-LPME was proposed, and the kinetic calibration (KC) of this method for plasma and urine samples was validated. The theoretical results were validated by examining the kinetics of the extraction and back-extraction processes of HF-LPME. The KC-HF-LPME method was successfully used to correct for matrix effects in plasma and urine samples during flunitrazepam analysis. The free amount of flunitrazepam was extracted from plasma for 10 min and analyzed by gas chromatography/mass spectrometry. The amount of pre-added standard and the standard remaining in the extraction phase after extraction were used for the quantification of flunitrazepam in plasma and urine samples. The new method not only significantly shortens the extraction time but also provides a new opportunity to determine the free concentration of analyte in biological systems. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Hollow fiber-liquid phase microextraction combined with gas chromatography for the determination of phenothiazine drugs in urine.

    Science.gov (United States)

    Xiao, Qin; Hu, Bin

    2010-06-01

    A simple method of hollow fiber-liquid phase microextraction (HF-LPME) combined with gas chromatography (GC) was developed for the analysis of four phenothiazine drugs (promethazine, promazine, chlorpromazine and trifluoperazine) in human urine samples. All variables affecting the extraction of target analytes including organic solvent type, stirring rate, extraction time, extraction temperature, pH of sample solution and ionic strength were carefully studied and optimized. Under the optimal conditions, the analytical performance of HF-LPME-GC-flame photometric detector (FPD) and HF-LPME-GC-flame ionization detector (FID) were evaluated and compared. The results showed that the HF-LPME-GC-FID was more sensitive than HF-LPME-GC-FPD for the determination of four target phenothiazine drugs, while the signal peak shape and resolution obtained by HF-LPME-GC-FPD was better than that obtained by HF-LPME-GC-FID. HF-LPME-GC-FPD/FID was successfully applied for the assay of the interested phenothiazine drugs in urine sample, and the excretion of the drugs was also investigated by monitoring the variation of the concentration of chlorpromazine in urine of a psychopath within 8 h after drug-taking. The proposed method provided an effective and fast way for the therapeutic drug monitoring (TDM) of phenothiazine. Copyright 2010 Elsevier B.V. All rights reserved.

  2. Comparison of hollow fiber liquid-phase microextraction and ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction for the determination of drugs of abuse in biological samples by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Meng, Liang; Zhang, Wenwen; Meng, Pinjia; Zhu, Binling; Zheng, Kefang

    2015-05-01

    Two microextraction techniques based on hollow fiber liquid-phase microextraction (HF-LPME) and ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction (UA-LDS-DLLME) had been applied for the determination of drugs of abuse (methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine, 3,4-methylenedioxyamphetamine, methcathinone, ketamine, meperidine, and methadone) in urine and blood samples by gas chromatography-mass spectrometry. Parameters affecting extraction efficiency have been investigated and optimized for both methods. Under the optimum conditions, linearities were observed for all analytes in the range 0.0030-10 μg/ml with the correlation coefficient (R) ranging from 0.9985 to 0.9995 for HF-LPME and in the range 0.0030-10 μg/ml with the R ranging from 0.9985 to 0.9994 for DLLME. The recovery of 79.3-98.6% with RSDs of 1.2-4.5% was obtained for HF-LPME, and the recovery of 79.3-103.4% with RSDs of 2.4-5.7% was obtained for DLLME. The LODs (S/N=3) were estimated to be in the range from 0.5 to 5 ng/ml and 0.5 to 4 ng/ml, respectively. Compared with HF-LPME, the UA-LDS-DLLME technique had the advantages of less extraction time, suitability for batches of sample pretreatment simultaneously, and higher extraction efficiency, while HF-LPME has excellent sample clean-up effect, and is a robust and suitable technique for various sample matrices with better repeatability. Both methods were successfully applied to the analysis of drugs of abuse in real human blood sample. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Hollow fiber-based liquid phase microextraction combined with high-performance liquid chromatography for extraction and determination of some antidepressant drugs in biological fluids.

    Science.gov (United States)

    Esrafili, Ali; Yamini, Yadollah; Shariati, Shahab

    2007-12-05

    The applicability of hollow fiber-based liquid phase microextraction (HF-LPME) was evaluated for the extraction and preconcentration of three antidepressant drugs (amitriptyline, imipramine and sertraline) prior to their determination by HPLC-UV. The target drugs were extracted from 11.0 mL of aqueous solution with pH 12.0 (source phase) into an organic extracting solvent (n-dodecane) impregnated in the pores of a hollow fiber and finally back extracted into 24 microL of aqueous solution located inside the lumen of the hollow fiber and adjusted to pH 2.1 using 0.1M of H3PO4 (receiving phase). The extraction was performed due to pH gradient between the inside and outside of the hollow fiber membrane. In order to obtain high extraction efficiency, the parameters affecting the HF-LPME including pH of the source and receiving phases, the type of organic phase, ionic strength and volume of the source phase, stirring rate and extraction time were studied and optimized. Under the optimized conditions, enrichment factors up to 300 were achieved and the relative standard deviation (R.S.D.%) of the method was in the range of 2-12%. The calibration curves were obtained in the range of 5-500 microg L(-1) with reasonable linearity (R2>0.998) and the limits of detection (LODs) ranged between 0.5 and 0.7 microg L(-1) (based on S/N=3). Finally, the applicability of the proposed method was evaluated by extraction and determination of the drugs in urine, plasma and tap water samples. The results indicated that hollow fiber microextraction method has excellent clean-up and high-preconcentration factor and can be served as a simple and sensitive method for monitoring of antidepressant drugs in the biological samples.

  4. Hollow fiber-stir bar sorptive extraction and microwave assisted derivatization of amino acids in biological matrices.

    Science.gov (United States)

    Li, Jia; Qi, Huan-Yang; Wang, Yan-Bin; Su, Qiong; Wu, Shang; Wu, Lan

    2016-11-25

    A kind of solid phase microextraction configuration combining the principles of hollow fiber solid phase microextraction (HF-SPME) and stir bar sorptive extraction (SBSE) is presented. The main feature of HF-SBSE is the use of microporous hollow fiber acting as the carrier and filter, while a thin stainless steel wire and silica microspheres in the lumen of hollow fiber respectively acting as the magnetic stirrer and the dispersed sorbents for the collection and extraction of the target analytes, thus affording extraction process like SBSE. Moreover, the prepared hollow fiber stir bar was applied to direct microextraction and microwave assisted derivatization with N,O-Bis(trimethylsilyl)trifluroacetamide (BSTFA) of four amino acids in rats' urine and cerebrospinal fluid followed by gas chromatography mass spectrometric analysis. The limits of detection for four amino acids were found to be in the range of 0.0003-0.017μgmL -1 , and all the analytes did not exhibit any lack of fit. The extraction recoveries using HF-SBSE techniques ranged from 71.8% to 102.3%. The results indicated that hollow fiber stir bar sorptive extraction was a promising technique for the enrichment and direct derivatization of analytes extracted from biological matrices without sample clean-up. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Maghemite nanoparticle-decorated hollow fiber electromembrane extraction combined with dispersive liquid-liquid microextraction for the determination of thymol from Carum copticum

    DEFF Research Database (Denmark)

    Khajeh, Mostafa; Pedersen-Bjergaard, Stig; Bohlooli, Mousa

    2017-01-01

    BACKGROUND A novel technique using maghemite nanoparticle-decorated hollow fibers to assist electromembrane extraction is proposed. Electromembrane extraction combined with dispersive liquid–liquid microextraction (EME-DLLME) was applied for the extraction of thymol from Carum copticum, followed...... by gas chromatography with flame ionization detection (GC-FID). RESULTS The use of maghemite nanoparticle-decorated hollow fibers was found to improve the extraction efficiency of thymol significantly. Important operational parameters, including pH of acceptor phase, extraction time, voltage.......2% respectively. The intra- and inter-day accuracy was higher than 93.6%. CONCLUSION The results indicated that EME-DLLME/GC-FID is a useful technique for the extraction and determination of thymol in C copticum. © 2016 Society of Chemical Industry...

  6. Microextração em fase líquida (LPME: fundamentos da técnica e aplicações na análise de fármacos em fluidos biológicos Liquid-phase microextraction (LPME: fundamentals and applications to the analysis of drugs in biological samples

    Directory of Open Access Journals (Sweden)

    Anderson Rodrigo Moraes de Oliveira

    2008-01-01

    Full Text Available The analysis of drugs and metabolites in biological fluids usually requires extraction procedures to achieve sample clean-up and analyte preconcentration. Commonly, extraction procedures are performed using liquid-liquid extraction or solid-phase extraction. Nevertheless, these extraction techniques are considered to be time-consuming and require a large amount of organic solvents. On this basis, microextraction techniques have been developed. Among them, liquid-phase microextraction has been standing out. This review describes the liquid-phase microextraction technique based on hollow fibers as a novel and promising alternative in sample preparation prior to chromatographic or electrophoretic analysis. The basic concepts related to this technique and its applicability in extraction of drugs are discussed.

  7. Hollow-fiber liquid-phase microextraction of amphetamine-type stimulants in human hair samples.

    Science.gov (United States)

    do Nascimento Pantaleão, Lorena; Bismara Paranhos, Beatriz Aparecida Passos; Yonamine, Mauricio

    2012-09-07

    A fast method was optimized and validated in order to quantify amphetamine-type stimulants (amphetamine, AMP; methamphetamine, MAMP; fenproporex, FPX; 3,4-methylenedioxymethamphetamine, MDMA; and 3,4-methylenedioxyamphetamine, MDA) in human hair samples. The method was based in an initial procedure of decontamination of hair samples (50 mg) with dichloromethane, followed by alkaline hydrolysis and extraction of the amphetamines using hollow-fiber liquid-phase micro extraction (HF-LPME) in the three-phase mode. Gas chromatography-mass spectrometry (GC-MS) was used for identification and quantification of the analytes. The LoQs obtained for all amphetamines (around 0.05 ng/mg) were below the cut-off value (0.2 ng/mg) established by the Society of Hair Testing (SoHT). The method showed to be simple and precise. The intra-day and inter-day precisions were within 10.6% and 11.4%, respectively, with the use of only two deuterated internal standards (AMP-d5 and MDMA-d5). By using the weighted least squares linear regression (1/x²), the accuracy of the method was satisfied in the lower concentration levels (accuracy values better than 87%). Hair samples collected from six volunteers who reported regular use of amphetamines were submitted to the developed method. Drug detection was observed in all samples of the volunteers. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Comparison of hollow fiber liquid phase microextraction and dispersive liquid-liquid microextraction for the determination of organosulfur pesticides in environmental and beverage samples by gas chromatography with flame photometric detection.

    Science.gov (United States)

    Xiong, Jun; Hu, Bin

    2008-06-06

    Two methods based on hollow fiber liquid phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME), have been critically compared for the analysis of organosulfur pesticides (OSPs) in environmental and beverage samples by gas chromatography-flame photometric detection (GC-FPD). Experimental conditions including extraction solvent, solvent volume, extraction time, temperature and ionic strength have been investigated for both HF-LPME and DLLME. Under the optimal conditions, the limits of detection for the six target OSPs (malathion, chlorpyrifos, buprofezin, triazophos, carbosulfan and pyridaben) obtained by HF-LPME-GC-FPD and DLLME-GC-FPD were ranged from 1.16 microg/L to 48.48 microg/L and 0.21 microg/L to 3.05 microg/L, respectively. The relative standard deviations (RSDs, n=5) were in the range of 3.4-8.0% and 8.5-13.7%with the enrichment factors (EFs) of 27-530 and 176-946 folds for HF-LPME-GC-FPD and DLLME-GC-FPD, respectively. Both methods were found to be simple, fast, efficient, and inexpensive. Compared with HF-LPME, the advantages of DLLME technique were less extraction time, suitable for batches of samples pretreatment simultaneously, a higher extraction capacity when analyzing simple samples such as water samples. While for the analysis of complicated matrix samples such as soil and beverage samples, HF-LPME was demonstrated to be more robust and more suitable. Both methods were applied to the analysis of six OSPs in different waters, soil and beverage samples, and no target OSPs was found in these samples. For analysis of the spiked samples, the recovery of 81.7-114.4% with RSDs of 0.6-9.6% were obtained for HF-LPME, and the recovery of 78.5-117.2% with RSDs of 0.6-11.9% were obtained for DLLME.

  9. Comparison of dispersive liquid-liquid microextraction and hollow fiber liquid-liquid-liquid microextraction for the determination of fentanyl, alfentanil, and sufentanil in water and biological fluids by high-performance liquid chromatography.

    Science.gov (United States)

    Saraji, Mohammad; Khalili Boroujeni, Malihe; Hajialiakbari Bidgoli, Ali Akbar

    2011-06-01

    Dispersive liquid-liquid microextraction (DLLME) and hollow fiber liquid-liquid-liquid microextraction (HF-LLLME) combined with HPLC-DAD have been applied for the determination of three narcotic drugs (alfentanil, fentanyl, and sufentanil) in biological samples (human plasma and urine). Different DLLME parameters influencing the extraction efficiency such as type and volume of the extraction solvent and the disperser solvent, concentration of NaOH, and salt addition were investigated. In the HF-LLLME, the effects of important parameters including organic solvent type, concentration of NaOH as donor solution, concentration of H(2)SO(4) as acceptor phase, salt addition, stirring rate, temperature, and extraction time were investigated and optimized. The results showed that both extraction methods exhibited good linearity, precision, enrichment factor, and detection limit. Under optimal condition, the limits of detection ranged from 0.4 to 1.9 μg/L and from 1.1 to 2.3 μg/L for DLLME and HF-LLLME, respectively. For DLLME, the intra- and inter-day precisions were 1.7-6.4% and 14.2-15.9%, respectively; and for HF-LLLME were 0.7-5.2% and 3.3-10.1%, respectively. The enrichment factors were from 275 to 325 and 190 to 237 for DLLME and HF-LLLME, respectively. The applicability of the proposed methods was investigated by analyzing biological samples. For analysis of human plasma and urine samples, HF-LLLME showed higher precision, more effective sample clean-up, higher extraction efficiency, lower organic solvent consumption than DLLME.

  10. Determination of ketamine, norketamine and dehydronorketamine in urine by hollow-fiber liquid-phase microextraction using an essential oil as supported liquid membrane.

    Science.gov (United States)

    Bairros, André Valle de; Lanaro, Rafael; Almeida, Rafael Menck de; Yonamine, Mauricio

    2014-10-01

    Here, we present a method for the determination of ketamine (KT) and its main metabolites, norketamine (NK) and dehydronorketamine (DHNK) in urine samples by using hollow-fiber liquid-phase microextraction (HF-LPME) in the three-phase mode. The fiber pores were filled with eucalyptus essential oil and a solution of 1.0mol/L of HCl was introduced into the lumen of the fiber (acceptor phase). The fiber was submersed in the alkalinized urine containing 10% NaCl, and the system was submitted to lateral shaking (2400rpm) during 30min. Acceptor phase was withdrawn from the fiber, dried and the residue was then derivatized with trifluoroacetic anhydride (TFAA) for further determination by gas chromatography-mass spectrometry (GC-MS). The calibration curves were linear over the specified range and limits of detection (LoDs) obtained for KT, NK and DHNK were below the cut-off value (1.0ng/mL) recommended by the United Nations Office on Drugs and Crime (UNODC). A totally "green chemistry" approach of the sample extraction was obtained by using essential oil as a supported liquid membrane in HF-LPME. The developed method was successfully validated and applied to urine samples collected from two clinical cases in which KT was suspected to be involved. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  11. Simultaneous determination of several phytohormones in natural coconut juice by hollow fiber-based liquid-liquid-liquid microextraction-high performance liquid chromatography.

    Science.gov (United States)

    Wu, Yunli; Hu, Bin

    2009-11-06

    A simple, selective, sensitive and inexpensive method of hollow fiber-based liquid-liquid-liquid microextraction (HF-LLLME) combined with high performance liquid chromatography (HPLC)-ultraviolet (UV) detection was developed for the determination of four acidic phytohormones (salicylic acid (SA), indole-3-acetic acid (IAA), (+/-) abscisic acid (ABA) and (+/-) jasmonic acid (JA)) in natural coconut juice. To the best of our knowledge, this is the first report on the use of liquid phase microextraction (LPME) as a sample pretreatment technique for the simultaneous analysis of several phytohormones. Using phenetole to fill the pores of hollow fiber as the organic phase, 0.1molL(-1) NaOH solution in the lumen of hollow fiber as the acceptor phase and 1molL(-1) HCl as the donor phase, a simultaneous preconcentration of four target phytohormones was realized. The acceptor phase was finally withdrawn into the microsyringe and directly injected into HPLC for the separation and quantification of the target phytohormones. The factors affecting the extraction efficiency of four phytohormones by HF-LLLME were optimized with orthogonal design experiment, and the data was analyzed by Statistical Product and Service Solutions (SPSS) software. Under the optimized conditions, the enrichment factors for SA, IAA, ABA and JA were 243, 215, 52 and 48, with the detection limits (S/N=3) of 4.6, 1.3, 0.9ngmL(-1) and 8.8 microg mL(-1), respectively. The relative standard deviations (RSDs, n=7) were 7.9, 4.9, 6.8% at 50ngmL(-1) level for SA, IAA, ABA and 8.4% at 500 microg mL(-1) for JA, respectively. To evaluate the accuracy of the method, the developed method was applied for the simultaneous analysis of several phytohormones in five natural coconut juice samples, and the recoveries for the spiked samples were in the range of 88.3-119.1%.

  12. In situ derivatization and hollow-fiber liquid-phase microextraction to determine sulfonamides in water using UHPLC with fluorescence detection.

    Science.gov (United States)

    Yang, Lihua; Shi, Yang; Li, Jinjin; Luan, Tiangang

    2017-12-30

    A sensitive method for determining sulfonamides in water was developed and validated through in situ derivatization and hollow-fiber liquid-phase microextraction with ultra-high performance liquid chromatography and fluorescence detection. The target sulfonamides were sulfadiazine, sulfacetamide, sulfamerazine, sulfamethazine, sulfamethoxypyridazine, sulfachloropyridazine, sulfamethoxazole, and sulfisoxazole. Following in situ derivatization with fluorescamine, three-phase hollow-fiber liquid-phase microextraction with an S 6/2 polypropylene hollow-fiber membrane was applied automatically using a multipurpose autosampler. Experimental parameters including derivatization time, choice of organic phase, pH of donor and acceptor phase, stirring rate, extraction temperature and time were optimized. Under optimized conditions, the target sulfonamides achieved excellent linearity with correlation coefficients of 0.9924-0.9994 within the concentration range of 0.05-5 μg/L. The limits of detection of the eight sulfonamides were 3.1-11.2 ng/L, and the limits of quantification were 10.3-37.3 ng/L. Enrichment factors of 0.1 and 5 μg/L sulfonamides spiked in lake water were 14-60, and recoveries were 56-113% with relative standard derivations of 3-19%. Applied with the developed method, sulfamerazine and sulfamethoxazole were measurable in both influent and effluent water of the three sewage treatment plants in Guangzhou, China. The developed method was sensitive and provided an alternative method for simultaneously enriching and quantifying multiple sulfonamides in environmental water. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Miniaturized hollow fiber assisted liquid-phase microextraction and gas chromatography-mass spectrometry for the measurement of progesterone in human serum.

    Science.gov (United States)

    Kawaguchi, Migaku; Takatsu, Akiko

    2009-01-15

    Miniaturized hollow fiber assisted liquid-phase microextraction (HF-LPME) and gas chromatography-mass spectrometry (GC-MS) for the determination of progesterone in human serum sample is described. The detection limit and the quantification limit of progesterone in human serum sample are 0.5 and 2 ng mL(-1) (ppb), respectively. The calibration curve for progesterone is linear with a correlation coefficient of >0.999 in the range of 2-500 ng mL(-1). The average recoveries of progesterone in human serum samples spiked with 5, 50 and 200 ng mL(-1) progesterone are 97.4% (R.S.D.: 9.3%), 100.3% (R.S.D.: 4.7%) and 99.8% (R.S.D.: 3.4%), respectively. This simple, accurate, sensitive and selective analytical method can be applicable for the determination of progesterone in human serum samples.

  14. Hollow fiber liquid-phase microextraction-gas chromatography-mass spectrometry method to analyze bisphenol A and other plasticizer metabolites.

    Science.gov (United States)

    Fernandez, Miriany A Moreira; André, Leiliane Coelho; Cardeal, Zenilda de Lourdes

    2017-01-20

    Phthalates and bisphenol A are important environmental pollutants due to their toxicity for humans and animals, including actions in the endocrine system. Their metabolites in urine can be used as biomarkers to assess human exposure. This paper describes the development of a new method to determine bisphenol A and eight phthalate metabolites in urine samples using hollow fiber liquid phase microextraction (HF-LPME) and gas chromatography-mass spectrometry (GC-MS). This method showed linearity, precision, limits of detection, and quantification suitable to analyze these compounds at low concentration levels in urine. Limits of detection ranged from 0.777 to 23.3μgL -1 , showing sensitivity for evaluating environmental exposure. Relative standard deviation (RSD) ranged from 11.7 to 19.7%. The developed method presented a good biomarker alternative for evaluating environmental exposure to bisphenol A and phthalates. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Residue analysis of tetracyclines in milk by HPLC coupled with hollow fiber membranes-based dynamic liquid-liquid micro-extraction.

    Science.gov (United States)

    Xu, Hui; Mi, Hong-Yu; Guan, Ming-Ming; Shan, Hong-Yan; Fei, Qiang; Huan, Yan-Fu; Zhang, Zhi-Quan; Feng, Guo-Dong

    2017-10-01

    A novel hollow fiber membranes-based dynamic liquid-liquid micro-extraction (HF-DLLME) coupled with HPLC-UV detection has been developed for the residue analysis of tetracyclines in milk samples without deproteinization and degreasing. The influences of experimental parameters were investigated and optimized. The method showed a good performance. The limits of detection (LOD) are in the range of 0.95-3.6μg/L. The recoveries in spiked samples range from 92.38 to 107.3%. The relative standard deviations (RSDs) are lower than 8.66%. The advantages of this method are simple operation, high efficiency, absence of sample carryover and low cost. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Hollow fiber-based liquid-phase microextraction (HF-LPME) of ibuprofen followed by FIA-chemiluminescence determination using the acidic permanganate-sulfite system.

    Science.gov (United States)

    Payán, María Ramos; López, Miguel Angel Bello; Fernández-Torres, Rut; Navarro, Mercedes Villar; Mochón, Manuel Callejón

    2009-08-15

    Hollow fiber-based liquid-phase microextraction (HF-LPME) is a relatively new technique employed in analytical chemistry for sample pretreatment which offers more selectivity and sensitivity than any traditional extraction technique. This paper describes a three-phase HF-LPME method for ibuprofen using a polypropylene membrane supporting dihexyl ether followed by a chemiluminescence (CL) determination using the CL enhancement on the acidic permanganate-sulfite system in a FIA configuration which is the first time that both techniques have been combined for analytical purposes. The CL intensity (peak area) was proportional to the log of ibuprofen concentration in the donor phase over the range 0.1-20 microg mL(-1). The detection limit was 0.03 microg mL(-1) of ibuprofen in the donor phase. The method was satisfactory reproducible and has been applied to the ibuprofen determination in pharmaceuticals and in real human urine samples.

  17. Development of a novel mixed hemimicelles dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene for the separation and preconcentration of fluoxetine in different matrices before its determination by fiber optic linear array spectrophotometry and mode-mismatched thermal lens spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kazemi, Elahe; Haji Shabani, Ali Mohammad [Department of Chemistry, Yazd University, Safaieh, 89195-741, Yazd (Iran, Islamic Republic of); Dadfarnia, Shayessteh, E-mail: sdadfarnia@yazd.ac.ir [Department of Chemistry, Yazd University, Safaieh, 89195-741, Yazd (Iran, Islamic Republic of); Abbasi, Amir [Department of Physics, Yazd University, Safaieh, 89195-741, Yazd (Iran, Islamic Republic of); Rashidian Vaziri, Mohammad Reza [Laser and Optics Research School, 14155-1339, Tehran (Iran, Islamic Republic of); Behjat, Abbas [Department of Physics, Yazd University, Safaieh, 89195-741, Yazd (Iran, Islamic Republic of)

    2016-01-28

    This study aims at developing a novel, sensitive, fast, simple and convenient method for separation and preconcentration of trace amounts of fluoxetine before its spectrophotometric determination. The method is based on combination of magnetic mixed hemimicelles solid phase extraction and dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene as a sorbent. The magnetic graphene was synthesized by a simple coprecipitation method and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The retained analyte was eluted using a 100 μL mixture of methanol/acetic acid (9:1) and converted into fluoxetine-β-cyclodextrin inclusion complex. The analyte was then quantified by fiber optic linear array spectrophotometry as well as mode-mismatched thermal lens spectroscopy (TLS). The factors affecting the separation, preconcentration and determination of fluoxetine were investigated and optimized. With a 50 mL sample and under optimized conditions using the spectrophotometry technique, the method exhibited a linear dynamic range of 0.4–60.0 μg L{sup −1}, a detection limit of 0.21 μg L{sup −1}, an enrichment factor of 167, and a relative standard deviation of 2.1% and 3.8% (n = 6) at 60 μg L{sup −1} level of fluoxetine for intra- and inter-day analyses, respectively. However, with thermal lens spectrometry and a sample volume of 10 mL, the method exhibited a linear dynamic range of 0.05–300 μg L{sup −1}, a detection limit of 0.016 μg L{sup −1} and a relative standard deviation of 3.8% and 5.6% (n = 6) at 60 μg L{sup −1} level of fluoxetine for intra- and inter-day analyses, respectively. The method was successfully applied to determine fluoxetine in pharmaceutical formulation, human urine and environmental water samples. - Graphical abstract: A novel, sensitive, fast, simple and convenient mixed hemimicelles

  18. Development of a novel mixed hemimicelles dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene for the separation and preconcentration of fluoxetine in different matrices before its determination by fiber optic linear array spectrophotometry and mode-mismatched thermal lens spectroscopy

    International Nuclear Information System (INIS)

    Kazemi, Elahe; Haji Shabani, Ali Mohammad; Dadfarnia, Shayessteh; Abbasi, Amir; Rashidian Vaziri, Mohammad Reza; Behjat, Abbas

    2016-01-01

    This study aims at developing a novel, sensitive, fast, simple and convenient method for separation and preconcentration of trace amounts of fluoxetine before its spectrophotometric determination. The method is based on combination of magnetic mixed hemimicelles solid phase extraction and dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene as a sorbent. The magnetic graphene was synthesized by a simple coprecipitation method and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The retained analyte was eluted using a 100 μL mixture of methanol/acetic acid (9:1) and converted into fluoxetine-β-cyclodextrin inclusion complex. The analyte was then quantified by fiber optic linear array spectrophotometry as well as mode-mismatched thermal lens spectroscopy (TLS). The factors affecting the separation, preconcentration and determination of fluoxetine were investigated and optimized. With a 50 mL sample and under optimized conditions using the spectrophotometry technique, the method exhibited a linear dynamic range of 0.4–60.0 μg L −1 , a detection limit of 0.21 μg L −1 , an enrichment factor of 167, and a relative standard deviation of 2.1% and 3.8% (n = 6) at 60 μg L −1 level of fluoxetine for intra- and inter-day analyses, respectively. However, with thermal lens spectrometry and a sample volume of 10 mL, the method exhibited a linear dynamic range of 0.05–300 μg L −1 , a detection limit of 0.016 μg L −1 and a relative standard deviation of 3.8% and 5.6% (n = 6) at 60 μg L −1 level of fluoxetine for intra- and inter-day analyses, respectively. The method was successfully applied to determine fluoxetine in pharmaceutical formulation, human urine and environmental water samples. - Graphical abstract: A novel, sensitive, fast, simple and convenient mixed hemimicelles dispersive micro solid

  19. A new concept of hollow fiber liquid-liquid-liquid microextraction compatible with gas chromatography based on two immiscible organic solvents.

    Science.gov (United States)

    Ghambarian, Mahnaz; Yamini, Yadollah; Esrafili, Ali; Yazdanfar, Najmeh; Moradi, Morteza

    2010-09-03

    A new concept of liquid-liquid-liquid microextraction (LLLME) was introduced based on applying two immiscible organic solvents in lumen and wall pores of hollow fiber (HF). With this methodology, analytes of interest can be extracted from aqueous sample, into a thin layer of organic solvent (dodecane) sustained in the pores of a porous hollow fiber, and further into a muL volume of organic acceptor (acetonitrile or methanol) located inside the lumen of the hollow fiber. Some chlorophenols (CPs) were selected as model compounds for developing and evaluating of the method performance. The analysis was performed by gas chromatography-electron capture detection (GC-ECD) without derivatization. The factors affecting the HF-LLLME of target compounds were investigated and the optimal extraction conditions were established. Under the optimum conditions, preconcentration factors in a range of 208-895 were obtained. The performance of the proposed method was studied in terms of linear dynamic ranges (LDRs from 0.02 to 100ngmL(-1)), linearity (R(2)> or =0.995), precision (RSD %HF-LLLME also served as a technique for sample clean-up. 2010 Elsevier B.V. All rights reserved.

  20. Multiplexed Colorimetric Solid-Phase Extraction

    Science.gov (United States)

    Gazda, Daniel B.; Fritz, James S.; Porter, Marc D.

    2009-01-01

    Multiplexed colorimetric solid-phase extraction (MC-SPE) is an extension of colorimetric solid-phase extraction (C-SPE) an analytical platform that combines colorimetric reagents, solid phase extraction, and diffuse reflectance spectroscopy to quantify trace analytes in water. In CSPE, analytes are extracted and complexed on the surface of an extraction membrane impregnated with a colorimetric reagent. The analytes are then quantified directly on the membrane surface using a handheld diffuse reflectance spectrophotometer. Importantly, the use of solid-phase extraction membranes as the matrix for impregnation of the colorimetric reagents creates a concentration factor that enables the detection of low concentrations of analytes in small sample volumes. In extending C-SPE to a multiplexed format, a filter holder that incorporates discrete analysis channels and a jig that facilitates the concurrent operation of multiple sample syringes have been designed, enabling the simultaneous determination of multiple analytes. Separate, single analyte membranes, placed in a readout cartridge create unique, analyte-specific addresses at the exit of each channel. Following sample exposure, the diffuse reflectance spectrum of each address is collected serially and the Kubelka-Munk function is used to quantify each water quality parameter via calibration curves. In a demonstration, MC-SPE was used to measure the pH of a sample and quantitate Ag(I) and Ni(II).

  1. Solid phase tube radioimmunoassay for digoxin detection

    International Nuclear Information System (INIS)

    Stellner, K.; Glatz, C.; Linke, R.

    1975-01-01

    A solid phase radioimmunoassay with 125 I is described for cardiac patients. The test for the digoxin determination and the poisoning due to cardiac glycosides can be measured very accurately and carried out easily. In addition, the test determination can be automatically performed in connection with other tests. (GSE/LH) [de

  2. Automated polyvinylidene difluoride hollow fiber liquid-phase microextraction of flunitrazepam in plasma and urine samples for gas chromatography/tandem mass spectrometry.

    Science.gov (United States)

    Cui, Shufen; Tan, Shuo; Ouyang, Gangfeng; Pawliszyn, Janusz

    2009-03-20

    A new polyvinylidene difluoride (PVDF) hollow fiber (200 microm wall thickness, 1.2mm internal diameter, 0.2 microm pore size) was compared with two other polypropylene (PP) hollow fibers (200, 300 microm wall thickness, 1.2mm internal diameter, 0.2 microm pore size) in the automated hollow fiber liquid-phase microextraction (HF-LPME) of flunitrazepam (FLNZ) in biological samples. With higher porosity and better solvent compatibility, the PVDF hollow fiber showed advantages with faster extraction efficiency and operational accuracy. Parameters of the CTC autosampler program for HF-LPME in plasma and urine samples were carefully investigated to ensure accuracy and reproducibility. Several parameters influencing the efficiency of HF-LPME of FLNZ in plasma and urine samples were optimized, including type of porous hollow fiber, organic solvent, agitation rate, extraction time, salt concentration, organic modifier, and pH. Under optimal conditions, extraction recoveries of FLNZ in plasma and urine samples were 6.5% and 83.5%, respectively, corresponding to the enrichment factor of 13 in plasma matrix and 167 in urine matrix. Excellent sample clean-up was observed and good linearities (r(2)=0.9979 for plasma sample and 0.9995 for urine sample) were obtained in the range of 0.1-1000 ng/mL (plasma sample) and 0.01-1000 ng/mL (urine sample). The limits of detection (S/N=3) were 0.025 ng/mL in plasma matrix and 0.001 ng/mL in urine matrix by gas chromatography/mass spectrometry/mass spectrometry.

  3. The investigation of exposure to benzene, toluene, ethylbenzene and xylene (BTEX with Solid Phase Microextr action Method in gas station in Yazd province

    Directory of Open Access Journals (Sweden)

    Mohammad Hossein Mosaddegh Mehrjerdi

    2014-01-01

    Full Text Available Abstract Background: Benzene, toluene, ethylbenzene and xylene (BTEX are volatile organic compounds which their physical and chemical characteristics are similar. Evaporation of BTEX from gasoline in petrol station into the air causes gasoline station attendants expose to them. A new extraction method of volatile organic compounds is solid phase microextraction (SPME. The aim of this study is to optimize extraction conditions of BTEX from air samples and then determination of gasoline station air contamination with BTEX in Yazd. Material and Methods: In this study air samples were collected using Tedlar bags and then extracted and analyzed with SPME fiber and gas chromatography equipped with a flame ionization detector. Results: Our results indicate that PDMS/CAR has the best peak area in comparison with two other fibers The Optimized extraction and desorption times are estimated 3 and 1 minutes, respectively Mean concentration of benzene, toluene, ethyl benzene and xylene in gas station’s air were 1932±807, 667±405, 148±89, 340±216 µg/m3 respectively. Conclusion: Benzene mean concentration is above threshold limit value (0.5PPM. Whereas, toluene, ethylbenzene and xylene mean concentration are lower than threshold limit values.

  4. Separation and determination of seleno amino acids using gas chromatography hyphenated with inductively coupled plasma mass spectrometry after hollow fiber liquid phase microextraction.

    Science.gov (United States)

    Duan, Jiankun; Hu, Bin

    2009-05-01

    A new derivatization-extraction method for preconcentration of seleno amino acids using hollow fiber liquid phase microextraction (HF-LPME) was developed for the separation and determination of seleno amino acids in biological samples by gas chromatography-inductively coupled plasma mass spectrometry (GC-ICP-MS). Derivatization was performed with ethyl chloroformate (ECF) to improve the volatility of seleno amino acids. Parameters influencing microextraction, including extraction solvent, pH of sample solution, extraction time, stirring speed, and inorganic salt concentration have been investigated. Under the optimal conditions, the limits of detection (LODs) obtained for Se-methyl-selenocysteine (SeMeCys), selenomethionine (SeMet), and selenoethionine (SeEth) were 23, 15, and 11 ng Se l(-1), respectively. The relative standard deviations (RSDs) were 14.6%, 16.4%, and 19.4% for SeMeCys, SeMet, and SeEth (c = 1.0 ng ml(-1), n = 7), respectively, and the RSDs for SeMeCys, SeMet could be improved obviously if SeEth was utilized as the internal standard. The proposed method was applied for the determination of seleno amino acids in extracts of garlic, cabbage, and mushroom samples, and the recoveries for the spiked samples were in the range of 96.8-108% and 93.4-115% with and without the use of SeEth as internal standard. The developed method was also applied to the analysis of SeMet in a certified reference material of SELM-1 yeast and the determined value is in good agreement with the certified value. 2008 John Wiley & Sons, Ltd.

  5. Hollow fiber liquid phase microextraction combined with electrothermal atomic absorption spectrometry for the speciation of arsenic (III) and arsenic (V) in fresh waters and human hair extracts

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Hongmei [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Hu Bin [Department of Chemistry, Wuhan University, Wuhan 430072 (China)], E-mail: binhu@whu.edu.cn; Chen Beibei; Xia Linbo [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

    2009-02-16

    A new method of hollow fiber liquid phase microextraction (HF-LPME) using ammonium pyrrolidine dithiocarbamate (APDC) as extractant combined with electrothermal atomic absorption spectrometry (ETAAS) using Pd as permanent modifier has been described for the speciation of As(III) and As(V). In a pH range of 3.0-4.0, the complex of As(III)-APDC complex can be extracted using toluene as the extraction solvent leaving As(V) in the aqueous layer. The post extraction organic phase was directly injected into ETAAS for the determination of As(III). To determine total arsenic in the samples, first As(V) was reduced to As(III) by L-cysteine, and then a microextraction method was performed prior to the determination of total arsenic. As(V) assay was based on subtracting As(III) form the total arsenic. All parameters, such as pH of solution, type of organic solvent, the amount of APDC, stirring rate and extraction time, affecting the separation of As(III) from As(V) and the extraction efficiency of As(III) were investigated, and the optimized extraction conditions were established. Under optimized conditions, a detection limit of 0.12 ng mL{sup -1} with enrichment factor of 78 was achieved. The relative standard deviation (R.S.D.) of the method for five replicate determinations of 5 ng mL{sup -1} As(III) was 8%. The developed method was applied to the speciation of As(III) and As(V) in fresh water and human hair extracts, and the recoveries for the spiked samples are 86-109%. In order to validate the developed method, three certified reference materials such as GBW07601 human hair, BW3209 and BW3210 environmental water were analyzed, and the results obtained were in good agreement with the certified values provided.

  6. High-throughput determination of nicotine in plasma by ultrasonication enhanced hollow fiber liquid-phase microextraction prior to gas chromatography.

    Science.gov (United States)

    Liu, Xiaotian; Liang, Shumei; Pan, Jie; Guo, Yugao; Luo, Huiru; Zhao, Qingsong; Guan, Shan

    2014-07-01

    In high-throughput ultrasonication enhanced hollow-fiber liquid-phase microextraction (H-U-HF-LPME), ultrasonication was introduced into HF-LPME to enhance the mass transfer rate of the analytes in the two immiscible liquid phases, which resulted in a very short time for extraction equilibrium and a high-throughput analysis. Several parameters were investigated and optimized (such as extraction solvent, temperature of sample, frequency and intensity of ultrasonication, volume of extractant, extraction time, ionic strength of the sample and sample concentration). Based on the results of this study, nicotine was first extracted from a 1.5 mL sample solution under the optimum conditions (ultrasonic power of 50 W with a frequency of 60 kHz, extraction time of 10 min, sodium chloride concentration of 5 mol/L and temperature of 37°C). Next, 0.5 µL of acceptor solution inside the hollow fiber was automatically injected into a gas chromatograph with a flame ionization detector. The results of this study illustrated that the limit of detection, relative standard deviation (n = 6), relative recovery and enrichment factor of nicotine were 0.06 µg/L, 3%, 99.8% and 16.6, respectively. Finally, H-U-HF-LPME was successfully applied for the determination of nicotine in plasma. © The Author [2013]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  7. Combination of liquid-phase hollow fiber membrane microextraction with gas chromatography-negative chemical ionization mass spectrometry for the determination of dichlorophenol isomers in water and urine.

    Science.gov (United States)

    Lai, Bin-Wei; Liu, Bo-Min; Malik, Pradip K; Wu, Hui-Fen

    2006-08-18

    A method for the determination of trace amount of dichlorophenol isomers in urine samples using the combination of liquid-phase hollow fiber microextraction (LPME-HF) with gas chromatography-negative chemical ionization mass spectrometry (GC-NCI-MS) has been demonstrated. The method has been optimized with respect to several parameters including the effects of negative chemical ionization (NCI) reagent pressure, the hollow fiber length, extraction time, stirring rate, sample pH and salt concentration for the determination of dichlorophenol isomers in water. The correlation coefficient (r2) of the calibration curves for 2,5-dichlorophenol, 2,3-dichlorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol and 3,4-dichlorophenol were 0.988, 0.981, 0.985, 0.971 and 0.994, respectively. The average recovery rates for 2,5-dichlorophenol, 2,3-dichlorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol and 3,4-dichlorophenol were 0.97, 0.93, 0.96, 0.95 and 0.95, respectively (n=3 for each dichlorophenol) indicate that the methodology is feasible for the determination of trace amounts of dichlorophenol isomers in water and urine samples. Limits of detection (LOD) have been found to be in the range of 5-20 ng/ml. In addition, differentiation of the five dichlorophenol isomers is an easy task using the current approach of combining LPME-HF with NCI-GC-MS technique since they exhibit different NCI spectra.

  8. Hollow fiber based liquid phase microextraction for the determination of organochlorine pesticides in ecological textiles by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Cai, Jin'an; Chen, Guosheng; Qiu, Junlang; Jiang, Ruifen; Zeng, Feng; Zhu, Fang; Ouyang, Gangfeng

    2016-01-01

    In this study, the hollow fiber-liquid phase microextraction (HF-LPME) coupled gas chromatograph/mass spectrometry (GC/MS) was firstly developed to determine 10 organochlorine pesticides (OCPs) in ecological textiles. The present method can offer high separation efficiencies with minimal sample and solvent consumption. The extraction conditions were optimized, including the types of hollow fiber and organic solvent, the extraction time, the stirring and the salinity. Under the optimized conditions, the linear ranges of OCPs in cotton, terylene and fur samples were 5-1000 ng/g, 10-1000 ng/g and 10-800 ng/g, respectively, and the detection limit of the three samples were 0.07-2.30 ng/g, 0.89-1.66 ng/g and 0.06-1.04 ng/g, respectively. The optimized method was then successfully used to determine the OCPs in 3 kinds of spiked real samples, including cotton, terylene and fur. The good recoveries and RSDs of the quantification in real textile samples were obtained and the results were confirmed by the traditional liquid extraction method (GB/T 18412-2006). This study proved that the HF-LPME method, which was simple, low-cost and virtually solvent-free, was reliable for the qualitative and quantitative analysis of the harmful OCP residues in ecological textiles. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Solid phase synthesis of purines from pyrimidines.

    Science.gov (United States)

    Di Lucrezia, R; Gilbert, I H; Floyd, C D

    2000-01-01

    In this paper the solid phase synthesis of various substituted purines is described starting from 4,6-dichloro-5-nitropyrimidine. The 4,6-dichloro-5-nitropyrimidine was coupled to Rink amide resin followed by displacement of the second chloride by an amino compound. Reduction of the nitro compound proved to be problematic but was achieved using lithium aluminum hydride/aluminum trichloride. The diamines (13) were then elaborated to purines by three different routes.

  10. DNA Extraction: Organic and Solid-Phase.

    Science.gov (United States)

    Altayari, Wafa

    2016-01-01

    DNA extraction remains a critical step in DNA profiling of biological material recovered from scenes of crime. In the forensic community several methods have gained popularity, including Chelex(®), organic extraction, and solid-phase extraction. While some laboratories streamlined their processes and only use one method we have retained several methods and continue to use these for different sample types. In this chapter we present three methods that have been used for several years in our laboratory.

  11. An improved hollow fiber solvent-stir bar microextraction for the preconcentration of anabolic steroids in biological matrix with determination by gas chromatography-mass spectrometry.

    Science.gov (United States)

    Liu, Wei; Zhang, Lan; Fan, Liangbiao; Lin, Zian; Cai, Yimin; Wei, Zhenyi; Chen, Guonan

    2012-04-13

    In this paper, a convenient and self-assembled hollow fiber solvent-stir bar microextraction (HF-SSBME) device was developed, which could stir by itself. In the extraction process, the proposed device made the solvent "bar" not floating at the sample solution and exposing to air while organic solvents outside hollow fiber always wrapped with donor phase solvent, which reduced the vaporization of organic solvents. This design could improve the precisions and recoveries of experiments. For evaluating the device, seven anabolic steroids (prasterone, 5α-androstane-3α, 17β-diol, methandriol, 19-norandrostenediol, androstenediol, methyltestosterone and methandienone) were used as model analytes and extraction conditions such as type and volume of organic solvents, agitation speed, extraction time, extraction temperature and salt addition were studied in detail. Under the optimum conditions (15 μL toluene, 40 °C, stirring at 750 rpm for 30 min with 1.5 g sodium chloride addition in 20.0 mL donor phase), the linear ranges of anabolic steroids were 0.25-200 ng mL(-1) with gas chromatography-mass spectrometry. The limits of detection were lower than 0.10 ng mL(-1). The recoveries and precisions in spiked urine and hair samples were between 73.97-93.56% and 2.18-4.47% (n=5). HF-SSBME method combined the intrinsical merits of hollow fiber with the superiority of the proposed self-stirring device which can be developed to two-phase, three-phase and in situ derivatization modes with wide prospect of application. Besides, the pedestal of this proposed device can be converted to fix stir bar in stir bar sorptive extraction (SBSE) method. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Solid-phase equilibria on Pluto's surface

    Science.gov (United States)

    Tan, Sugata P.; Kargel, Jeffrey S.

    2018-03-01

    Pluto's surface is covered by volatile ices that are in equilibrium with the atmosphere. Multicomponent phase equilibria may be calculated using a thermodynamic equation of state and, without additional assumptions, result in methane-rich and nitrogen-rich solid phases. The former is formed at temperature range between the atmospheric pressure-dependent sublimation and condensation points, while the latter is formed at temperatures lower than the sublimation point. The results, calculated for the observed 11 μbar atmospheric pressure and composition, are consistent with recent work derived from observations by New Horizons.

  13. Silica Modified with Polyaniline as a Potential Sorbent for Matrix Solid Phase Dispersion (MSPD and Dispersive Solid Phase Extraction (d-SPE of Plant Samples

    Directory of Open Access Journals (Sweden)

    Ireneusz Sowa

    2018-03-01

    Full Text Available Polyaniline (PANI is one of the best known conductive polymers with multiple applications. Recently, it was also used in separation techniques, mostly as a component of composites for solid-phase microextraction (SPME. In the present paper, sorbent obtained by in situ polymerization of aniline directly on silica gel particles (Si-PANI was used for dispersive solid phase extraction (d-SPE and matrix solid–phase extraction (MSPD. The efficiency of both techniques was evaluated with the use of high performance liquid chromatography with diode array detection (HPLC-DAD quantitative analysis. The quality of the sorbent was verified by Raman spectroscopy and microscopy combined with automated procedure using computer image analysis. For extraction experiments, triterpenes were chosen as model compounds. The optimal conditions were as follows: protonated Si-PANI impregnated with water, 160/1 sorbent/analyte ratio, 3 min of extraction time, 4 min of desorption time and methanolic solution of ammonia for elution of analytes. The proposed procedure was successfully used for pretreatment of plant samples.

  14. Methods of liquid phase microextraction for the determination of cadmium in environmental samples.

    Science.gov (United States)

    Pires Santos, Analú; das Graças Andrade Korn, Maria; Azevedo Lemos, Valfredo

    2017-08-09

    Liquid phase microextraction (LPME) has been widely used in extraction and preconcentration systems as an excellent alternative to conventional liquid phase extraction. In this work, a critical review is presented on liquid phase microextraction techniques used in the determination of cadmium in environmental samples. LPME techniques are classified into three main groups: single-drop liquid phase microextraction (SDME), hollow fiber liquid phase microextraction (HF-LPME), and dispersive liquid-liquid microextraction (DLLME). Methods involving these liquid phase microextraction techniques are described, addressing advantages and disadvantages, samples, figures of merit, and trends.

  15. Determination of phthalic acid esters in water samples by hollow fiber liquid-phase microextraction prior to gas chromatography tandem mass spectrometry.

    Science.gov (United States)

    González-Sálamo, Javier; González-Curbelo, Miguel Ángel; Socas-Rodríguez, Bárbara; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Ángel

    2018-06-01

    A new hollow fiber liquid-phase microextraction (HF-LPME) method has been developed for the extraction of a group of phthalic acid esters (PAEs) of interest from different water samples prior to gas chromatography tandem mass spectrometry analysis. HF-LPME was carried out using 1-octanol as extraction solvent followed by a back extraction step with cyclohexane. The different parameters that affect HF-LPME such as sample pH, ionic strength, extraction time, stirring rate, extraction temperature and back extraction conditions were investigated. The optimized conditions involved the extraction of 10 mL of sample without pH adjustment or addition of salt during 75 min under a stirring of 850 rpm at 60 °C and subsequent desorption with 200 μL of cyclohexane for 10 min in an ultrasonic bath. The method was validated in terms of calibration and recovery studies using dibutyl phthalate-d 4 as internal standard. The developed procedure gave satisfactory recovery (74-120%) and relative standard deviation values (<20%) for the studied PAEs in mineral, tap, pond and waste water samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Determination of trace benzene derivatives in aqueous samples by ultrasonic enhanced hollow fiber liquid-phase microextraction prior to gas chromatography.

    Science.gov (United States)

    Wang, Lei; Guo, Yugao; Liang, Shumei; Yang, Qingqing; Wei, Junfu

    2011-10-01

    A new method was developed for the determination of trace compounds in water samples using ultrasonic-enhanced hollow fiber liquid-phase microextraction (U-HF-LPME). The ultrasonic radiation, which produces mechanical vibration and ultrasonic cavitation, could be used for accelerating the diffusion mass transfer process. Thus, ultrasonic was introduced into the HF-LPME procedure to enhance the mass-transfer rate during the aqueous and extraction solvent phases. Experimental parameters such as the extraction solvent, the extraction time, the ultrasonic frequency and power, the extractant volume, and ionic strength of the sample were assessed and optimized. Under optimal conditions, HF-LPME was achieved within 10 min. The high enrichment factor in the range of 120-666 and a good relative recovery in the range of 97-103% were evaluated with the relative standard deviations (RSDs, n = 5) of 0.3-7.0%. The limit of detection was in the range of 0.8-3.0 µg/L. The method was applied to the analysis of groundwater, lake water, and seawater. The results showed that the method can determine trace benzene derivatives in real samples with RSD values of 1.1-4.2%. The results demonstrated that U-HF- LPME is a rapid, accurate, and effective sample preparation method, and could be successfully applied for the determination of trace compounds in analytical chemistry.

  17. Miniaturized hollow fiber assisted liquid-phase microextraction with in situ derivatization and gas chromatography-mass spectrometry for analysis of bisphenol A in human urine sample.

    Science.gov (United States)

    Kawaguchi, Migaku; Ito, Rie; Okanouchi, Noriya; Saito, Koichi; Nakazawa, Hiroyuki

    2008-07-01

    A new method that involves miniaturized hollow fiber assisted liquid-phase microextraction (HF-LPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS) is described for the determination of trace amounts of bisphenol A (BPA) in human urine samples. The detection limit and the quantification limit of BPA in human urine sample are 0.02 and 0.1 ng ml(-1) (ppb), respectively. The calibration curve for BPA is linear with a correlation coefficient of >0.999 in the range of 0.1-50 ng ml(-1). The average recoveries of BPA in human urine samples spiked with 1 and 5 ng ml(-1) BPA are 101.0 (R.S.D.: 6.7%) and 98.8 (R.S.D.: 1.8%), respectively, with correction using the added surrogate standard, bisphenol A-(13)C12. This simple, accurate, sensitive and selective analytical method can be applicable to the determination of trace amounts of BPA in human urine samples.

  18. Miniaturized hollow fiber assisted liquid-phase microextraction and gas chromatography-mass spectrometry for determination of benzophenone and derivates in human urine sample.

    Science.gov (United States)

    Kawaguchi, Migaku; Ito, Rie; Honda, Hidehiro; Koganei, Youji; Okanouchi, Noriya; Saito, Koichi; Seto, Yasuo; Nakazawa, Hiroyuki

    2009-01-15

    The determination of benzophenones (BPs) in human urine sample by miniaturized hollow fiber assisted liquid-phase microextraction (HF-LPME) and gas chromatography-mass spectrometry (GC-MS) is described. As analytes, BP, its metabolites benzhydrol (BP-OH) and 2-hydroxybenzophenone (2OH-BP), and its derivatives 2-hydroxy-4-methoxybenzophenone (BP-3) and 2-hydroxy-4-methoxy-4'-methylbenzophenone (BP-10) were selected. The detection limit and the quantification limit of BPs in human urine sample are 5-10 and 20-50 pg mL(-1), respectively. The calibration curve for BPs is linear with correlation coefficient higher than 0.99 in the range of 0.02-10 or 0.05-10 ng mL(-1). The average recoveries of BPs in human urine samples spiked with 0.5 and 5 ng mL(-1) BPs are 89.8-100.2% (RSD: 2.5-9.3%) and 89.3-99.9% (RSD: 2.9-3.7%), respectively. Ten human urine samples were analyzed using the present method. BP-OH and BP-3 were detected in all the samples within the range of 0.24-5.91 and 0.43-5.17 ng mL(-1), respectively. This simple, sensitive, and selective analytical method was successfully applied to the determination of trace amounts of BPs in human urine samples.

  19. Hollow-fiber-supported liquid phase microextraction with in situ derivatization and gas chromatography-mass spectrometry for determination of chlorophenols in human urine samples.

    Science.gov (United States)

    Ito, Rie; Kawaguchi, Migaku; Honda, Hidehiro; Koganei, Youji; Okanouchi, Noriya; Sakui, Norihiro; Saito, Koichi; Nakazawa, Hiroyuki

    2008-09-01

    A simple and highly sensitive method that involves hollow-fiber-supported liquid phase microextraction (HF-LPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS) was developed for the determination of chlorophenols (CPs) such as 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TrCP), 2,3,4,6-tetrachlorophenol (TeCP) and pentachlorophenol (PCP) in human urine samples. Human urine samples were enzymatically de-conjugated with beta-glucuronidase and sulfatase. After de-conjugation, HF-LPME with in situ derivatization was performed. After extraction, 2 microl of extract was carefully withdrawn into a syringe and injected into the GC-MS system. The limits of detection (S/N=3) and quantification (S/N>10) of CPs in the human urine samples are 0.1-0.2 ng ml(-1) and 0.5-1 ng ml(-1), respectively. The calibration curve for CPs is linear with a correlation coefficient of >0.99 in the range of 0.5-500 ng ml(-1) for DCP and TrCP, and of 1-500 ng ml(-1) for TeCP and PCP, respectively. The average recoveries of CPs (n=6) in human urine samples are 81.0-104.0% (R.S.D.: 1.9-6.6%) with correction using added surrogate standards. When the proposed method was applied to human urine samples, CPs were detected at sub-ng ml(-1) level.

  20. Comparative study of hollow-fiber liquid-phase micro-extraction and an aqueous two-phase system for determination of phytohormones in soil.

    Science.gov (United States)

    Dong, She Ying; Yang, Zhen; Zhang, Penghui H; Hu, Qing; Huang, Ting Lin

    2012-06-01

    Two methods, hollow-fiber liquid-phase micro-extraction (HF-LPME) and an aqueous two-phase system (ATPS), have been systematically optimized and compared for extraction and determination of phytohormones in soil by high-performance liquid chromatography (HPLC). The effects on extraction of conditions including solvent type and volume, extraction time, temperature, and amount of salt were evaluated. It was shown that ATPS was superior to HF-LPME for determination of paclobutrazol and uniconazole under the optimum conditions. The limits of detection (LODs) of ATPS were 0.002 μg g(-1) for uniconazole and 0.01 μg g(-1) for paclobutrazol, whereas LODs of HF-LPME were 0.005 μg g(-1) and 0.03 μg g(-1), respectively. Relative standard deviations (RSDs, n=5) and recovery were in the range 1.7-5.3 % and 86-102 %, respectively, for ATPS and 6.7-7.9 % and 40-60 % for HF-LPME. In addition, the advantages of ATPS were shorter extraction time, suitable for simultaneous pretreatment of batches of samples, and higher extraction capacity. ATPS was therefore applied to the determination of paclobutrazol and uniconazole in real soil samples. Uniconazole was detected in all the samples analyzed whereas paclobutrazol was not found.

  1. Estimation of the toxicity of sulfadiazine to Daphnia magna using negligible depletion hollow-fiber liquid-phase microextraction independent of ambient pH

    Science.gov (United States)

    Liu, Kailin; Xu, Shiji; Zhang, Minghuan; Kou, Yahong; Zhou, Xiaomao; Luo, Kun; Hu, Lifeng; Liu, Xiangying; Liu, Min; Bai, Lianyang

    2016-12-01

    The toxicity of ionizable organic compounds to organisms depends on the pH, which therefore affects risk assessments of these compounds. However, there is not a direct chemical method to predict the toxicity of ionizable organic compounds. To determine whether hollow-fiber liquid-phase microextraction (HF-LPME) is applicable for this purpose, a three-phase HF-LPME was used to measure sulfadiazine and estimate its toxicity to Daphnia magna in solutions of different pH. The result indicated that the sulfadiazine concentrations measured by HF-LPME decreased with increasing pH, which is consistent with the decreased toxicity. The concentration immobilize 50% of the daphnids (EC50) in 48 h calculated from nominal concentrations increased from 11.93 to 273.5 mg L-1 as the pH increased from 6.0 to 8.5, and the coefficient of variation (CV) of the EC50 values reached 104.6%. When calculated from the concentrations measured by HF-LPME (pH 12 acceptor phase), the EC50 ranged from 223.4 to 394.6 mg L-1, and the CV decreased to 27.60%, suggesting that the concentrations measured by HF-LPME can be used to estimate the toxicity of sulfadiazine irrespective of the solution pH.

  2. Evaluation of a completely automated cold fiber device using compounds with varying volatility and polarity.

    Science.gov (United States)

    Jiang, Ruifen; Carasek, Eduardo; Risticevic, Sanja; Cudjoe, Erasmus; Warren, Jamie; Pawliszyn, Janusz

    2012-09-12

    A fully automated cold fiber solid phase microextraction device has been developed by coupling to a GERSTEL multipurpose (MPS 2) autosampler and applied to the analysis of volatiles and semi-volatiles in aqueous and solid matrices. The proposed device was thoroughly evaluated for its extraction performance, robustness, reproducibility and reliability by gas chromatograph/mass spectrometer (GC/MS). With the use of a septumless head injector, the entire automated setup was capable of analyzing over 200 samples without any GC injector leakages. Evaluation of the automated cold fiber device was carried out using a group of compounds characterized by different volatilities and polarities. Extraction efficiency as well as analytical figures of merit was compared to commercial solid phase microextraction fibers. The automated cold fiber device showed significantly improved extraction efficiency compared to the commercial polydimethylsiloxane (PDMS) and cold fiber without cooling for the analysis of aqueous standard samples due to the low temperature of the coating. Comparing results obtained from cold fiber and commercial divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber temperature profile demonstrated that the temperature gap between the sample matrix and the coating improved the distribution coefficient and therefore the extraction amount. The linear dynamic range of the cold fiber device was 0.5 ng mL(-1) to 100 ng mL(-1) with a linear regression coefficient ≥0.9963 for all compounds. The limit of detection for all analytes ranged from 1.0 ng mL(-1) to 9.4 ng mL(-1). The newly automated cold fiber device presents a platform for headspace analysis of volatiles and semi-volatiles for large number of samples with improved throughput and sensitivity. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Hollow-fiber liquid-phase microextraction for the determination of pesticides and metabolites in soils and water samples using HPLC and fluorescence detection.

    Science.gov (United States)

    Asensio-Ramos, María; Hernández-Borges, Javier; González-Hernández, Guillermo; Rodríguez-Delgado, Miguel Ángel

    2012-07-01

    A new and simple method has been developed for the determination of a group of four benzimidazole pesticides (carbendazim/benomyl, thiabendazole, and fuberidazole), a carbamate (carbaryl), and an organophosphate (triazophos), together with two of their main metabolites (2-aminobenzimidazole, metabolite of carbendazim/benomyl, and 1-naphthol, metabolite of carbaryl) in soils. First, an ultrasound-assisted extraction (UAE) was performed, followed by evaporation and reconstitution in water. Then, extraction and preconcentration of the analytes was accomplished by two-phase hollow-fiber liquid-phase microextraction (HF-LPME) using 1-octanol as extraction solvent. Parameters that affect the extraction efficiency in HF-LPME technique (organic solvent, pH of the sample, extraction time, stirring speed, temperature, and ionic strength) were deeply investigated. Optimum HF-LPME conditions involved the use of a 2.0 cm polypropylene fiber filled with 1-octanol to extract 10 mL of an aqueous soil extract at pH 9.0 containing 20% (v/v) of NaCl for 30 min at 1440 rpm. Separation and quantification was achieved by HPLC with fluorescence detection (FD). The proposed optimum UAE-HF-LPME-HPLC-FD methodology provided good calibration, precision, and accuracy results for two soils of different physicochemical properties. LODs were in the range 0.001-6.94 ng/g (S/N = 3). With the aim of extending the validation, the HF-LPME method was also applied to different types of waters (Milli-Q, mineral and run-off), obtaining LODs in the range 0.0002-0.57 μg/L. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Determination of melamine in soil samples using surfactant-enhanced hollow fiber liquid phase microextraction followed by HPLC–UV using experimental design

    Directory of Open Access Journals (Sweden)

    Ali Sarafraz Yazdi

    2015-11-01

    Full Text Available Surfactant-enhanced hollow fiber liquid phase (SE-HF-LPME microextraction was applied for the extraction of melamine in conjunction with high performance liquid chromatography with UV detection (HPLC–UV. Sodium dodecyl sulfate (SDS was added firstly to the sample solution at pH 1.9 to form hydrophobic ion-pair with protonated melamine. Then the protonated melamine–dodecyl sulfate ion-pair (Mel–DS was extracted from aqueous phase into organic phase immobilized in the pores and lumen of the hollow fiber. After extraction, the analyte-enriched 1-octanol was withdrawn into the syringe and injected into the HPLC. Preliminary, one variable at a time method was applied to select the type of extraction solvent. Then, in screening step, the other variables that may affect the extraction efficiency of the analyte were studied using a fractional factorial design. In the next step, a central composite design was applied for optimization of the significant factors having positive effects on extraction efficiency. The optimum operational conditions included: sample volume, 5 mL; surfactant concentration, 1.5 mM; pH 1.9; stirring rate, 1500 rpm and extraction time, 60 min. Using the optimum conditions, the method was analytically evaluated. The detection limit, relative standard deviation and linear range were 0.005 μg mL−1, 4.0% (3 μg mL−1, n = 5 and 0.01–8 μg mL−1, respectively. The performance of the procedure in extraction of melamine from the soil samples was good according to its relative recoveries in different spiking levels (95–109%.

  5. Extraction and preconcentration of tylosin from milk samples through functionalized TiO₂ nanoparticles reinforced with a hollow fiber membrane as a novel solid/liquid-phase microextraction technique.

    Science.gov (United States)

    Sehati, Negar; Dalali, Nasser; Soltanpour, Shahla; Dorraji, Mir Saeed Seyed

    2014-08-01

    The aim of this study was to introduce a novel, simple, and highly sensitive preparation method for determination of tylosin in different milk samples. In the so-called functionalized TiO2 hollow fiber solid/liquid-phase microextraction method, the acceptor phase is functionalized TiO2 nanoparticles that are dispersed in the organic solvent and held in the pores and lumen of a porous polypropylene hollow fiber membrane. An effective functionalization of TiO2 nanoparticles has been done in the presence of aqueous H2 O2 and a mild acidic ambient under UV irradiation. This novel extraction method showed excellent extraction efficiency and a high enrichment factor (540.2) in comparison with conventional hollow fiber liquid-phase microextraction. All the experiments were monitored at λmax = 284 nm using a simple double beam UV-visible spectrophotometer. A Taguchi orthogonal array experimental design with an OA16 (4(5) ) matrix was employed to optimize the factors affecting the efficiency of hollow fiber solid/liquid-phase microextraction such as pH, stirring rate, salt addition, extraction time, and the volume of donor phase. This developed method was successfully applied for the separation and determination of tylosin in milk samples with a linear concentration range of 0.51-7000 μg/L (r(2) = 0.991) and 0.21 μg/L as the limit of detection. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Graphene-Based Materials as Solid Phase Extraction Sorbent for Trace Metal Ions, Organic Compounds, and Biological Sample Preparation.

    Science.gov (United States)

    Ibrahim, Wan Aini Wan; Nodeh, Hamid Rashidi; Sanagi, Mohd Marsin

    2016-07-03

    Graphene is a new carbon-based material that is of interest in separation science. Graphene has extraordinary properties including nano size, high surface area, thermal and chemical stability, and excellent adsorption affinity to pollutants. Its adsorption mechanisms are through non-covalent interactions (π-π stacking, electrostatic interactions, and H-bonding) for organic compounds and covalent interactions for metal ions. These properties have led to graphene-based material becoming a desirable adsorbent in a popular sample preparation technique known as solid phase extraction (SPE). Numerous studies have been published on graphene applications in recent years, but few review papers have focused on its applications in analytical chemistry. This article focuses on recent preconcentration of trace elements, organic compounds, and biological species using SPE-based graphene, graphene oxide, and their modified forms. Solid phase microextraction and micro SPE (µSPE) methods based on graphene are discussed.

  7. SOLID-PHASE PEPTIDE SYNTHESIS OF ISOTOCIN WITH AMIDE ...

    African Journals Online (AJOL)

    SOLID-PHASE PEPTIDE SYNTHESIS OF ISOTOCIN WITH AMIDE OF ASPARAGINE PROTECTED WITH 1-TETRALINYL. TRIFLUOROMETHANESULPHONIC ACID (TFMSA) DEPROTECTION, CLEAVAGE AND AIR OXIDATION OF MERCAPTO GROUPS TO DISULPHIDE.

  8. Simultaneous quantification of amphetamines, caffeine and ketamine in urine by hollow fiber liquid phase microextraction combined with gas chromatography-flame ionization detector.

    Science.gov (United States)

    Xiong, Jun; Chen, Jie; He, Man; Hu, Bin

    2010-08-15

    A method of hollow fiber (HF) liquid phase microextraction (LPME) combined with gas chromatography (GC)-flame ionization detection (FID) was developed for the simultaneous quantification of trace amphetamine (AP), methamphetamine (MA), methylenedioxyamphetamine (MDA), methylenedioxymethamphetamine (MDMA), caffeine and ketamine (KT) in drug abuser urine samples. The factors affecting on the extraction of six target analytes by HF-LPME were investigated and optimized, and the subsequent analytical performance evaluation and real sample analysis were performed by the extraction of six target analytes in sample solution containing 30% NaCl (pH 12.5) for 20 min with extraction temperature of 30 degrees C and stirring rate of 1000 rpm. Under such optimal conditions, the limits of detection (LODs, S/N=3) for the six target analytes were ranged from 8 microg/L (AP, KT) to 82 microg/L (MDA), with the enrichment factors (EFs) of 5-227 folds, and the relative standard deviations (RSDs, n=7) were in the range of 6.9-14.1%. The correlation coefficients of the calibration for the six target analytes over the dynamic linear range were higher than 0.9958. The application feasibility of HF-LPME-GC-FID in illegal drug monitoring was demonstrated by analyzing drug abuser urine samples, and the recoveries of target drugs for the spiked sample ranging from 75.2% to 119.3% indicated an excellent anti-interference capability of the developed method. The proposed method is simple, effective, sensitive and low-cost, and provides a much more accurate and sensitive detection platform over the conventional analytical techniques (such as immunological assay) for drug abuse analysis. Copyright 2010 Elsevier B.V. All rights reserved.

  9. Hollow fiber-based liquid-liquid-liquid micro-extraction with osmosis: II. Application to quantification of endogenous gibberellins in rice plant.

    Science.gov (United States)

    Wu, Qian; Wu, Dapeng; Duan, Chunfeng; Shen, Zheng; Guan, Yafeng

    2012-11-23

    The phenomenon and benefits of osmosis in hollow fiber-based liquid-liquid-liquid micro-extraction (HF-LLLME) were theoretically discussed in part I of this study. In this work, HF-LLLME with osmosis was coupled with high performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-triple quadrupole MS/MS) to analyze eight gibberellins (gibberellin A(1), gibberellin A(3), gibberellin A(4), gibberellin A(7), gibberellin A(8), gibberellin A(9), gibberellin A(19) and gibberellin A(20)) in rice plant samples. According to the theory of HF-LLLME with osmosis, single factor experiments, orthogonal design experiments and mass transfer simulation of extraction process were carried out to select the optimal conditions. Cyclohexanol - n-octanol (1:3, v/v) was selected as organic membrane. Donor phase of 12 mL was adjusted to pH 2 and 20% NaCl (w/v) was added. Acceptor phase with an initial volume of 20 μL was the solution of 0.12 mol L(-1) Na(2)CO(3)-NaHCO(3) buffer (pH 9). Temperature was chosen to be 30 °C and extraction time was selected to be 90 min. Under optimized conditions, this method provided good linearity (r, 0.99552-0.99991) and low limits of detection (0.0016-0.061 ng mL(-1)). Finally, this method was applied to the analysis of endogenous gibberellins from plant extract which was obtained with traditional solvent extraction of rice plant tissues, and the relative recoveries were from 62% to 166%. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. [Determination of seven phenoxyacid herbicides in environmental water by high performance liquid chromatography coupled with three phase hollow fiber liquid phase microextraction].

    Science.gov (United States)

    Peng, Xiaojun; Pang, Jinshan; Deng, Aihua

    2011-12-01

    A novel method for the simultaneous determination of seven phenoxyacid herbicides such as dicamba, fluroxypyr, 4-chlorophenoxyacetic acid (4-CPA), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2, 4-dichlorophenoxyacetic acid (2,4-D), 2,4-dichlorophenoxybutyric acid (2,4-DB) and 4-(2-methyl-4-chlorophenoxy) butyric acid (MCPB) in environmental water by three phase hollow fiber liquid phase microextraction (HF-LPME) coupled with high performance liquid chromatography (HPLC) was developed. In order to optimize the experimental conditions, the orthogonal test has been used. The effects of extraction solvent, pH of the donor phase and acceptor phase, extraction time, stirring speed and salt concentration on the detection were investigated. The optimal experimental conditions were as follows: octanol as organic solvent, pH 3 of donor phase, pH 12 of acceptor phase, extraction time of 30 min, stirring speed of 400 r/min. The results showed that the proposed method provided a wide linear range for 7 phenoxyacid herbicides with correlation coefficients of 0.995 3 - 0.998 8. The detection limits ranged from 0.2 to 1.0 microg/L. The enrichment factors were in the range of 76.7 - 121. The recoveries were in the range of 68% - 104% and the relative standard deviations (RSDs) were less than 8.1% for the environmental water samples. The method has the advantages of sensitivity, simplicity, fastness and the use of very small amounts of organic solvent. The method can meet the requirements of the determination of trace phenoxyacid herbicides in the environmental water samples, and the study provided a useful method for the analysis of trace substances in water samples.

  11. Hollow-fiber micro-extraction combined with HPLC for the determination of sitagliptin in urine samples

    Directory of Open Access Journals (Sweden)

    Rezaee Raheme

    2015-01-01

    Full Text Available This study successfully developed a three-phase hollow-fiber liquid phase micro extraction coupled with high performance liquid chromatography for determination of trace levels of an anti-diabetic drug, sitagliptin (STG, in urine samples. Sitagliptin was extracted from 15 mL of the basic sample solution with a pH of 8.5 into an organic extracting solvent (n-octanol impregnated in the pores of a hollow fiber and then back extracted into an acidified aqueous solution in the lumen of the hollow fiber with a pH of 3. After extraction, 20 µL of the acceptor phase was injected into HPLC. In order to obtain high extraction efficiency, the parameters affecting the HF-LPME including pH of the source and receiving phases, type of organic phase, ionic strength, stirring rate, extraction time, the volume ratio of donor phase to acceptor phase and temperature were studied and optimized. Under the optimized conditions, enrichment factors up to 88 were achieved and the relative standard deviation of the method was in the range of 3 % to 6%. The results indicated that HF-LPME method has an excellent clean-up capacity and a high preconcentration factor and can serve as a simple and sensitive method for monitoring the drug in the urine samples.

  12. Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials.

    Science.gov (United States)

    Gao, Jun; Manard, Benjamin T; Castro, Alonso; Montoya, Dennis P; Xu, Ning; Chamberlin, Rebecca M

    2017-05-15

    Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of nine materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. The microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Hollow fiber-based liquid phase microextraction with factorial design optimization and gas chromatography-tandem mass spectrometry for determination of cannabinoids in human hair.

    Science.gov (United States)

    Emídio, Elissandro Soares; de Menezes Prata, Vanessa; de Santana, Fernando José Malagueño; Dórea, Haroldo Silveira

    2010-08-15

    A new method, based on hollow fiber liquid-phase microextraction (HF-LPME) and gas chromatography-tandem mass spectrometry (GC-MSMS), was developed for determination of Delta(9)-tetrahydrocannabinol (THC), cannabidiol (CBD) and cannabinol (CBN) in samples of human hair. Since hair is a solid matrix, the samples were subjected to alkaline digestion using NaOH. The aqueous solutions obtained were extracted using a 6cm polypropylene fiber (600microm i.d., 200microm wall thickness, 0.2microm pore size) for each extraction. A 2(5-1) fractional factorial design for screening, and a central composite design for optimization of significant variables, was applied during development of the extraction method. The variables evaluated were the type of extraction solvent, pH, stirring speed, extraction time, and acceptor phase volume. The optimized conditions for the proposed extraction procedure were 10mg of hair sample; 20microL of butyl acetate; aqueous (pH 14) donor phase containing 6.8% NaCl; 600rpm stirring speed; 20min extraction time. A linear response was obtained in the ranges 1-500pgmg(-1) (CBD and CBN) and 20-500pgmg(-1) (THC), with regression coefficients >0.99. Precision, determined as the relative standard deviation, was 3.3-8.9% (intra-day) and 4.4-13.7% (inter-day). Absolute recoveries varied in the ranges 4.4-4.8% (CBD), 7.6-8.9% (THC) and 7.7-8.2% (CBN). Limits of detection (LOD, S/N=3) and quantification (LOQ, S/N=10) were 0.5-15pgmg(-1) and 1-20pgmg(-1), respectively. The method was successfully used to determine CBD, THC and CBN in hair samples from patients in a drug dependency rehabilitation center. Concentrations varied in the ranges 1-18pgmg(-1) (CBD), 20-232pgmg(-1) (THC) and 9-107pgmg(-1) (CBN), confirming the suitability of the method for monitoring studies. Copyright 2010 Elsevier B.V. All rights reserved.

  14. Study on the Solid Phase Extraction and Spectrophotometric ...

    African Journals Online (AJOL)

    NJD

    By solid phase extraction of the. Hg(II)-ABTR chelate with a C18 disk, an enrichment factor of 50 was achieved. Combining the new reagent with solid phase extraction allowed the development of a highly sensitive, selective and rapid method for the determination of mercury in water and biological samples. 2. Experimental.

  15. Solid-Phase Extraction Combined with High Performance Liquid ...

    African Journals Online (AJOL)

    Methods: Solid-phase extraction method was employed for the extraction of the estrogen from milk and ... Solid phase extraction is recognized as the most common sample pre- treatment technique to enhance the concentration of a target in biological samples. [17]. The aim ... pure water (solvent B) in HPLC experiment. The.