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Sample records for gas chromatography-mass spectrophotometry

  1. ANALYSIS OF TECHNICAL CHLORDANE BY GAS CHROMATOGRAPHY MASS SPECTROMETRY

    EPA Science Inventory

    The composition of technical chlordane has been investigated by combined gas chromatography/mass spectrometry, employing a column commonly used for pesticide residue analysis. Partial or complete structure identification have been assigned to some 45 individual constituents. Many...

  2. Specialized Gas Chromatography--Mass Spectrometry Systems for Clinical Chemistry.

    ERIC Educational Resources Information Center

    Gochman, Nathan; And Others

    1979-01-01

    A discussion of the basic design and characteristics of gas chromatography-mass spectrometry systems used in clinical chemistry. A comparison of three specific systems: the Vitek Olfax IIA, Hewlett-Packard HP5992, and Du Pont DP-102 are included. (BB)

  3. Identification of polychlorinated styrene compounds in heron tissues by gas-liquid chromatography-mass spectrometry

    USGS Publications Warehouse

    Reichel, W.L.; Prouty, R.M.; Gay, M.L.

    1977-01-01

    Unknown compounds detected in Ardea herodias tissues are identified by gas-liquid chromatography-mass spectrometry as residues of octachlorostyrene. Heptachlorostyrene and hexachlorostyrene were tentatively identified.

  4. Gas chromatography-mass spectrometric studies of canine urinary metabolism.

    PubMed

    Matsumoto, M; Zhang, C H; Kosugi, C; Matsumoto, I

    1995-04-01

    After the urine was treated with urease, lyophilized, and trimethylsilylated, it was examined for metabolic profiles in Dalmatian dogs and Shetland sheepdogs by gas chromatography-mass spectrometry (GC/MS), which simultaneously analyzes organic acids, amino acids, sugars, sugar alcohols, purine and pyrimidine bases, and nucleosides. The profiles were compared with those from human specimens. As clarified in past studies, Dalmatian dogs showed an extreme decrease in allantoin, which is the final product of purine metabolism in the canine of other species, and a marked detection of uric acid peak. This finding suggests that purine metabolism in Dalmatian dogs is different from that in the other species. Only two Shetland sheepdogs, whose mother had chronic renal failure, showed a marked excretion of uric acid, as in Dalmatian dogs. In addition, some Dalmatian dogs, who were maintained on a protein-restricted diet, showed a little excretion of uric acid. A large amount of uric acid is detected in combination with pentose-monosaccharides, hexose-monosaccharides and sugar alcohols in neonatal human urine in comparison with the present dog samples. A marked difference between the canine and the humans is that phenylacetylglycine, which is derived from the aromatic amino acid phenylalanine, is excreted in the canine urine. Phenylacetylglycine is not detected in the human urine, and there have been no reports of its excretion in canine urine. PMID:7492634

  5. Multiresidue pesticide analysis by capillary gas chromatography-mass spectrometry.

    PubMed

    Wong, Jon W; Zhang, Kai; Hayward, Douglas G; Kai-Meng, Chin

    2011-01-01

    A multiresidue pesticide method using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) procedure and capillary gas chromatography-mass spectrometry (GC-MS) is described for the determination of 166 organochlorine, organophosphorus, and pyrethroid pesticides, metabolites, and isomers in spinach. The pesticides from spinach were extracted using acetonitrile saturated with magnesium sulfate and sodium chloride, followed by solid-phase dispersive cleanup using primary-secondary amine and graphitized carbon black sorbents and toluene. Analysis is performed using different GC-MS techniques emphasizing the benefits of non-targeted acquisition and targeted screening procedures. Non-targeted data acquisition of pesticides in the spinach was demonstrated using GC coupled to a single quadrupole mass spectrometery (GC-MS) in full scan mode or multidimensional GC-time-of-flight mass spectrometery (GC ? ?GC-TOF/MS), along with deconvolution software and libraries. Targeted screening was achieved using GC-single quadrupole mass spectrometry in selective ion monitoring (GC-MS/SIM) mode or -tandem mass spectrometry (GC-MS/MS) in multiple reaction monitoring mode. The development of these techniques demonstrates the powerful use of GC-MS for the screening, identification, and quantitation of pesticide residues in foods. PMID:21643907

  6. Classification of natural resins by liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry using chemometric analysis.

    PubMed

    Rhourrhi-Frih, B; West, C; Pasquier, L; Andr, P; Chaimbault, P; Lafosse, M

    2012-09-21

    Twenty-six resins from six botanical sources belonging to the class Magnoliopsida were compared based on gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry data. The extracts were analysed by GC after silylation and by reversed phase LC combined with atmospheric pressure photoionisation (APPI) mass spectrometry. The chromatograms were re-organized in data matrices, where each sample was represented by a single column comprising 2755 observations (intensity, time, m/z) in GC-MS and 360 observations in LC-MS. A simple comparison of resin fingerprints was attempted by organizing data according to a three dimensional bubble chart (retention time against m/z where each point was a bubble which size represented the ion intensity) where it is possible to easily superimpose the fingerprints. Thus the common and different species can be easily observed enabling to classify the resins. Hierarchical cluster analysis based on characteristics of GC-MS and LC-MS profiles affords a complete description of the classes of the resins and shows that 26 resins are divided into five main clusters Commiphora mukul, Daniella oliveri, Gardenia gummifera, Canarium madagascariensis, Boswellia dalzielii and Boswellia serrata, respectively. In conclusion, the proposed method has been applied to three other resinous samples from the Burseraceae family to evaluate their alteration state. PMID:22885042

  7. Chemical Composition of Latent Fingerprints by Gas Chromatography-Mass Spectrometry

    ERIC Educational Resources Information Center

    Hartzell-Baguley, Brittany; Hipp, Rachael E.; Morgan, Neal R.; Morgan, Stephen L.

    2007-01-01

    An experiment in which gas chromatography-mass spectrometry (GC-MS) is used for latent fingerprint extraction and analysis on glass beads or glass slides is conducted. The results determine that the fingerprint residues are gender dependent.

  8. AN EPA MANUAL FOR ORGANICS ANALYSIS USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY

    EPA Science Inventory

    This procedural manual defines the areas of applicability of gas chromatography-mass spectrometry in environmental analysis. The manual includes sample preparation methods specifically adapted to this measurement technique, data processing and interpretation methods, quality cont...

  9. VACUUM DISTILLATION COUPLED WITH GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR THE ANALYSIS OF ENVIRONMENTAL SAMPLES

    EPA Science Inventory

    A procedure is presented that uses a vacuum distillation/gas chromatography/mass spectrometry system for analysis of problematic matrices of volatile organic compounds. The procedure compensates for matrix effects and provides both analytical results and confidence intervals from...

  10. DEVELOPMENTS IN DIRECT THERMAL EXTRACTION GAS CHROMATOGRAPHY-MASS SPECTROMETRY OF FINE AEROSOLS

    EPA Science Inventory

    This examines thermal extraction gas chromatography-mass spectrometry (TE/GC/MS) applied to aerosols collected on filters. Several different TE/GC/MS systems as a group have speciated hundreds of individual organic constituents in ambient fine aerosols. Molecular marker source ap...

  11. Identification of Synthetic Polymers and Copolymers by Analytical Pyrolysis-Gas Chromatography/Mass Spectrometry

    ERIC Educational Resources Information Center

    Kusch, Peter

    2014-01-01

    An experiment for the identification of synthetic polymers and copolymers by analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was developed and performed in the polymer analysis courses for third-year undergraduate students of chemistry with material sciences, and for first-year postgraduate students of polymer sciences. In

  12. Incorporation of Gas Chromatography-Mass Spectrometry into the Undergraduate Organic Chemistry Laboratory Curriculum

    ERIC Educational Resources Information Center

    Giarikos, Dimitrios G.; Patel, Sagir; Lister, Andrew; Razeghifard, Reza

    2013-01-01

    Gas chromatography-mass spectrometry (GC-MS) is a powerful analytical tool for detection, identification, and quantification of many volatile organic compounds. However, many colleges and universities have not fully incorporated this technique into undergraduate teaching laboratories despite its wide application and ease of use in organic

  13. Identification of Synthetic Polymers and Copolymers by Analytical Pyrolysis-Gas Chromatography/Mass Spectrometry

    ERIC Educational Resources Information Center

    Kusch, Peter

    2014-01-01

    An experiment for the identification of synthetic polymers and copolymers by analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was developed and performed in the polymer analysis courses for third-year undergraduate students of chemistry with material sciences, and for first-year postgraduate students of polymer sciences. In…

  14. Incorporation of Gas Chromatography-Mass Spectrometry into the Undergraduate Organic Chemistry Laboratory Curriculum

    ERIC Educational Resources Information Center

    Giarikos, Dimitrios G.; Patel, Sagir; Lister, Andrew; Razeghifard, Reza

    2013-01-01

    Gas chromatography-mass spectrometry (GC-MS) is a powerful analytical tool for detection, identification, and quantification of many volatile organic compounds. However, many colleges and universities have not fully incorporated this technique into undergraduate teaching laboratories despite its wide application and ease of use in organic…

  15. Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

    NASA Technical Reports Server (NTRS)

    Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

    1989-01-01

    On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

  16. Quantification of carbonate by gas chromatography-mass spectrometry.

    PubMed

    Tsikas, Dimitrios; Chobanyan-Jrgens, Kristine

    2010-10-01

    Carbon dioxide and carbonates are widely distributed in nature, are constituents of inorganic and organic matter, and are essential in vegetable and animal organisms. CO(2) is the principal greenhouse gas in the atmosphere. In human blood, CO(2)/HCO(3)(-) is an important buffering system. Quantification of bicarbonate and carbonate in inorganic and organic matter and in biological fluids such as blood or blood plasma by means of the GC-MS technology has been impossible so far, presumably because of the lack of suitable derivatization reactions to produce volatile and thermally stable derivatives. Here, a novel derivatization reaction is described for carbonate that allows for its quantification in aqueous alkaline solutions and alkalinized plasma and urine. Carbonate in acetonic solutions of these matrices (1:4 v/v) and added (13)C-labeled carbonate for use as the internal standard were heated in the presence of the derivatization agent pentafluorobenzyl (PFB) bromide for 60 min and 50 C. Investigations with (12)CO(3)(2-), (13)CO(3)(2-), (CH(3))(2)CO, and (CD(3))(2)CO in alkaline solutions and GC-MS and GC-MS/MS analyses under negative-ion chemical ionization (NICI) or electron ionization (EI) conditions of toluene extracts of the reactants revealed formation of two minor [i.e., PFB-OCOOH and O=CO(2)-(PFB)(2)] and two major [i.e., CH(3)COCH(2)-C(OH)(OPFB)(2) and CH(3)COCH=C(OPFB)(2)] carbonate derivatives. The latter have different retention times (7.9 and 7.5 min, respectively) but virtually identical EI and NICI mass spectra. It is assumed that CH(3)COCH(2)-C(OH)(OPFB)(2) is formed from the reaction of the carbonate dianion with two molecules of PFB bromide to form the diPFB ester of carbonic acid, which further reacts with one molecule of acetone. Subsequent loss of water finally generates the major derivative CH(3)COCH=C(OPFB)(2). This derivatization reaction was utilized to quantify total CO(2)/HCO(3)(-)/CO(3)(2-) (tCO(2)) in human plasma and urine by GC-MS in the NICI mode by selected ion monitoring of the anions [M-H](-) of CH(3)COCH=C(OPFB)(2) at m/z 461 for the endogenous species and m/z 462 for the internal standard (13)CO(3)(2-). Oral intake of the carboanhydrase inhibitor drug acetazolamide by two healthy volunteers resulted in temporary increased excretion of tCO(2) in the urine. The method is specific for carbonate, accurate, sensitive and should be applicable to various matrices including human fluids and environmental samples. PMID:20553048

  17. Detection of new propofol metabolites in human urine using gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry techniques.

    PubMed

    Favetta, P; Dufresne, C; Désage, M; Païssé, O; Perdrix, J P; Boulieu, R; Guitton, J

    2000-01-01

    Using hyphenated analytical techniques, gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/mass spectrometry (LC/MS), a study on minor propofol metabolites in human urine was conducted. These techniques allowed identification of two new phase I metabolites (2-(omega-propanol)-6-isopropylphenol and 2-(omega-propanol)-6-isopropyl-1,4-quinol). In addition, their four corresponding conjugates (three glucuronides and one sulphate) were detected. Thus in human urine at least eight conjugate metabolites are produced, derived from four different aglycones (propofol; 2, 6-diisopropyl-1,4-quinol; 2-(omega-propanol)-6-isopropylphenol and 2-(omega-propanol)-6-isopropyl-1,4-quinol). PMID:11013422

  18. Chemical discrimination in turbulent gas mixtures with MOX sensors validated by gas chromatography-mass spectrometry.

    PubMed

    Fonollosa, Jordi; Rodrguez-Lujn, Irene; Trincavelli, Marco; Vergara, Alexander; Huerta, Ramn

    2014-01-01

    Chemical detection systems based on chemo-resistive sensors usually include a gas chamber to control the sample air flow and to minimize turbulence. However, such a kind of experimental setup does not reproduce the gas concentration fluctuations observed in natural environments and destroys the spatio-temporal information contained in gas plumes. Aiming at reproducing more realistic environments, we utilize a wind tunnel with two independent gas sources that get naturally mixed along a turbulent flow. For the first time, chemo-resistive gas sensors are exposed to dynamic gas mixtures generated with several concentration levels at the sources. Moreover, the ground truth of gas concentrations at the sensor location was estimated by means of gas chromatography-mass spectrometry. We used a support vector machine as a tool to show that chemo-resistive transduction can be utilized to reliably identify chemical components in dynamic turbulent mixtures, as long as sufficient gas concentration coverage is used. We show that in open sampling systems, training the classifiers only on high concentrations of gases produces less effective classification and that it is important to calibrate the classification method with data at low gas concentrations to achieve optimal performance. PMID:25325339

  19. Chemical Discrimination in Turbulent Gas Mixtures with MOX Sensors Validated by Gas Chromatography-Mass Spectrometry

    PubMed Central

    Fonollosa, Jordi; Rodríguez-Luján, Irene; Trincavelli, Marco; Vergara, Alexander; Huerta, Ramón

    2014-01-01

    Chemical detection systems based on chemo-resistive sensors usually include a gas chamber to control the sample air flow and to minimize turbulence. However, such a kind of experimental setup does not reproduce the gas concentration fluctuations observed in natural environments and destroys the spatio-temporal information contained in gas plumes. Aiming at reproducing more realistic environments, we utilize a wind tunnel with two independent gas sources that get naturally mixed along a turbulent flow. For the first time, chemo-resistive gas sensors are exposed to dynamic gas mixtures generated with several concentration levels at the sources. Moreover, the ground truth of gas concentrations at the sensor location was estimated by means of gas chromatography-mass spectrometry. We used a support vector machine as a tool to show that chemo-resistive transduction can be utilized to reliably identify chemical components in dynamic turbulent mixtures, as long as sufficient gas concentration coverage is used. We show that in open sampling systems, training the classifiers only on high concentrations of gases produces less effective classification and that it is important to calibrate the classification method with data at low gas concentrations to achieve optimal performance. PMID:25325339

  20. [Analysis of cracking gas compressor fouling by pyrolysis gas chromatography-mass spectrometry].

    PubMed

    Hu, Yunfeng; Fang, Fei; Wei, Tao; Liu, Shuqing; Jiang, Guangshen; Cai, Jun

    2013-06-01

    The fouling from the different sections of the cracked gas compressor in Daqing Petrochemical Corporation was analyzed by pyrolysis gas chromatography-mass spectrometry (Py/GC-MS). All the samples were cracked in RJ-1 tube furnace cracker at the cracking temperature of 500 degrees C, and separated with a 60 m DB-1 capillary column. An electron impact ionization (EI) source was used with the ionizing voltage of 70 eV. The results showed the formation of fouling was closely related with cyclopentadiene which accounted for about 50% of the cracking products. Other components detected were 1-butylene, propylene, methane and n-butane. This Py/GC-MS method can be used as an effective approach to analyze the causes of fouling in the petrochemical plants. PMID:24063202

  1. Characterisation of beeswax in works of art by gas chromatography-mass spectrometry and pyrolysis-gas chromatography-mass spectrometry procedures.

    PubMed

    Bonaduce, Ilaria; Colombini, Maria Perla

    2004-03-01

    Pyrolysis (Py) with in situ derivatisation with hexamethyldisilazane-gas chroma-break tography-mass spectrometry (GC-MS) and a gas chromatography-mass spectrometry procedure based on microwave-assisted saponification were used to identify the organic components in small sized beeswax samples. With the latter procedure quantitative recoveries can be made and hydrocarbons, alcohols and omega-1-diols in the neutral fraction, and fatty acids and omega-1-hydroxy acids in the acidic fraction can be efficiently separated and detected. Both procedures were used to characterise a wax anatomic sculpture "The Plague" (1691-1694) by Gaetano Zumbo, resulting in the identification of beeswax and a Pinaceae resin. The GC-MS analysis brought to light some essential differences in beeswax composition between the raw material and the old modelled wax thus giving some clear indications about the recipe used by the sculptor. PMID:14989483

  2. Acetic acid improves the sensitivity of theophylline analysis by gas chromatography-mass spectrometry.

    PubMed

    Saka, Kanju; Uemura, Koichi; Shintani-Ishida, Kaori; Yoshida, Ken-Ichi

    2007-02-01

    In the analysis of theophylline by gas chromatography-mass spectrometry (GC-MS), we found that the addition of acetic acid to the solvent (ethyl acetate) decreased the adsorption of theophylline to the glass wool packed into the inlet liner. The addition of acetic acid to ethyl acetate improved the sensitivity for theophylline (optimum concentration of 3%). This simple and sensitive method without derivatization can be applied to the quantification of theophylline in serum samples in clinical and toxicological practice. PMID:17011247

  3. Formation of dehydroalanine from mimosine and cysteine: artifacts in gas chromatography/mass spectrometry based metabolomics

    SciTech Connect

    Kim, Young-Mo; Metz, Thomas O.; Hu, Zeping; Wiedner, Susan D.; Kim, Jong Seo; Smith, Richard D.; Morgan, William F.; Zhang, Qibin

    2011-08-15

    Trimethylsilyation is a chemical derivatization procedure routinely applied in gas chromatography-mass spectrometry (GC-MS)-based metabolomics. In this report, through de novo structural elucidation and comparison with authentic standards, we demonstrate that mimosine can be completely converted into dehydroalanine and 3,4-dihydroxypyridine during the trimethylsilyating process. Similarly, dehydroalanine can be formed from derivatization of cysteine. This conversion is a potential interference in GC-MS-based global metabolomics, as well as in analysis of amino acids.

  4. Analysis of radioactive mixed hazardous waste using derivatization gas chromatography/mass spectrometry, liquid chromatography, and liquid chromatography/mass spectrometry

    SciTech Connect

    Campbell, J.A.; Lerner, B.D.; Bean, R.M.; Grant, K.E.; Lucke, R.B.; Mong, G.M.; Clauss, S.A.

    1994-08-01

    Six samples of core segments from Tank 101-SY were analyzed for chelators, chelator fragments, and several carboxylic acids by derivatization gas chromatography/mass spectrometry. The major components detected were ethylenediaminetetraacetic acid, nitroso-iminodiacetic acid, nitrilotriacetic acid, citric acid, succinic acid, and ethylenediaminetriacetic acid. The chelator of highest concentration was ethylenediaminetetraacetic acid in all six samples analyzed. Liquid chromatography was used to quantitate low molecular weight acids including oxalic, formic, glycolic, and acetic acids, which are present in the waste as acid salts. From 23 to 61% of the total organic carbon in the samples analyzed was accounted for by these acids.

  5. Comprehensive Urine Drug Screen by Gas Chromatography/Mass Spectrometry (GC/MS).

    PubMed

    Ramoo, Bheemraj; Funke, Melissa; Frazee, Clint; Garg, Uttam

    2016-01-01

    Drug screening is an essential component of clinical toxicology laboratory service. Some laboratories use only automated chemistry analyzers for limited screening of drugs of abuse and few other drugs. Other laboratories use a combination of various techniques such as immunoassays, colorimetric tests, and mass spectrometry to provide more detailed comprehensive drug screening. Mass spectrometry, gas or liquid, can screen for hundreds of drugs and is often considered the gold standard for comprehensive drug screening. We describe an efficient and rapid gas chromatography/mass spectrometry (GC/MS) method for comprehensive drug screening in urine which utilizes a liquid-liquid extraction, sample concentration, and analysis by GC/MS. PMID:26660182

  6. Comparison of photoacoustic radiometry to gas chromatography/mass spectrometry methods for monitoring chlorinated hydrocarbons

    SciTech Connect

    Sollid, J.E.; Trujillo, V.L.; Limback, S.P.; Woloshun, K.A.

    1996-03-01

    A comparison of two methods of gas chromatography mass spectrometry (GCMS) and a nondispersive infrared technique, photoacoustic radiometry (PAR), is presented in the context of field monitoring a disposal site. First is presented an historical account describing the site and early monitoring to provide an overview. The intent and nature of the monitoring program changed when it was proposed to expand the Radiological Waste Site close to the Hazardous Waste Site. Both the sampling methods and analysis techniques were refined in the course of this exercise.

  7. Analysis of the anthraquinones aloe-emodin and aloin by gas chromatography/mass spectrometry.

    PubMed

    ElSohly, Mahmoud A; Gul, Waseem; Murphy, Timothy P

    2004-12-20

    A procedure was developed for the determination of low levels of the anthraquinones aloe-emodin and aloin A (barbalin) in aloe products based on gas chromatography/mass spectrometry (GC/MS) of the trimethyl silyl (TMS) derivatives of these analytes in the presence of Chrysophanol used as internal standard. The method was used to analyze several aloe based commercial products (liquids, gels and solids). Wide variation in the level of these anthraquinones was observed among the different products. The method had a sensitivity of 0.005 ppm of aloe-emodin and 0.05 ppm of aloin. PMID:15531290

  8. Analysis of volatile organic compounds in groundwater samples by gas chromatography-mass spectrometry

    SciTech Connect

    Bernhardt, J.

    1995-08-23

    The Savannah River Site contains approximately 1500 monitoring wells from which groundwater samples are collected. Many of these samples are sent off-site for various analyses, including the determination of trace volatile organic compounds (VOCs). This report describes accomplishments that have been made during the past year which will ultimately allow VOC analysis to be performed on-site using gas chromatography-mass spectrometry. Through the use of the on-site approach, it is expected that there will be a substantial cost savings. This approach will also provide split-sample analysis capability which can serve as a quality control measure for off-site analysis.

  9. Gas chromatography/mass spectrometry characterization of historical varnishes of ancient Italian lutes and violin.

    PubMed

    Echard, J P; Benoit, C; Peris-Vicente, J; Malecki, V; Gimeno-Adelantado, J V; Vaiedelich, S

    2007-02-12

    The organic constituents of historical vanishes from two ancient Italian lutes and a Stradivari violin, kept in the Musée de la musique in Paris, have been characterized using gas chromatography-mass spectrometry. Results have been compared with the chromatograms and mass spectra of recent as well as old naturally aged reference materials. The three historical varnishes analyzed have been shown to be oil varnishes, probably mixtures of linseed oil with resins. Identification of diterpenoids and triterpenoids compounds, and of the resins that may have been ingredients of the varnishes, are discussed in this paper. PMID:17386601

  10. Study on volatile components in salami by reverse carrier gas headspace gas chromatography-mass spectrometry.

    PubMed

    Procida, G; Conte, L S; Fiorasi, S; Comi, G; Favretto, L G

    1999-01-01

    Salami are a typical seasoned sausage of Italy; a number of types are produced, according to local traditional recipes. As industrial production has taken place, a number of problems rise in obtaining products similar to the traditional ones. The use of selected microbial starters is permitted by Italian law for some years and at present, microbiological research is engaged in selecting starters similar to the ones isolated from traditional products, with the aim of obtaining organoleptic characteristics close to the ones of traditional recipes. A study was carried out concerning the characterisation of volatile components of salami by headspace capillary gas chromatography-mass spectrometry. As during the sampling step, analytes could reach the analytical column, the carrier gas rate was back flushed in the latter, while a pre column was used as cold trap. Then GC-MS analysis follows. By these techniques, we were able to highlight typical profiles of different salami, as well as monitoring the ripening of a traditional and a starter added salami. Main peaks are of fermentative origin, while also peaks from spices were detected. Ethyl propionate was used as internal standard to be able to normalise the peaks amounts. PMID:10023625

  11. Gas chromatography/mass spectrometry and pyrolysis-gas chromatography/mass spectrometry for the chemical characterisation of modern and archaeological figs (Ficus carica).

    PubMed

    Ribechini, Erika; Prez-Arantegui, Josefina; Colombini, Maria Perla

    2011-06-24

    Gas chromatography/mass spectrometry (GC/MS) after alkaline hydrolysis, solvent extraction and trimethylsilylation, and analytical pyrolysis using hexamethyldisilazane (HMDS) for in situ derivatisation followed by gas chromatographic/mass spectrometric analysis (Pyrolysis-silylation-GC/MS) were used to investigate the hydrolysable and soluble constituents, and the polymerised macromolecules of an archaeological fig (Ficus carica) recovered in Zaragoza (Spain), as well as of modern figs. The main aim was to study the compositional alterations undergone by the fig tissues in a particular archaeological environment: the fig was in a vessel and covered by a layer of a mixture of orpiment and gypsum. A comparison between the GC/MS results from modern and archaeological figs revealed that degradative reactions took place, leading to the disappearance/depletion of reactive (unsaturated fatty acids) and sensitive compounds (phytosterols and triterpenes). Py-silylation-GC/MS data provided evidence of a significant degradation of the saccharide and lipid components of the fig tissue, which left a residue enriched in polyphenols and polyesters. PMID:21570079

  12. Simultaneous determination of cinnamaldehyde and its metabolite in rat tissues by gas chromatography-mass spectrometry.

    PubMed

    Zhao, Hang; Yang, Qian; Xie, Yanhua; Sun, Jiyuan; Tu, Honghai; Cao, Wei; Wang, Siwang

    2015-02-01

    Cinnamaldehyde (CA), an active ingredient isolated from the traditional Chinese medicine Cortex Cinnamomi, has a wide range of bioactivities. To clarify the distribution characteristics of CA, a selective and sensitive method utilizing gas chromatography-mass spetrometry was initially developed for simultaneously determining the concentration of CA and its metabolite cinnamyl alcohol in rat tissues. Selected ion masses of m/z 131, 105 and 92 were chosen, and separation of the analytes was performed on a DB-5?ms (30?m??0.25?mm, 0.25?m, thickness) capillary column by gas chromatography-mass spectrometry. The calibration curves demonstrated good linearity and reproducibility over the range of 20-2000 and 20-4000?ng/mL for various tissue samples. Recoveries ranged from 86.8 to 107.5%, while intra- and interday relative standard deviations were all <11.3%. The analysis method was successfully applied in tissue distribution studies for CA and cinnamyl alcohol. As CA and cinnamyl alcohol may inter-convert to one another, simultaneous determination of both analytes provides a comparative and accurate data for tissue study. The concentrations of CA and cinnamyl alcohol remaining in spleen were the highest among the main organs, including heart, liver, spleen, lung, kidney and brain. In addition, there was no long-term accumulation of CA in rat tissues. PMID:24898181

  13. Headspace analysis of engine oil by gas chromatography/mass spectrometry.

    PubMed

    Levermore, D M; Josowicz, M; Rees, W S; Janata, J

    2001-03-15

    This study establishes the rationale necessary for determining the time to change engine oil. This is based on identifying gaseous components in new and used automobile lubricants. Key compounds, so-called "signature", are separated and identified qualitatively by coupled gas chromatography/mass spectrometry. Volatile antioxidants at zero miles and fuel contaminants at low mileage are observed in the headspace of engine oil. Several oxidative degradation components have been positively identified in the used oil, which include the following: acetaldehyde, acetone, butanal, 2-propanol, acetic acid, 2-hexanol, benzoic acid, benzaldehyde, and 1-pentanol. This study strongly suggests that the status of lubricating oil can be determined by the analysis of the gas phase above the oil. Most importantly, it opens the possibility of performing conditional maintenance of the combustion engine based on information obtained from gas sensors. PMID:11305675

  14. Derivatization of pinacolyl alcohol with phenyldimethylchlorosilane for enhanced detection by gas chromatography-mass spectrometry.

    PubMed

    Albo, Rebecca L F; Valdez, Carlos A; Leif, Roald N; Mulcahy, Heather A; Koester, Carolyn

    2014-08-01

    A derivatization procedure for the qualitative gas chromatography-mass spectrometry (GC-MS) analysis of pinacolyl alcohol (PA) that employs phenyldimethylchlorosilane (PhDMClS) and the promoter N-methylimidazole is described. While PA, underivatized, can be detected using conventional gas chromatographic methods, its polarity and low boiling point make its detection in complex matrices challenging. The silylation procedure described herein generates a PA-derivative exhibiting an increased on-column retention time, thus shifting its GC-MS signal away from commonly encountered, volatile, interfering analytes. Derivatized PA could be distinguished from other PhDMClS-derivatized isomeric alcohols by its unique retention time and mass spectrum. The derivatization was demonstrated to perform well in the GC-MS analysis and identification of PA in samples from Proficiency Tests administered by the Organisation for the Prohibition of Chemical Weapons (OPCW). PMID:24481624

  15. Routine analysis of plasma busulfan by gas chromatography-mass fragmentography.

    PubMed

    Lai, W K; Pang, C P; Law, L K; Wong, R; Li, C K; Yuen, P M

    1998-12-01

    Busulfan (BU) is a widely used alkylating agent for antineoplastic therapy and marrow ablation in preparation for bone marrow transplantation (BMT). High-dose BU often leads to successful preparation and low relapse but is associated with veno-occlusive disease of liver. We established a protocol to determine postdosage plasma BU concentrations by gas chromatography-mass fragmentography in an attempt to relate clinical outcome to plasma BU concentrations. We used nonisotopic pusulfan as the internal standard. After extraction into ethyl acetate, BU and pusulfan were iodinated into 1, 4-diiodobutane and 1,5-diiodopentane, respectively. Gas chromatography-mass spectrometry (GC-MS) analysis was carried out on an Hewlett-Packard (HP) 5890II gas chromatograph with a 30-m 100% methyl silicon narrow bore, fused-silica capillary column interfaced with an HP 5970A mass spectrometer. Helium was the carrier gas. The sample molecules were identified by total ion monitoring and quantified by selective ion monitoring of m/z 183 and 197. The calibration curve was linear to 4 mg/L. The limit of quantification was 0.04 mg/L, and the analytical recovery was approximately 97%. The within-day and between-day imprecision (CV) was <6% and 9%, respectively. In a preliminary study of 12 children, the BU areas under the BU-time curve were 616-949 micromol. min/L after the first dose and 793-1143 micromol. min/L after the fifth dose. We conclude that the GC-MS procedure is suitable for routine analysis of plasma BU. PMID:9836718

  16. Community air monitoring for pesticides-part 2: multiresidue determination of pesticides in air by gas chromatography, gas chromatography-mass spectrometry, and liquid chromatography-mass spectrometry.

    PubMed

    Hengel, Matt; Lee, P

    2014-03-01

    Two multiresidue methods were developed to determine pesticides in air collected in California. Pesticides were trapped using XAD-4 resin and extracted with ethyl acetate. Based on an analytical method from the University of California Davis Trace Analytical Laboratory, pesticides were detected by analyzing the extract by gas chromatography-mass spectrometry (GC-MS) to determine chlorothalonil, chlorthal-dimethyl, cycloate, dicloran, dicofol, EPTC, ethalfluralin, iprodione, mefenoxam, metolachlor, PCNB, permethrin, pronamide, simazine, trifluralin, and vinclozolin. A GC with a flame photometric detector was used to determine chlorpyrifos, chlorpyrifos oxon, diazinon, diazinon oxon, dimethoate, dimethoate oxon, fonophos, fonophos oxon, malathion, malathion oxon, naled, and oxydemeton. Trapping efficiencies ranged from 78 to 92 % for low level (0.5 μg) and 37-104 % for high level (50 and 100 μg) recoveries. Little to no degradation of compounds occurred over 31 days; recoveries ranged from 78 to 113 %. In the California Department of Food and Agriculture (CDFA) method, pesticides were detected by analyzing the extract by GC-MS to determine chlorothalonil, chlorpyrifos, cypermethrin, dichlorvos, dicofol, endosulfan 1, endosulfan sulfate, oxyfluorfen, permethrin, propargite, and trifluralin. A liquid chromatograph coupled to a MS was used to determine azinphos-methyl, chloropyrifos oxon, DEF, diazinon, diazinon oxon, dimethoate, dimethoate oxon, diuron, EPTC, malathion, malathion oxon, metolachlor, molinate, norflurazon, oryzalin, phosmet, propanil, simazine and thiobencarb. Trapping efficiencies for compounds determined by the CDFA method ranged from 10 to 113, 22 to 114, and 56 to 132 % for 10, 5, and 2 μg spikes, respectively. Storage tests yielded 70-170 % recovery for up to 28 days. These multiresidue methods represent flexible, sensitive, accurate, and cost-effective ways to determine residues of various pesticides in ambient air. PMID:24370860

  17. Improvements in bis(cyclopentadienyl)magnesium purity as determined with gas chromatography-mass spectroscopy

    SciTech Connect

    BARTRAM,MICHAEL E.

    2000-03-08

    Bis(cyclopentadienyl)magnesium (MgCp2) is used commonly as a source for doping nitride materials with magnesium. Increased oxygen incorporation known to accompany the use of MgCp2 makes the purity of this precursor an important consideration in nitride CVD. Gas chromatography-mass spectroscopy (GCMS) methods have now been developed for the identification of volatile impurities in MgCp2. Diethylether, an oxygen containing organic compound (CH{sub 3}CH{sub 2}OCH{sub 2}CH{sub 3}), and additional organic impurities were found in the MgCp2 supplied by three manufacturers. Subsequent refinements in the synthetic processes by these companies have resulted in the availability of MgCp2 free of ether and other organic impurities as determined by GCMS.

  18. Gas chromatography/mass spectrometry for the determination of nitrosamines in red wine.

    PubMed

    Lona-Ramirez, Fernando J; Gonzalez-Alatorre, Guillermo; Rico-Ramírez, Vicente; Perez-Perez, Ma Cristina I; Castrejón-González, Edgar O

    2016-04-01

    N-nitrosamines (NAms) are highly active carcinogens that have been detected in food and beverages. Currently certain studies report their presence in red wine, while others fail to detect their presence. In this study the head space solid phase micro-extraction technique coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS) was applied to quantify four NAms in different types of red wine. The technique was found to be a simple, precise, fast and environmentally friendly alternative for the quantification of volatile NAms. A factorial analysis was carried out to evaluate the influence of the parameters on the HS-SPME technique. This is the first study that such analysis has been reported and where NAms in red wine have been quantified using HS-SPME-GC-MS. The method was validated by calculating the linearity, limit of detection and quantification. Two of the four NAms analyzed were found to be present in red wine samples. PMID:26593598

  19. Quantitative Analysis and Fingerprint Profiles for Quality Control of Fructus Schisandrae by Gas Chromatography: Mass Spectrometry

    PubMed Central

    Xia, Yong-Gang; Yang, Bing-You; Liang, Jun; Yang, Qi; Wang, Di; Kuang, Hai-Xue

    2014-01-01

    This paper describes a simple, rapid, and effective quality assessment method for Fructus Schisandrae by gas chromatography-mass spectrum (GC-MS). The method was established by using specific lignan fingerprint profiles and quantitation of characteristic compounds in this herbal medicine. The GC-MS fingerprints of 15 batches of Schisandra samples from different regions of China showed similar lignan profiles. Five peaks were selected as characteristic peaks, and all of these were identified by using GC-MS techniques. The relative retention times of these characteristic peaks in the GC-MS fingerprint were established as an important parameter for identification of Schisandra samples. Meanwhile, relative peak areas may be a feasible approach to discriminate the S. chinensis and S. sphenanthera. Finally, these pharmacologically active constituents in the titled plant, schisandrins AC and schizandrols A and B, were quantitatively determined using a validated GC-MS method. PMID:24574919

  20. Verification of chemical composition of commercially available propolis extracts by gas chromatography-mass spectrometry analysis.

    PubMed

    Czy?ewska, Urszula; Kono?czuk, Joanna; Teul, Joanna; Dr?gowski, Pawe?; Pawlak-Morka, Renata; Sura?y?ski, Arkadiusz; Miltyk, Wojciech

    2015-05-01

    Propolis is a resin that is collected by honeybees from various plant sources. Due to its pharmacological properties, it is used in commercial production of nutritional supplements in pharmaceutical industry. In this study, gas chromatography-mass spectrometry was applied for quality control analysis of the three commercial specimens containing aqueous-alcoholic extracts of bee propolis. More than 230 constituents were detected in analyzed products, including flavonoids, chalcones, cinnamic acids and their esters, phenylpropenoid glycerides, and phenylpropenoid sesquiterpenoids. An allergenic benzyl cinnamate ester was also identified in all tested samples. This analytical method allows to evaluate biological activity and potential allergenic components of bee glue simultaneously. Studies on chemical composition of propolis samples may provide new approach to quality and safety control analysis in production of propolis supplementary specimens. PMID:25198412

  1. Subsurface detection of fossil fuel pollutants by photoionization and gas chromatography/mass spectrometry.

    PubMed

    Robbat, Albert; Considine, Thomas; Antle, Patrick M

    2010-09-01

    This paper describes analysis of environmental pollutants at depth without bringing sample to the surface. It is based on an improved 3-stage Peltier freeze trap, which efficiently pre-concentrates volatile coal tar and petroleum hydrocarbons, and an integrated system for detecting pollutants on-line, in real-time by photoionization detection and quantitation by gas chromatography/mass spectrometry (GC/MS) as the probe is advanced into the subsurface. Findings indicate measurement precision and accuracy for volatiles meet EPA criteria for hazardous waste site investigations. When a Teflon membrane inlet is used to detect contaminants in groundwater, its 140 degrees C temperature limit restricts analyte collection in soil to C(2)-phenanthrenes. Two case studies demonstrate the probe is well-suited to tracking petroleum and coal tar plumes from source to groundwater. PMID:20594575

  2. Identification of several human urinary metabolites of 6-benzoyl benzoxazolinone by gas chromatography/mass spectrometry.

    PubMed

    Bastide, M; Chabard, J L; Lartigue, C; Bargnoux, H; Petit, J; Berger, J A; Mansour, H A; Lesieur, D; Buch, N

    1991-08-01

    The biotransformation of 6-benzoyl benzoxazolinone (6-BB), a non-narcotic peripheral analgesic, was studied in eight healthy volunteers after oral administration of a single dose of 1 g. Urinary metabolites were extracted either with ethyl acetate at different pH values or by percolating at pH 5 through Amberlite XAD 2 ion-exchange resin. Eluates were concentrated under vacuum, purified by thin-layer chromatography and analysed by gas chromatography/mass spectrometry or direct insertion probe mass spectrometry. Metabolites were identified with reference to the mass spectra of various synthesized compounds assumed to be metabolites of 6-BB, as N-methylated or monohydroxylated compounds. Another metabolic pathway was cleavage of the benzoxazolinone heterocycle giving 2-amino-5-benzoyl phenol after hydrolysis and decarboxylation. N-methyl, N-acetyl and hydroxylated metabolites having an amino-5-benzoyl phenol structure were also found. PMID:1768705

  3. Use of Gas Chromatography-Mass Spectrometry (GC-MS) in Nonscience Major Course Laboratory Experiments

    NASA Astrophysics Data System (ADS)

    Kostecka, Keith S.; Lerman, Zafra M.; Angelos, Sanford A.

    1996-06-01

    Gas chromatography-mass spectrometry (GC-MS) has been utilized with nonscience majors in the courses: "Modern Methods in Science: Discovering Molecular Secrets"; "The Extraordinary Chemistry of Ordinary Things"; "From Ozone to Oil Spills: Chemistry, the Environment and You"; and "Crime Lab Chemistry: Solving Crime through Analytical Chemistry". Our efforts have centered on introducing prospective science communicators (film, video, radio, television, and journalism majors) to science relative to their majors and personal interests. Quality lecture-discussion topics, "mystery"-based laboratory activities have assisted in introducing and/or explaining specific areas of chemistry that attempt to reduce fear of subject matter. Students have also used GC-MS, as a form of alternative assessment, in course projects that have been based on their majors, personal interests, and cultural backgrounds. Students have also conducted advanced independent work in different areas of chemistry, including the analysis of nail polishes and lacquers and eleven aromatic compounds present in three different brands of gasoline.

  4. Analysis of beechwood creosote by gas chromatography-mass spectrometry and high-performance liquid chromatography.

    PubMed

    Ogata, N; Baba, T

    1989-12-01

    Compounds in beechwood creosote were analyzed by gas chromatography-mass spectrometry, and 22 major constituents were identified. Of these, 19 were phenolic compounds, i. e., guaiacol, phenol, two cresol isomers, four methylguaiacol (creosol) isomers, six xylenol isomers, two trimethylphenol isomers, 4-ethylguaiacol, 4-ethyl-5-methylguaiacol, and 4-propylguaiacol. The remaining three were hitherto unpredicted five-membered ring compounds, i. e., 3-methyl-2-hydroxy-2-cyclopenten-1-one, 3,5-dimethyl-2-hydroxy-2-cyclopenten-1-one, and 3-ethyl-2-hydroxy-2-cyclopenten-1-one. The relative quantities of these compounds were also compared with those obtained by high-resolution high-performance liquid chromatography. This report probably represents the first extensive analysis of beechwood creosote. PMID:2609018

  5. [Structure determination of alkyd resins by simultaneous pyrolysis methylation gas chromatography-mass spectometry].

    PubMed

    Cao, J Y; Fu, D H; Zhang, F; Liang, D

    2000-09-01

    Several types of alkyd resins have been analyzed by simultaneous pyrolysis methylation gas chromatography mass spectrometry (SPM-GC-MS). The samples were mixed with tetramethylammonium hydroxide, and the process included simultaneous pyrolysis derivatization and mass spectrometry determination. SPM-GC-MS conditions: a vertical microfurnace-type pyrolyzer was directly attached to a gas chromatograph-mass spectrometer. About 20 ug of the mixed alkyd resin sample was introduced into the center of the pyrolyzer at 450 degrees C under the flow of helium carrier gas. The inlet mode was split with an injection interval of 10 s and the inlet pressure was 82.7 kPa. The gas chromatograph was fitted with a fused-silica capillary column ( SE-54 30 m x0.25 mm i.d. x 0.25 um). Temperature program settings were: initial temperature, 40 degrees C, hold 2 min; increase at 6 degrees C min 1 to 220 degrees C, hold 14 min; increase at 10 degrees C min 1 to 280 degrees C, hold 8 min. All pyrolysis products referred to were identified by mass spectrometry. The temperature of the ion source was 210 degrees C and that of the transfer line was 250 degrees C. The technique could give additional information about the composition of the dibasic acids, polyols, six types of drying oils, and modified alkyd resins. The method is sensitive, accurate, convenient, and involves minimal sample manipulation. PMID:12549427

  6. Quantitation of Phenol Levels in Oil of Wintergreen Using Gas Chromatography-Mass Spectrometry with Selected Ion Monitoring

    ERIC Educational Resources Information Center

    Sobel, Robert M.; Ballantine, David S.; Ryzhov, Victor

    2005-01-01

    Industrial application of gas chromatography-mass spectrometry (GC-MS) analysis is a powerful technique that could be used to elucidate components of a complex mixture while offering the benefits of high-precision quantitative analysis. The natural wintergreen oil is examined for its phenol concentration to determine the level of refining

  7. DETERMINATION OF VOLATILE ORGANIC COMPOUNDS IN SOILS USING EQUILIBRIUM HEADSPACE ANALYSIS AND CAPILLARY COLUMN GAS CHROMATOGRAPHY/MASS SPECTROMETRY

    EPA Science Inventory

    Existing methods for determination of volatile organic compounds (VOCs) in soil matrices using the purge and trap technique with gas chromatography/mass spectrometry (GC/MS) have several problems, which include preserving sample integrity from collection to analysis and efficient...

  8. ANALYSIS OF TRACE-LEVEL ORGANIC COMBUSTION PROCESS EMISSIONS USING NOVEL MULTIDIMENSIONAL GAS CHROMATOGRAPHY-MASS SPECTROMETRY PROCEDURES

    EPA Science Inventory

    The paper discusses the analysis of trace-level organic combustion process emissions using novel multidimensional gas chromatography-mass spectrometry (MDGC-MS) procedures. It outlines the application of the technique through the analyses of various incinerator effluent and produ...

  9. Quantitation of Phenol Levels in Oil of Wintergreen Using Gas Chromatography-Mass Spectrometry with Selected Ion Monitoring

    ERIC Educational Resources Information Center

    Sobel, Robert M.; Ballantine, David S.; Ryzhov, Victor

    2005-01-01

    Industrial application of gas chromatography-mass spectrometry (GC-MS) analysis is a powerful technique that could be used to elucidate components of a complex mixture while offering the benefits of high-precision quantitative analysis. The natural wintergreen oil is examined for its phenol concentration to determine the level of refining…

  10. An Advanced Analytical Chemistry Experiment Using Gas Chromatography-Mass Spectrometry, MATLAB, and Chemometrics to Predict Biodiesel Blend Percent Composition

    ERIC Educational Resources Information Center

    Pierce, Karisa M.; Schale, Stephen P.; Le, Trang M.; Larson, Joel C.

    2011-01-01

    We present a laboratory experiment for an advanced analytical chemistry course where we first focus on the chemometric technique partial least-squares (PLS) analysis applied to one-dimensional (1D) total-ion-current gas chromatography-mass spectrometry (GC-TIC) separations of biodiesel blends. Then, we focus on n-way PLS (n-PLS) applied to

  11. THE IDENTIFICATION OF POLYCHLORINATED TERPHENYLS AT TRACE LEVELS IN HUMAN ADIPOSE TISSUE BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY

    EPA Science Inventory

    Pooled samples of human adipose extracts representative of the general population of the United States were examined by gas chromatography-mass spectrometry. The use of gel permeation chromatography for cleanup was found to offer a significant improvement in detection capability....

  12. An Advanced Analytical Chemistry Experiment Using Gas Chromatography-Mass Spectrometry, MATLAB, and Chemometrics to Predict Biodiesel Blend Percent Composition

    ERIC Educational Resources Information Center

    Pierce, Karisa M.; Schale, Stephen P.; Le, Trang M.; Larson, Joel C.

    2011-01-01

    We present a laboratory experiment for an advanced analytical chemistry course where we first focus on the chemometric technique partial least-squares (PLS) analysis applied to one-dimensional (1D) total-ion-current gas chromatography-mass spectrometry (GC-TIC) separations of biodiesel blends. Then, we focus on n-way PLS (n-PLS) applied to…

  13. Morphological and Chemoprofile (Liquid Chromatography-mass Spectroscopy and Gas Chromatography-mass Spectroscopy) Comparisons of Cyperus scariosus R. Br and Cyperus rotundus L.

    PubMed Central

    Kakarla, Lavanya; Katragadda, Suresh Babu; Botlagunta, Mahendran

    2015-01-01

    Background: Cyperus scariosus (CS) R.Br and Cyperus rotundus (CR) L. belongs to Cyperaceae family which is well-reputed in the traditional systems of medicine. Although they grow in different agro-climatic conditions, they are often considered to be synonymous with each other. Objective: The present study was aimed to systematically classify both the species CS and CR through their morphological features and chemical profiling using liquid chromatography-mass spectroscopy (LC-MS), gas chromatography-mass spectroscopy (GC-MS) and thin layer chromatography patterns of the rhizome extracts. Materials and Methods: A method (LC-MS analysis) has been developed on Agilent LC-MSD Trap SL mass spectrometer equipped with Waters HR C18 column (3.9 mm × 300 mm, 6 μm) using isocratic elution with acetonitrile and water (70:30% v/v ratio). GC-MS analysis was performed on a Shimadzu GC-MS-QP 2010 equipped with DB-5 capillary column (30 m × 0.25 mm × 0.25 μm). Results: Chemoprofiling of CS and CR using LC-MS and GC-MS suggested that these two are different based on their deferential spectral pattern, however, some of the common peaks were found in both the species. In addition, we also performed the preliminary phytochemical investigation of hexane and chloroform extracts of these species, which led to the isolation of stigmasterol, β-sitosterol and lupeol as major constituents in CS. Conclusion: In summary, we have developed optimal chromatographic conditions (LC-MS and GC-MS) and morphological profiles to classify both the species, that is, CS and CR. Collectively, our analytical results coupled with the morphological data clearly suggested that CS and CR are morphologically different. SUMMARY The huge demand for herbal medicine has put pressure on the supply of natural resources which ultimately results in use of substandard materials or substitution and adulteration. The medicinal plants, Cyperus rotundus L and Cyperus scariosus R.Br which belongs to cyperaceae family and extensively used in the traditional systems of medicine. Although these two species are grown in different soil conditions, Cyperus scariosus R.Br often treated as synonymous of Cyperus rotundus. Thus, the present study was undertaken to classify these two species systematically using the modern analytical techniques as a powerful tools. Further, we also carried out the preliminary phytochemical investigation of hexane and chloroform extracts of cyperus scariosus rhizomes, which resulted in the isolation of three compounds namely Sitosterol, Stigmasterol and Lupeol. PMID:26929579

  14. Determination of toxic compounds in paper-recycling process waters by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.

    PubMed

    Rigol, A; Latorre, A; Lacorte, S; Barcel, D

    2002-07-19

    Three analytical methods were developed for the determination of toxic compounds in recirculating waters of a paper-recycling industry. Three main groups of compounds were considered: (i) wood extractives originated from the raw material; (ii) biocides added during the production process and (iii) surfactants and other adjuvants present in the formulates of these biocides. Wood extractives considered in this study included fatty and resin acids. They were analysed by liquid-liquid extraction using methyl tert.-butyl ether, followed by gas chromatography-mass spectrometry for previous formation of the respective trimethylsilyl esters. Water samples were also extracted with Oasis HLB (copolymer [poly(divinylbenzene-co-N-vinylpyrrolidone]) solid-phase extraction cartridges of 60 mg and analysed by liquid chromatography-electrospray mass spectrometry for the determination of additives and biocides. Using these two approaches levels up to 15 mg/l for total resin and fatty acids, 5 mg/l for alkylbenzene sulfonates and 2-(thiocyanomethylthio)benzotiazol, 100 microg/l for bisphenol A and 2,2-dibromo-3-nitrilepropionamide, and 300 microg/l for nonylphenol ethoxycarboxylate were detected in process waters at different production treatment stages. These levels are of relevance since poor water quality affects the paper-recycling process, the primary water treatment process and eventually, the environmental water quality. PMID:12187979

  15. Development of a technique for mercury speciation and quantification using gas chromatography/mass spectrometry

    SciTech Connect

    Barshick, S.A.; Barshick, C.M.; Britt, P.F.; Vance, M.A.; Duckworth, D.C.

    1997-07-01

    One element of concern to DOE is mercury. Mercury was used extensively at the DOE facilities in Oak Ridge, Tennessee from 1950 to 1963 in the process of making lithium deuteride, a component of nuclear weapons. Although both the inorganic and organometallic forms of mercury are toxic to humans, the organic compounds are often more toxic. Since the toxicity of mercury is a function of its chemical form, an understanding of the interactions between commercially discharged mercury, naturally occurring mercury, and the environment in which they are present is vital. In this report, the authors have been investigating gas chromatography/mass spectrometry (GC/MS) for the analysis of both the organometallic and inorganic forms of mercury in the same environmental sample (e.g., solutions, soils, and sludges). Although gas chromatography is the classical technique for analyzing organic molecules, (e.g., organometallic compounds) little has been done on the analysis of inorganic compounds. In a previous publication, the authors described how a solid phase microextraction (SPME) fiber could be used to sample organomercurials from aqueous samples. An alkylation reaction was then carried out to transform chemically mercury nitrate into dimethylmercury; subsequent GC/MS analysis of this compound permitted quantification of the inorganic constituent. Subsequently, several different alkylation reagents have been synthesized that methylate any inorganic mercury compound to methylmercury iodide. Here, the authors report results on alkylation reaction time and the effect of pH on the population of the product.

  16. Determination of ortho-phenylphenol in human urine by gas chromatography-mass spectrometry.

    PubMed

    Bartels, M J; Brzak, K A; Bormett, G A

    1997-12-01

    A sensitive gas chromatographic-mass spectrometric method was developed to quantitate total o-phenylphenol (OPP) (free plus conjugates) in human urine. Conjugates of OPP were acid-hydrolyzed to free OPP, derivatized to the pentafluorobenzoyl ester derivative and analyzed via negative-ion chemical ionization gas chromatography-mass spectrometry. Two stable isotope analogs of OPP were shown to be suitable as internal standards for this method (D2-phenol ring, 13C6-phenyl ring). A synthetic method is presented for the preparation of the D2-OPP internal standard. The 13C6-OPP analog was also shown to be useful as an alternate test material for laboratory-based exposure studies. The limit of quantitation for this method was 1 ng OPP/ml urine. Calibration curves were linear for the analyte over the concentration range of 0.5-1117 ng OPP/ml urine. Relative recovery of OPP from urine ranged from 97.0 to 104.7%. Low levels of OPP (mean=6+/-7 ng/ml; n=22) were found in control human urine samples. The method was validated with urine samples obtained from human volunteers undergoing a dermal exposure study with 12C-/13C6-/14C-OPP. This method was developed to aid in assessments of human exposure to OPP during a variety of uses of the compound. PMID:9448066

  17. Gas Chromatography-Mass Spectroscopy Study of tert-Butylarsine Stability and Purification

    SciTech Connect

    Bartram, M.E.; Breiland, W.G.; Bruskas, L.A.; Killeen, K.P.

    1999-07-20

    TBA (tert-butylarsine, H{sub 2}AsC(CH{sub 3}){sub 3}) has been demonstrated to be an effective arsenic precursor for the deposition of compound semiconductors such as GaAs by MOCVD (metal organic chemical vapor deposition). TBA is used as a liquid (bubbler) source in MOCVD and is a less toxic alternative to the more commonly used gaseous arsine (AsH{sub 3}). Materials and device performance using TBA have in many cases equaled or surpassed those using arsine. This includes the first observation of fractional quantum Hall behavior in a two dimensional electron gas structure grown by MOCVD. Despite the beneficial characteristics, the use of TBA in our laboratories has revealed some inconsistent behavior. Small pressure rises have been observed in the TBA bubbler sources when left unused over a period of many days. Measurements of the TBA partial pressure using UV absorption revealed that new absorption peaks could be observed after storage. The features of the absorption profile were insufficient to ascribe to a specific chemical species. Attempts to remove the gaseous impurities with liquid nitrogen freeze-pump-thaw techniques had limited success. Unfortunately, there is no published information on the room temperature decomposition of TBA. In this paper, we present a series of GCMS (gas chromatography-mass spectroscopy) analyses designed to determine the stability of TBA and identify its decomposition products in storage containers. The GCMS is also used to evaluate several methods for in-situ purification of TBA.

  18. Determination of methomyl in the stomach contents of baited wildlife by gas chromatography-mass spectrometry.

    PubMed

    Buchweitz, John P; Bokhart, Mark; Johnson, Margaret; Lehner, Andreas

    2013-11-01

    The poisoning of wildlife with fly-bait containing the active ingredient methomyl is an intentional and illegal act in many jurisdictions. A case of 2 animals poisoned by methomyl through consumption of tainted bait at multiple stations is described. Although thermally and ultraviolet-labile, methomyl can be identified by gas chromatography-mass spectrometry and is detected in abundance in bait samples; however, it is not readily observed in tissues, owing to its rapid metabolism and elimination. The application of derivatizing functionalities, such as trimethylsilyl groups, stabilizes the methomyl-oxime metabolite to facilitate its detectability during exposure to the relatively harsh conditions of gas chromatography. This brief communication reports on the analytical detection of methomyl in baits and biological samples from poisoned wildlife. Essential to the case were the added determination of a fly-bait coactive ingredient, (Z)-9-tricosene, and identification of a chemical indicator, caffeine, to confirm both the type of pesticide product involved in the poisoning incident and the vehicle used to perpetrate its delivery. PMID:24105381

  19. Multivariate analysis of progressive thermal desorption coupled gas chromatography-mass spectrometry.

    SciTech Connect

    Van Benthem, Mark Hilary; Mowry, Curtis Dale; Kotula, Paul Gabriel; Borek, Theodore Thaddeus, III

    2010-09-01

    Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.

  20. Laser desorption fast gas chromatography-mass spectrometry in supersonic molecular beams.

    PubMed

    Shahar, T; Dagan, S; Amirav, A

    1998-06-01

    A novel method for fast analysis is presented. It is based on laser desorption injection followed by fast gas chromatography-mass spectrometry (GC-MS) in supersonic molecular beams. The sample was placed in an open air or purged laser desorption compartment, held at atmospheric pressure and near room temperature conditions. Desorption was performed with a XeCl Excimer pulsed laser with pulse energy of typically 3 mJ on the surface. About 20 pulses at 50 Hz were applied for sample injection, resulting in about 0.4 s injection time and one or a few micrograms sample vapor or small particles. The laser desorbed sample was further thermally vaporized at a heated frit glass filter located at the fast GC inlet. Ultrafast GC separation and quantification was achieved with a 50-cm-long megabore column operated with a high carrier gas flow rate of up to 240 mL/min. The high carrier gas flow rate provided effective and efficient entrainment of the laser desorbed species in the sweeping gas. Following the fast GC separation, the sample was analyzed by mass spectrometry in supersonic molecular beams. Both electron ionization and hyperthermal surface ionization were employed for enhanced selectivity and sensitivity. Typical laser desorption analysis time was under 10 s. The laser desorption fast GC-MS was studied and demonstrated with the following sample/matrices combinations, all without sample preparation or extraction: (a) traces of dioctylphthalate plasticizer oil on stainless steel surface and the efficiency of its cleaning; (b) the detection of methylparathion and aldicarb pesticides on orange leaves; (c) water surface analysis for the presence of methylparathion pesticide; (d) caffeine analysis in regular and decaffeinated coffee powder; (e) paracetamol and codeine drug analysis in pain relieving drug tablets; (f) caffeine trace analysis in raw urine; (g) blood analysis for the presence of 1 ppm lidocaine drug. The features and advantages of the laser desorption fast GC-MS are demonstrated and discussed. PMID:9879375

  1. Headspace Analysis of Philippine Civet Coffee Beans Using Gas Chromatography-Mass Spectrometry and Electronic Nose

    NASA Astrophysics Data System (ADS)

    Ongo, E.; Sevilla, F.; Antonelli, A.; Sberveglieri, G.; Montevecchi, G.; Sberveglieri, V.; de Paola, E. L.; Concina, I.; Falasconi, M.

    2011-11-01

    Civet coffee, the most expensive and best coffee in the world, is an economically important export product of the Philippines. With a growing threat of food adulteration and counterfeiting, a need for quality authentication is essential to protect the integrity and strong market value of Philippine civet coffee. At present, there is no internationally accepted method of verifying whether a bean is an authentic civet coffee. This study presented a practical and promising approach to identify and establish the headspace qualitative profile of Philippine civet coffee using electronic nose (E-nose) and gas chromatography-mass spectrometry (GC-MS). E-nose analysis revealed that aroma characteristic is one of the most important quality indicators of civet coffee. The findings were supported by GC-MS analysis. Principal component analysis (PCA) exhibited a clearly separated civet coffees from their control beans. The chromatographic fingerprints indicated that civet coffees differed with their control beans in terms of composition and concentration of individual volatile constituents.

  2. Impurity profiling of trinitrotoluene using vacuum-outlet gas chromatography-mass spectrometry.

    PubMed

    Brust, Hanneke; Willemse, Sander; Zeng, Tuoyu; van Asten, Arian; Koeberg, Mattijs; van der Heijden, Antoine; Bolck, Annabel; Schoenmakers, Peter

    2014-12-29

    In this work, a reliable and robust vacuum-outlet gas chromatography-mass spectrometry (GC-MS) method is introduced for the identification and quantification of impurities in trinitrotoluene (TNT). Vacuum-outlet GC-MS allows for short analysis times; the analysis of impurities in TNT was performed in 4min. This study shows that impurity profiling of TNT can be used to investigate relations between TNT samples encountered in forensic casework. A wide variety of TNT samples were analyzed with the developed method. Dinitrobenzene, dinitrotoluene, trinitrotoluene and amino-dinitrotoluene isomers were detected at very low levels (<1wt.%) by applying the MS in selected-ion monitoring (SIM) mode. Limits of detection ranged from 6ng/mL for 2,6-dinitrotoluene to 43ng/mL for 4-amino-2,6-dinitrotoluene. Major impurities in TNT were 2,4-dinitrotoluene and 2,3,4-trinitrotoluene. Impurity profiles based on seven compounds showed to be useful to TNT samples from different sources. Statistical analysis of these impurity profiles using likelihood ratios demonstrated the potential to investigate whether two questioned TNT samples encountered in forensic casework are from the same source. PMID:25488253

  3. Metabolic products in urine of preterm infants characterized via gas chromatography-mass spectrometry

    PubMed Central

    Hao, Hu; Li, Sitao; Zhou, Wei; Wang, Hong; Liu, Mengxian; Shi, Congcong; Chen, Jing; Xiao, Xin

    2015-01-01

    Objective: To characterize the metabolic products of urine associated with preterm birth, thus providing clinical guidelines for intestinal and parenteral nutrition in preterm infants. Methods: Urine samples of 47 preterm infants and 45 full-term infants were collected and prepared for trimethylsilylation by treatment with urease. The levels of lysine, phenylalanine, histidine, ornithine, fumaric acid, malic acid, succinic acid, lactose, stearic acid, and 4-hydroxyphenylacetic acid were detected by gas chromatography-mass spectrometry (GC/MS), and statistically analyzed. Results: The normalized concentrations of the following metabolites in preterm infant urine samples were significantly lower than that of full-term infant urine samples: lysine (P = 0.003), phenylalanine (P = 0.001), histidine (P = 0.006), ornithine (P = 0.000), fumaric acid (P = 0.002), malic acid (P = 0.006), succinic acid (P = 0.000), lactose (P = 0.000), stearic acid (P = 0.000) and 4-hydroxyphenylacetic acid (P = 0.000). Conclusions: The results of the GC/MS analysis indicated that amino acid, carbohydrate, and fatty acid metabolism defects exist in preterm infants. The use of GC/MS to determine metabolic products in urine samples could be helpful for prospectively evaluating the nutritional status of preterm infants, and therefore providing clinical guidelines on reasonable nutritional support. PMID:26629171

  4. Temperature-programmed retention indices for gas chromatography-mass spectroscopy analysis of plant essential oils.

    PubMed

    Zhao, Chen-Xi; Liang, Yi-Zeng; Fang, Hong-Zhuang; Li, Xiao-Ning

    2005-11-25

    A total of 95 volatile compounds from the essential oil in buds of Syringa oblata Lindl (lilac) were identified by gas chromatography-mass spectrometry (GC-MS) combined with heuristic evolving latent projections (HELP) and moving subwindow searching (MSS). The identified compounds are mainly aliphatic, terpenes and aromatic compounds. Their temperature-programmed retention indices (PTRIs) on HP-5MS and DB-35MS at three heating rates of 2, 4 and 6 degrees C/min from 80 to 290 degrees C were obtained, which showed that aliphatic compounds give nearly constant PTRIs and PTRIs of terpenoids do not vary much at different heating rates. But PTRIs of aromatic compounds exhibit relatively large temperature dependence. PTRIs vary much more on DB-35MS than those on HP-5MS according to the compound types. In general, differences of PTRIs between the two columns increase from aliphatic compounds to terpenoids to polycyclic aromatic compounds. The PTRIs in different heating rates were used as cross-references in the identification of components in the essential oil. When they were used in analysis of essential oil from flowers of lilac, good results were obtained. These PTRIs would be a part of our PTRI database being constructed on components from plant essential oils. The results also showed that efficiency and reliability were improved greatly when chemometric method and PTRIs were used as assistants of GC-MS in identification of chemical components in plant essential oils. PMID:16289121

  5. Determination of free and ethoxylated alkylphenols in leather with gas chromatography-mass spectrometry.

    PubMed

    Ma, He-Wei; Cheng, Ya

    2010-12-10

    An analytical approach was developed to determine nonylphenol (NP), octylphenol (OP), nonylphenol ethoxylates (NPEO(n)) and octylphenol ethoxylates (OPEO(n)) in leather samples involving the conversion of NPEO(n) and OPEO(n) into the corresponding NP and OP. The four targets were extracted from samples using ultrasonic-assisted acetonitrile extraction. NP and OP in the extracts were directly isolated with hexane and quantitatively determined with 4-n-nonylphenol as internal standard by gas chromatography-mass spectrometry (GC-MS). For NPEO(n) and OPEO(n) in the extracts, they were first converted into NP and OP with aluminum triiodide as cleavage agent, and the yielded NP and OP were determined by GC-MS. The contents of NPEO(n) and OPEO(n) were calculated by normalizing to NPEO(9) and OPEO(9), respectively. This method was properly validated and the real sample tests revealed the pollution significance of leather by NPEO(n) and OPEO(n). PMID:21067757

  6. Determination of 4-hydroxyproline in collagen by gas chromatography/mass spectrometry.

    PubMed

    Tredget, E E; Falk, N; Scott, P G; Hogg, A M; Burke, J F

    1990-11-01

    Derivatization of 4-hydroxyproline (Hyp) in collagen using trifluoroacetylation and methanol esterification produces two derivatives when analyzed by gas chromatography/mass spectrometry (GC/MS). The diacyl derivative N,O-bis(trifluoroacetyl)-4-hydroxy-L-proline methyl ester (N,O-TFA-Hyp) formed in this manner has a shorter retention time and different fragmentation pattern by GC/MS as compared to the slower eluting monoacetylated species N-trifluoroacetyl-4-hydroxy-L-proline methyl ester (N-TFA-Hyp). By selected ion monitoring of the appropriate ions of either N,O-TFA-Hyp (m/z 164, 278) or N-TFA-Hyp (m/z 164, 182) efficient quantitation of Hyp in collagen is possible within the broad range of 5-1000 ng with a lower limit of detection of 0.5 ng per injection. Measurement of 18O2 incorporation into collagen is possible by selected ion monitoring of the m/z 182 ion formed only from the monoacetylated derivative, N-TFA-Hyp, produced by methanol solvolysis of the N,O-TFA-Hyp derivative, as proposed herein. PMID:2291469

  7. Presence of phthalate esters in intravenous solution evaluated using gas chromatography-mass spectrometry method.

    PubMed

    Strac, Ivona Vidi?; Pui?, Maja; Gajski, Goran; Garaj-Vrhovac, Vera

    2013-03-01

    Di-(2-ethylhexyl) phthalate (DEHP) is a plasticizer widely used in the production of poly-(vinyl) chloride (PVC) materials. It is a reproductive and developmental toxicant in animals and a suspected endocrine modulator in humans. DEHP is not covalently bound within the PVC molecule, which is why migration into a suitable medium can be expected. Since application of infusion solutions is one of the most common medical treatments, the objective of this study was to determine the migration of phthalates from softened PVC storage bags into infusion solution in different time periods within one year from date of production using a gas chromatography-mass spectrometry method. The measured values of DEHP ranged between 0.22 and 14.00?g l(-1) , but the unexpected presence of other phthalate esters was also detected. It was concluded that values obtained in infusion solutions match the reference data and represent a minor risk for the patient. The presence of other phthalate esters leads to the conclusion that the pharmacopeic requirement for polymer cleanness was not fully met. Since phthalate esters are among the most extensively used industrial chemicals and are widely distributed in the environment, special precautions and further monitoring should be conducted to minimize any possible health risks. PMID:22034089

  8. [Simultaneous determination of nine preservatives in fruits using gas chromatography-mass spectrometry].

    PubMed

    Peng, Shunü; Wang, Qiuquan; Fang, Lanlan; Guo, Shanyong; Zeng, Zhouhua; Lin, Zhuguang

    2014-01-01

    A gas chromatography-mass spectrometry (GC-MS) method was established for the simultaneous determination of nine typical preservatives (pyrimethanil, chlorothalonil, chlorpyrifos, triadimefon, thiabendazole, imazalil, myclobutanil, iprodione, prochloraz) in fruits. The fruit samples were subjected to ultrasonic extraction with hexane/ethyl acetate (1/1, v/v), and followed by purification using diatomite column chromatography with hexane/ethyl acetate (1/3, v/v) eluant. Qualitative and quantitative analysis of the nine preservatives were performed on the GC-MS at full-scan (SCAN) and selected ion monitoring (SIM) modes, in which triphenylphosphate was used as the internal standard. The detection limits obtained for the nine preservatives were ranged from 0.10 microg/kg to 2.16 microg/kg. The average recoveries were in the range of 75.3% to 128% at the spiked levels of 50, 100 and 200 microg/kg with the relative standard deviations (RSDs) of 1.57% to 11.6% (n = 5). The results showed that the developed method is sensitive and accurate for the determination of the nine preservatives in fruits. PMID:24783871

  9. Determination of Sudan dye residues in eggs by liquid chromatography and gas chromatography-mass spectrometry.

    PubMed

    He, Limin; Su, Yijuan; Fang, Binghu; Shen, Xiangguang; Zeng, Zhenling; Liu, Yahong

    2007-06-26

    A sensitive and cheap high performance liquid chromatography (HPLC) with ultraviolet-visible (UV-VIS) was developed for the determination of Sudan dyes (I, II, III, and IV) residues in various types of eggs. The chromatographic separation was achieved on a reverse phase C18 column with gradient elution, using a mobile phase of 0.1% formic acid acetonitrile/0.1% formic acid aqueous solution; detector was set at 478 nm for Sudan I and 520 nm for Sudan II, III and IV. The suspected egg samples were derivatized with N,O-bis (trimethylsilyl) trifluoro-acetamide and confirmed by gas chromatography-mass spectrometry (GC-MS) in EI. Mass spectra of trimethylsilyl derivatives of the Sudan dyes were built up in EI mode. Recoveries of the Sudan dyes ranged between 79.8 and 95.7% in eggs by HPLC-UV, with all the relative standard deviations of less than 5%. Limit of detection (LOD), limit of quantification (LOQ) were in the range of 4.0-4.8 and 12.3-13.8 microg kg(-1) in eggs, respectively. Identification and confirmation could be validated in the range of 2.0-4.2 microg kg(-1) with the GC-MS method. This method is suitable for routine fast monitoring, screening and confirmation of Sudan dyes residues in eggs, as mandated by regulatory agencies. PMID:17560395

  10. In situ Analysis of Organic Compounds on Mars using Chemical Derivatization and Gas Chromatography Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Glavin, D. P.; Buch, A.; Cabane, M.; Coll, P.; Navarro-Gonzalez, R.; Mahaffy, P. R.

    2005-01-01

    One of the core science objectives of NASA's 2009 Mars Science Laboratory (MSL) mission is to determine the past or present habitability of Mars. The search for key organic compounds relevant to terrestrial life will be an important part of that assessment. We have developed a protocol for the analysis of amino acids and carboxylic acids in Mars analogue materials using gas chromatography mass spectrometry (GCMS). As shown, a variety of carboxylic acids were readily identified in soil collected from the Atacama Desert in Chile at part-per-billion levels by GCMS after extraction and chemical derivatization using the reagent N,N-tert.-butyl (dimethylsilyl) trifluoroacetamide (MTBSTFA). Several derivatized amino acids including glycine and alanine were also detected by GCMS in the Atacama soil at lower concentrations (chromatogram not shown). Lacking derivatization capability, the Viking pyrolysis GCMS instruments could not have detected amino acids and carboxylic acids, since these non-volatile compounds require chemical transformation into volatile species that are stable in a GC column. We are currently optimizing the chemical extraction and derivatization technique for in situ GCMS analysis on Mars. Laboratory results of analyses of Atacama Desert samples and other Mars analogue materials using this protocol will be presented.

  11. Isolation and derivatization of plasma taurine for stable isotope analysis by gas chromatography-mass spectrometry

    SciTech Connect

    Irving, C.S.; Klein, P.D.

    1980-09-01

    A method for the isolation and derivatization of plasma taurine is described that allows stable isotope determinations of taurine to be made by gas chromatography-mass spectrometry. The isolation procedure can be applied to 0.1 ml of plasma; the recovery of plasma taurine was 70 to 80%. For gc separation, taurine was converted to its dimethylaminomethylene methyl ester derivative which could not be detected by hydrogen flame ionization, but could be monitored readily by NH/sub 3/ chemical ionization mass spectrometry. The derivatization reaction occurred partially on-column and required optimization of injection conditions. Using stable isotope ratiometry multiple ion detection, (M + 2 + H)/sup +//(M + H)/sup +/ ion ratio of natural abundance taurine was determined with a standard deviation of less than +-0.07% of the ratio. The (1,2-/sup 13/C)taurine/taurine mole ratios of standard mixtures could be accurately determined to 0.001. This stable isotope gc-ms method is suitable for studying the plasma kinetics of (1,2-/sup 13/C)taurine in infants who are at risk with respect to taurine depletion.

  12. Compound Identification Using Partial and Semi-partial Correlations for Gas Chromatography Mass Spectrometry Data

    PubMed Central

    Kim, Seongho; Koo, Imhoi; Jeong, Jaesik; Wu, Shiwen; Shi, Xue; Zhang, Xiang

    2012-01-01

    Compound identification is a key component of data analysis in the applications of gas chromatographymass spectrometry (GC-MS). Currently, the most widely used compound identification is mass spectrum matching, in which dot product and its composite version are employed as spectral similarity measures. Several forms of transformations for fragment ion intensities have also been proposed to increase the accuracy of compound identification. In this study, we introduced partial and semi-partial correlations as mass spectral similarity measures and applied them to identify compounds along with different transformations of peak intensity. The mixture versions of the proposed method were also developed to further improve the accuracy of compound identification. To demonstrate the performance of the proposed spectral similarity measures, the National Institute of Standard Technology (NIST) mass spectral library and replicate spectral library were used as the reference library and the query spectra, respectively. Identification results showed that the mixture partial and semi-partial correlations always outperform both the dot-product and its composite measure. The mixture similarity with semi-partial correlation has the highest accuracy of 84.6% in compound identification with a transformation of (0.53, 1.3) for fragment ion intensity and m/z value, respectively. PMID:22794294

  13. Comparative Analysis of Mass Spectral Matching-based Compound Identification in Gas Chromatography Mass Spectrometry

    PubMed Central

    Koo, Imhoi; Kim, Seongho; Zhang, Xiang

    2013-01-01

    Compound identification in gas chromatographymass spectrometry (GC-MS) is usually achieved by matching query spectra to spectra present in a reference library. Although several spectral similarity measures have been developed and compared using a small reference library, it still remains unknown how the relationship between the spectral similarity measure and the size of reference library affects on the identification accuracy as well as the optimal weight factor. We used three reference libraries to investigate the dependency of the optimal weight factor, spectral similarity measure and the size of reference library. Our study demonstrated that the optimal weight factor depends on not only spectral similarity measure but also the size of reference library. The mixture semi-partial correlation measure outperforms all existing spectral similarity measures in all tested reference libraries, in spite of the computational expense. Furthermore, the accuracy of compound identification using a larger reference library in future is estimated by varying the size of reference library. Simulation study indicates that the mixture semi-partial correlation measure will have the best performance with the increase of reference library in future. PMID:23726352

  14. Headspace gas chromatography-mass spectrometry of volatile compounds in murici (Byrsonima crassifolia l. Rich).

    PubMed

    Alves, G L; Franco, M R B

    2003-01-24

    Northern and Northeastern Brazil have a natural diversity of fruits, many of which are considered exotic, presenting different flavors and aromas. The enormous diversity of fruits represents a promising area for research on aromas. There is also a great potential for the manufacture of juices, desserts or other processed products. Murici is a typical fruit from these regions presenting a different flavor, reminiscent of that of cheese. This fruit is consumed mainly as juice, ice cream or as liquor, greatly appreciated by the local population. Headspace volatile compounds of three lots of the fruit from Cear (Fortaleza) were collected by suction on Porapak Q for 2 h and desorbed with 300 microl of acetone. The isolated volatile compounds were separated by high resolution GC. Forty-six volatile compounds were detected, of which 41 were identified by gas chromatography-mass spectrometry and Kovats indices. The most abundant compounds were ethanol (28.3%) and ethyl hexanoate (25.1%). Butanoic acid (5.1%), hexanoic acid (5.1%) and methyl butyrate (2.8%) were also detected in the headspace of the fruit and confirm its unusual cheese aroma. PMID:12580497

  15. Determination of phthalate esters in teas and tea infusions by gas chromatography-mass spectrometry.

    PubMed

    Du, Liping; Ma, Lijuan; Qiao, Yang; Lu, Yan; Xiao, Dongguang

    2016-04-15

    Phthalate esters (PAEs), a group of environmental pollutants which are carcinogenic to human body, have been detected in teas. In this work, five PAEs in teas and tea infusions were quantitatively determined by a modified simultaneous distillation extraction (SDE) coupled with gas chromatography-mass spectrometry. After the optimization of SDE, the proposed method afforded a wide range of linearity and high linear regression coefficients with the limits of detection range of 0.24-3.72μg/kg. The average recoveries were 79.83-116.67% for tea samples and 78.22-101.64% for tea infusions with all the relative standard deviations below 20%. The total content of five PAEs in teas was 1.135-3.734mg/kg and the total dissolving ratio of five PAEs from tea to infusion was 19.05-28.07% for the selected tea samples. The risk assessment result of all the selected tea samples demonstrated that the population with the habit of drinking tea won't cause risk to human health. PMID:26675858

  16. Metabolomic profiling in inner ear fluid by gas chromatography/mass spectrometry in guinea pig cochlea.

    PubMed

    Fujita, Takeshi; Yamashita, Daisuke; Irino, Yasuhiro; Kitamoto, Junko; Fukuda, Yuriko; Inokuchi, Go; Hasegawa, Shingo; Otsuki, Naoki; Yoshida, Masaru; Nibu, Ken-ichi

    2015-10-01

    The composition and homeostasis of inner ear fluids are important in hearing function. The purpose of this study was to perform metabolomic analysis of the inner ear fluid in guinea pig cochlea, which has not been previously reported in literature, using gas chromatography/mass spectrometry (GC/MS). Seventy-seven kinds of metabolites were detected in the inner ear fluid. Six metabolites, ascorbic acid, fructose, galactosamine, inositol, pyruvate+oxaloacetic acid, and meso-erythritol, were significantly more abundant, and nine metabolites, phosphate, valine, glycine, glycerol, ornithine, glucose, citric acid+isocitric acid, mannose, and trans-4-hydroxy-L-proline, were less abundant in the inner ear fluid than in plasma. The levels of ten metabolites, 3-hydroxy-butyrate, glycerol, fumaric acid, galactosamine, pyruvate+oxaloacetic acid, phosphate, meso-erythritol, citric acid+isocitric acid, mannose, and inositol, in the inner ear fluid significantly changed after loud noise exposure. These observations may help to elucidate various clinical conditions of sensorineural hearing loss, including noise-induced hearing loss. PMID:26343935

  17. [Comparison of metabolite extraction from Boea hygrometrica by gas chromatography/mass spectrometry].

    PubMed

    Zhang, Xiaofei; Duan, Lixin; Gong, Yuehua; Deng, Xin

    2014-02-01

    This study is aiming to establish an efficient metabolite extraction method for exploration of molecular mechanisms of desiccation tolerance of the resurrection plant Boea hygrometrica using a metabolomics approach. The extracts of metabolite in B. hygrometrica using methanol solution (method A) and methanol-chloroform-water solution (method B) were analyzed by gas chromatography-mass spectrometry (GC-MS). The total numbers of chromatographic peaks, extraction efficiency, retention time and the peak stability were compared. The results showed that for fresh materials, the total chromatographic peak number of method B is more than that of method A; the extraction efficiency of nine representative metabolites by method B is higher than that by method A; the comparison of 10 random chromatographic peaks revealed that the relative standard deviation (RSD) values of the retention time are less than 1% for both methods, whereas the RSD values of the extraction efficiency is different. The percentage of peaks that owned RSD values of the extraction efficiency higher than 10% is 50% for method A and 100% for method B. In addition, method B was also efficient for dry materials from B. hygrometrica. The number of chromatographic peaks, RSD value of retention time and extraction efficiency of dry materials was similar to that of fresh materials using method B, but decreased sharply using method A. Putting together, our study provided evidence that method B is an efficient extraction method for further analysis of metabolites from this resurrection species. PMID:24941750

  18. Simultaneous analysis of termiticides in indoor air by using gas chromatography mass spectrometry.

    PubMed

    Tsuji, Kiyomi; Fushiwaki, Yuichi; Mori, Yasuaki; Arashidani, Keiichi; Nakajima, Daisuke; Fujimaki, Hidekazu; Goto, Sumio

    2005-06-01

    We have established a method for simultaneously analyzing termiticides (13 kinds) in indoor air based on collection by combination of quartz filter and C18 Empore extraction disks, and measurement using gas chromatography mass spectrometry (GC/MS). The lower limit of determination for each substance was 0.02 microg/m3 when 2 m3 of air was sampled. The recovery was 66-100%, and the relative standard deviation was 3.7-14.2%. In experiments using a model box with commercial termiticides, we verified that emissions of bis (2, 3, 3, 3-tetrachloropropyl) ether (S421) increased with a rise in temperature from 10 degrees C to 20 degrees C to 40 degrees C, whereas almost no etofenprox was released into the air regardless of temperature. In addition, decanal, nonanal and alkanes (C13 and C14), which are major components of termiticides, were detected in relatively high concentrations. In the present study, regardless of low vapor pressure of the termiticides, several compounds were detected with the model box experiment. The conclusion that can be drawn is that it is necessary to survey the indoor environmental pollution. PMID:15986770

  19. Characterisation of whiskeys using solid-phase microextraction with gas chromatography-mass spectrometry.

    PubMed

    Fitzgerald, G; James, K J; MacNamara, K; Stack, M A

    2000-10-27

    The application of solid-phase microextraction and gas chromatography-mass spectrometry to the detection of flavour volatiles present in Irish and Scottish whiskeys was investigated. A method was developed to characterise these volatiles which included the extraction, identification and quantification of 17 congeners which included fusel alcohols, acetates and esters. The method validation produced the optimum fibre [85 microm poly(acrylate)], extraction time (35 min), sample volume size (3 ml) and desorption time (5 min). The impact of salt on the absorption process was also studied. Characteristic profiles were determined for each whiskey and the flavour congeners were quantified using 4-methyl-2-pentanol as the internal standard. Calibration ranges were determined for each of the congeners with coefficients of linearity ranging from 0.993 (butan-1-ol) to 0.999 (ethyl laurate) and relative standard deviations ranging from 2.5% (2-methylbutan-1-ol) to 21% (furfural) at a concentration of 18.2 mg/l. Detection limits ranged from 0.1 mg/l (ethyl caprate) to 21 mg/l (butan-2-ol). PMID:11093670

  20. Valid internal standard technique for arson detection based on gas chromatography-mass spectrometry.

    PubMed

    Salgueiro, Pedro A S; Borges, Carlos M F; Bettencourt da Silva, Ricardo J N

    2012-09-28

    The most popular procedures for the detection of residues of accelerants in fire debris are the ones published by the American Society for Testing and Materials (ASTM E1412-07 and E1618-10). The most critical stages of these tests are the conservation of fire debris from the sampling to the laboratory, the extraction of residues of accelerants from the debris to the activated charcoal strips (ACS) and from those to the final solvent, as well as the analysis of sample extract by gas chromatography-mass spectrometry (GC-MS) and the interpretation of the instrumental signal. This work proposes a strategy for checking the quality of the sample conservation, the accelerant residues transference to final solvent and GC-MS analysis, using internal standard additions. It is used internal standards ranging from a highly volatile compound for checking debris conservation to low volatile compound for checking GC-MS repeatability. The developed quality control (QC) parameters are not affected by GC-MS sensitivity variation and, specifically, the GC-MS performance control is not affected by ACS adsorption saturation that may mask test performance deviations. The proposed QC procedure proved to be adequate to check GC-MS repeatability, ACS extraction and sample conservation since: (1) standard additions are affected by negligible uncertainty and (2) observed dispersion of QC parameters are fit for its intended use. PMID:22920302

  1. Urinary Succinylacetone Analysis by Gas Chromatography-Mass Spectrometry (GC-MS).

    PubMed

    Chen, Hongjie; Yu, Chunli

    2016-01-01

    Succinylacetone (SA) is used for the diagnosis and monitoring of patients with tyrosinemia type I (Tyr I). SA is exclusively elevated in blood and urine of patients with Tyr I. As urinary SA concentration is much higher than blood, SA is usually tested in urine samples. Urinary SA quantitation by gas chromatography mass spectrometry (GC-MS) is described in this chapter. The urine sample in the amount of 1 ?mol creatinine is used for testing. 3,4,5,6,7-(13)C5-succinylacetone ((13)C5-SA) is used as an internal standard (IS). SA and (13)C5-SA are oximated and extracted from urine with organic solvents, and then derivatized to form trimethylsilane (TMS) derivatives. TMS derivatives of SA and (13)C5-SA are detected and quantified by GC-MS using selective ion monitoring (SIM). The assay is linear from 0.05 to 450 mmol/mol creatinine to cover the broad range of urinary SA concentrations. PMID:26602140

  2. Automated thermochemolysis reactor for detection of Bacillus anthracis endospores by gas chromatography-mass spectrometry.

    PubMed

    Li, Dan; Rands, Anthony D; Losee, Scott C; Holt, Brian C; Williams, John R; Lammert, Stephen A; Robison, Richard A; Tolley, H Dennis; Lee, Milton L

    2013-05-01

    An automated sample preparation system was developed and tested for the rapid detection of Bacillus anthracis endospores by gas chromatography-mass spectrometry (GC-MS) for eventual use in the field. This reactor is capable of automatically processing suspected bio-threat agents to release and derivatize unique chemical biomarkers by thermochemolysis (TCM). The system automatically controls the movement of sample vials from one position to another, crimping of septum caps onto the vials, precise delivery of reagents, and TCM reaction times and temperatures. The specific operations of introduction of sample vials, solid phase microextraction (SPME) sampling, injection into the GC-MS system, and ejection of used vials from the system were performed manually in this study, although they can be integrated into the automated system. Manual SPME sampling is performed by following visual and audible signal prompts for inserting the fiber into and retracting it from the sampling port. A rotating carousel design allows for simultaneous sample collection, reaction, biomarker extraction and analysis of sequential samples. Dipicolinic acid methyl ester (DPAME), 3-methyl-2-butenoic acid methyl ester (a fragment of anthrose) and two methylated sugars were used to compare the performance of the autoreactor with manual TCM. Statistical algorithms were used to construct reliable bacterial endospore signatures, and 24 out of 25 (96%) endospore-forming Bacillus species were correctly identified in a statistically designed test. PMID:23601976

  3. Analysis of endogenous aldehydes in human urine by static headspace gas chromatography-mass spectrometry.

    PubMed

    Serrano, María; Gallego, Mercedes; Silva, Manuel

    2016-03-11

    Endogenous aldehydes (EAs) generated during oxidative stress and cell processes are associated with many pathogenic and toxicogenic processes. The aim of this research was to develop a solvent-free and automated analytical method for the determination of EAs in human urine using a static headspace generator sampler coupled with gas chromatography-mass spectrometry (HS-GC-MS). Twelve significant EAs used as markers of different biochemical and physiological processes, namely short- and medium-chain alkanals, α,β-unsaturated aldehydes and dicarbonyl aldehydes have been selected as target analytes. Human urine samples (no dilution is required) were derivatized with O-2,3,4,5,6-pentafluorobenzylhydroxylamine in alkaline medium (hydrogen carbonate-carbonate buffer, pH 10.3). The HS-GC-MS method developed renders an efficient tool for the sensitive and precise determination of EAs in human urine with limits of detection from 1 to 15ng/L and relative standard deviations, (RSDs) from 6.0 to 7.9%. Average recoveries by enriching urine samples ranged between 92 and 95%. Aldehydes were readily determined at 0.005-50μg/L levels in human urine from healthy subjects, smokers and diabetic adults. PMID:26879451

  4. The gas chromatography/mass spectrometry can be used for dose estimation in irradiated pork

    NASA Astrophysics Data System (ADS)

    D'Oca, M. C.; Bartolotta, A.; Cammilleri, M. C.; Giuffrida, S. A.; Parlato, A.; Di Noto, A. M.; Caracappa, S.

    2009-07-01

    Food safety can be improved using ionizing radiation to reduce food spoilage and to extend its shelf life. The gas chromatography/mass spectrometry (GC/MS) has been validated by the European Community as a powerful method to identify irradiated food containing fat. The preliminary goals of our research were: (i) to set up this method, based on the detection of radiation induced 2-dodecylcyclobutanones (2-DCB) in pork muscle samples and (ii) to check the microbiological efficacy of the treatment. The main objective was to render the GC/MS a quantitative technique for dose estimation, through the measurement of the 2-DCB concentration in the irradiated sample. Our results show that the reduction of the microbial population is substantially reduced even at 2 kGy, and that a clear identification of irradiated samples can be achieved also one month after irradiation at 2 kGy in frozen-stored samples. The 2-DCB concentration showed a linear dependence on dose in the range 1-10 kGy, no matter the origin of the sample; a unique calibration function was obtained, that allowed dose estimation in irradiated pork samples. A retrospective evaluation on the quality of the treatment could be carried out this way.

  5. Analysis of Tropical Forest Fire Emissions Using in Situ Gas Chromatography/Mass Spectrometry during Sambba

    NASA Astrophysics Data System (ADS)

    Minaeian, J.; Lewis, A. C.; Edwards, P. M.; Evans, M. J.; Hopkins, J. R.; Lee, J. D.; Purvis, R.

    2014-12-01

    Vertical atmospheric profiles of volatile organic compounds (VOCs) were made over Amazonia using an in situ gas chromatography/mass spectrometer (GC/MS), including isoprene, methacrolein, methyl vinyl ketone and products of biomass burning such as benzene. Measurements were made in the Amazonian (Rondnia and Amazonas) region during September 2012, a period of extensive biomass burning. Data was obtained between 100m and 8500m from the FAAM BAe 146 research aircraft. Isoprene was observed to be constrained overwhelmingly to the boundary layer (height typically ~2500m) with mean boundary layer mixing ratio of ~2 ppbv and a peak of ~5 ppbv at the lowest flight levels of 100 m. First generation isoprene oxidation products, methyl vinyl ketone and methacrolein, were quantified individually rather than as the sum of the pair, which is more commonly found in the literature. Both MACR and MVK were constrained primarily to the boundary layer, however trace quantities could be seen in the free troposphere to a height of 8000 m. Benzene from biomass burning was observed in both boundary layer and free troposphere, with a peak mixing ratio of ~0.8 ppbv at 750 m. This work will present the spatial distribution of isoprene within the boundary as a function of underlying surface type. The vertical profiles of all species are then compared to representative simulations from the GEOS-Chem chemistry transport model and conclusions drawn on the success of the model in representing emissions and oxidation chemistry.

  6. Toward automated chromatographic fingerprinting: A non-alignment approach to gas chromatography mass spectrometry data.

    PubMed

    Vestner, Jochen; de Revel, Gilles; Krieger-Weber, Sibylle; Rauhut, Doris; du Toit, Maret; de Villiers, André

    2016-03-10

    In contrast to targeted analysis of volatile compounds, non-targeted approaches take information of known and unknown compounds into account, are inherently more comprehensive and give a more holistic representation of the sample composition. Although several non-targeted approaches have been developed, there's still a demand for automated data processing tools, especially for complex multi-way data such as chromatographic data obtained from multichannel detectors. This work was therefore aimed at developing a data processing procedure for gas chromatography mass spectrometry (GC-MS) data obtained from non-targeted analysis of volatile compounds. The developed approach uses basic matrix manipulation of segmented GC-MS chromatograms and PARAFAC multi-way modelling. The approach takes retention time shifts and peak shape deformations between samples into account and can be done with the freely available N-way toolbox for MATLAB. A demonstration of the new fingerprinting approach is presented using an artificial GC-MS data set and an experimental full-scan GC-MS data set obtained for a set of experimental wines. PMID:26893085

  7. Magnetic solid phase extraction and gas chromatography-mass spectrometrical analysis of sixteen polycyclic aromatic hydrocarbons.

    PubMed

    Cai, Ying; Yan, Zhihong; NguyenVan, Manh; Wang, Lijia; Cai, Qingyun

    2015-08-01

    Fluorenyl functionalized superparamagnetic core/shell magnetic nanoparticles (MNPs, Fe3O4@SiO2@Flu) were prepared and characterized by transmission electron microscope, X-ray diffraction and infrared spectroscopy. The MNPs having an average diameter of 200nm were then used as solid-phase extraction sorbent for the determination of 16 priority pollutants polycyclic aromatic hydrocarbons (PAHs) in water samples designated by United States Environmental Protection Agency (U.S. EPA). The main influencing parameters, including sorbent amount, desorption solvent, sample volume and extraction time were optimized. Analyses were performed on gas chromatography-mass spectrometry (GC-MS) using selected ion monitoring (SIM) mode. Method validation proved the feasibility of the developed sorbents for the quantitation of the investigated analytes at trace levels. Limit of detection ranging from 0.5 to 4.0ng/L were obtained. The repeatability was investigated by evaluating the intra- and inter-day precisions with relative standard deviations (RSDs) lower than 13.1%. Finally, the proposed method was successfully applied for the determination of PAHs in water samples with the recoveries in the range of 96.0-106.7%. PMID:26122856

  8. Multi-class method for biomonitoring of hair samples using gas chromatography-mass spectrometry.

    PubMed

    Martín, Julia; Möder, Monika; Gaudl, Alexander; Alonso, Esteban; Reemtsma, Thorsten

    2015-11-01

    Currently, non-invasive biomonitoring of human exposure to organic pollutants bases upon the analysis mainly of urine and human breast milk. While mostly persistent organic pollutants are the center of interest, the aim of our study was to develop a method for the determination of different chemical classes of emerging pollutants (organophosphorus flame retardants, plastic additives such as phthalates, bisphenol A, insecticides, antimicrobials, preservatives and musk fragrances) in hair by gas chromatography-mass spectrometry. The preferred sample preparation included hydrolysis of the hair with trifluoroacetic acid in methanol followed by a liquid-liquid extraction using hexane/ethyl acetate. The validated method is characterized by recoveries higher than 77 % for most analytes, relative standard deviations below 16 % and limits of detection between 2 pg mg(-1) (HHCB) and 292 pg mg(-1) (propylparaben) using 50 mg of dry hair. After respective blank corrections, bis-(2-ethylhexyl)phthalate (DEHP) and the musk fragrance HHCB were the predominant compounds determined in all hair samples at concentrations between 32 and 59 ng mg(-1) and 0.8-13 ng mg(-1), respectively. The bactericide triclosan and the insect repellent N,N-diethyl-3-methylbenzamide (DEET) were detected in selected hair samples at 2 and 0.8 ng mg(-1), respectively. PMID:26427497

  9. Determination of Menthol in Plasma and Urine by Gas Chromatography/Mass Spectrometry (GC/MS).

    PubMed

    Peat, Judy; Frazee, Clint; Kearns, Gregory; Garg, Uttam

    2016-01-01

    Menthol, a monoterpene, is a principal component of peppermint oil and is used extensively in consumer products as a flavoring aid. It is also commonly used medicinally as a topical skin coolant; to treat inflammation of the mucous membranes, digestive problems, and irritable bowel syndrome (IBS); and in preventing spasms during endoscopy and for its spasmolytic effect on the smooth muscle of the gastrointestinal tract. Menthol has a half life of 3-6 h and is rapidly metabolized to menthol glucuronide which is detectable in urine and serum following menthol use. We describe a method for the determination of total menthol in human plasma and urine using liquid/liquid extraction, gas chromatography/mass spectrometry (GC/MS) in selected ion monitoring mode and menthol-d4 as the internal standard. Controls are prepared with menthol glucuronide and all samples undergo enzymatic hydrolysis for the quantification of total menthol. The method has a linear range of 5-1000 ng/mL, and coefficient of variation <10 %. PMID:26660189

  10. Pharmaceuticals in grocery market fish fillets by gas chromatography-mass spectrometry.

    PubMed

    Mottaleb, Musavvir Arafat; Stowe, Carly; Johnson, Daniel R; Meziani, Mohammed J; Mottaleb, M Abdul

    2016-01-01

    Occurrences of pharmaceuticals are evident in aquatic organisms. A reproducible gas chromatography-mass spectrometry (GC-MS) method using selected ion monitoring (SIM) has been used to determine the anti-histamine diphenhydramine (DPH), anti-anxiety diazepam (DZP), anti-seizure carbamazepine (CZP) drugs and their metabolites in grocery stores fish that were homogenized, extracted, pre-concentrated, cleaned up, and examined. Identifications of the compounds in extracts were obtained by comparing similar mass spectral features and retention properties with standards. Among nine frequently detected drugs, only DPH and DZP were observed and ranged from 0.61 to 6.21 and 1.99 to 16.57 ng/g, respectively, in fourteen fish species. These concentration values were lower than the environmental fish. Mean spike recoveries of analytes exceeded 75% with relative standard deviations (RSD)<10%. The statistically-derived method detection limits (MDLs) for nine compounds ranged from 0.13 to 5.56 ng/g. Average surrogate recoveries were 80-85% with 4-9% RSD. PMID:26213006

  11. Structural identification of petroleum acids by conversion to hydrocarbons and multidimensional gas chromatography-mass spectrometry.

    PubMed

    Wilde, Michael J; Rowland, Steven J

    2015-08-18

    Identification of individual petroleum acids ("naphthenic" acids, NA) has proved challenging for decades, due to the extreme complexity of many petroleum acid mixtures. This has hindered detailed understanding of the role of NA in petroleum generation and oil production processes, refinery corrosion, as wood preservatives, and as environmental toxicants. Some recent advances have been made due to improved chromatographic separation of esters of the acids by multidimensional gas chromatography-mass spectrometry (GC GC-MS), but relatively few reference spectra of esters are available for comparison. Here we report a complementary method based on a combination of a modified historical approach of converting NA to the corresponding hydrocarbons, followed by analysis by GC GC-MS. Many published spectra exist for reference hydrocarbons making comparisons of reference spectra with those of the unknowns, much more feasible. As an example, we report identification of over 30 individual bicyclic naphthenic acids as the bicyclane hydrocarbons. These include both fused and bridged acids possessing methyl, dimethyl, and ethyl alkyl substituents as well as some terpenoid-derived acids. The study provides the most comprehensive analysis of one of the major classes of NA (the bicyclic acids) to date. There is now clear potential for this method to be used for the structural elucidation of other unknown acids (e.g., oil sands acids) and functionalized biomarkers in complex mixtures. PMID:26171636

  12. Identification of tartary buckwheat tea aroma compounds with gas chromatography-mass spectrometry.

    PubMed

    Qin, Peiyou; Ma, Tingjun; Wu, Li; Shan, Fang; Ren, Guixing

    2011-08-01

    Tartary buckwheat tea, which is an important and healthy product, has a distinct malty aroma. However, its characteristic aroma compounds have not been elucidated. The aims of present study were identification and quantification of its aroma compounds. The analyses were performed by gas chromatography-mass spectrometry (GC-MS) after 3 different isolation techniques. Seventy-seven compounds were identified. Among these compounds, 35 were quantified by available standards. The compounds with a high probability of contribution to the tartary buckwheat tea aroma (OAV ≥ 10) were as follows: 2,5-dimethyl-4-hydroxy-3(2H)-furanone, nonanal, 2,3-diethyl-5-methylpyrazine, benzeneacetaldehyde, maltol, 2,5-dimethylpyrazine, 2-ethyl-5-methylpyrazine, trimethylpyrazine. Some nutritional and bioactive compounds were also identified in this study, such as linoleic acid, niacin, vanillic acid, 7-hydroxycoumarin, butylated hydroxytoluene. Practical Application: Tartary buckwheat, one type of buckwheat, has gained much attention from nutritionists and medical doctors in recent years. It is rich in rutin, quercetin, and other nutrients that are good for health. Tartary buckwheat-based product such as tartary buckwheat tea is an important and popular healthy product in China, Japan,South Korea, European countries as well as in American countries. It has a distinct malty aroma. The present study first identified and quantified of its aroma compounds. The results will draw attention to other researchers in food flavor and buckwheat filed. PMID:22417522

  13. Identification of monoacylglycerol regio-isomers by gas chromatography-mass spectrometry.

    PubMed

    Destaillats, Frdric; Cruz-Hernandez, Cristina; Nagy, Kornl; Dionisi, Fabiola

    2010-02-26

    Monoacylglycerols (MAGs) are lipids found in trace amounts in plants and animal tissues. While they are widely used in various industrial applications, accurate determination of the regio-specific distribution is hindered by the lack of stable, commercially available standards. Indeed, unsaturated beta-MAG (or Sn-2 MAG) readily undergoes isomerization into alpha-MAG (acyl chain is attached to the Sn-1 or the Sn-3 position). In the present study, we describe structural elucidation of alpha- and beta-regio-isomers of monopalmitoyl-glycerol (MAG C16:0) as model compounds in their silylated forms using gas chromatography-mass spectrometry (GC-MS) with electronic impact (EI) ionization. MS fragmentation of alpha-MAG C16:0 is characterized by the loss of methylene(trimethylsilyl)oxonium (103 amu) and the consecutive loss of acyl chain yielding a fragment ion at m/z 205. The fragmentation pattern of beta-MAG C16:0 shows a series of diagnostic fragments at m/z 218, 203, 191 and 103 that are not formed from the alpha-isomer and hereby enable reliable distinction of these regio-isomers. Possible fragmentation scenarios are postulated to explain the formation of these marker ions, which were also applied to characterize the regio-isomer composition of a complex mixture of MAG sample containing n-3 long-chain polyunsaturated fatty acids. PMID:20097347

  14. Analysis of sugars in environmental samples by gas chromatography-mass spectrometry.

    PubMed

    Medeiros, Patricia M; Simoneit, Bernd R T

    2007-02-01

    Many environmental samples contain complex mixtures of organic compounds with different sources, polarities and reactivities. This study reports a method for the analysis of both polar/water-soluble and apolar organic compounds in several kinds of environmental samples. The analytical method consists of extraction with a mixture of dichloromethane:methanol (2:1, v/v), silylation using BSTFA (N,O-bis-(trimethylsilyl)trifluoroacetamide) and analysis by gas chromatography-mass spectrometry (GC-MS), a common device in chemical and environmental laboratories. Fifty individual sugar standards, including monosaccharides, sugar alcohols, anhydrosugars, disaccharides and trisaccharides, were analyzed for the determination of their fragmentation patterns and retention times. Recoveries (at three concentrations) and limits of detection (LOD) were determined for a standard mixture containing glucose (monosaccharide), sorbitol (sugar alcohol), levoglucosan (anhydrosugar) and sucrose (disaccharide), and they varied from 68 to 119% and 130 to 360 ng mL(-1), respectively. The method was used for the analysis of aerosol particle, soil and sediment samples, and demonstrated its feasibility in detecting not only several important environmental sugars (e.g., glucose, fructose, inositol, mannitol, sorbitol, levoglucosan, sucrose, mycose), but also a large range of organic compound classes from other polar components (e.g., dicarboxylic acids) to apolar compounds such as n-alkanes. Therefore, the analytical method presented here demonstrated its usefulness for a better understanding of sources and transport of various organic compounds in different environmental compartments. PMID:17207493

  15. Identification of floral scent in chrysanthemum cultivars and wild relatives by gas chromatography-mass spectrometry.

    PubMed

    Sun, Hainan; Zhang, Ting; Fan, Qingqing; Qi, Xiangyu; Zhang, Fei; Fang, Weimin; Jiang, Jiafu; Chen, Fadi; Chen, Sumei

    2015-01-01

    The objective of this study was to identify the major volatile compounds and their relative concentrations in flowers of different chrysanthemum cultivars and their wild relatives. The volatile organic components of fresh flowers were analyzed using a headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry. In total, 193 volatile organic components were detected; the major scent components were monoterpenoids and oxygenated monoterpenoids, which accounted for 68.59%-99.93% of the total volatiles in all tested materials except for Chrysanthemum indicum collected from Huangshan, in which they accounted for only 37.45% of total volatiles. The major volatile compounds were camphor, ?-pinene, chrysanthenone, safranal, myrcene, eucalyptol, 2,4,5,6,7,7ab-hexahydro-1H-indene, verbenone, ?-phellandrene and camphene. In a hierarchical cluster analysis, 39 accessions of Chrysanthemum and its relatives formed six clusters based on their floral volatile compounds. In a principal component analysis, only spider type flowers were located closely on the score plot. The results of this study provide a basis for breeding chrysanthemum cultivars which desirable floral scents. PMID:25816078

  16. Curie-point pyrolysis-gas chromatography/mass spectrometry in the art field. 2--The characterization of proteinaceous binders.

    PubMed

    Carbini, M; Stevanato, R; Rovea, M; Traldi, P; Favretto, D

    1996-01-01

    Curie point pyrolysis with gas chromatography/mass spectrometry has been employed to characterize some proteinaceous media used in the art field as painting binders: milk casein, egg yolk, egg albumin, bone glue, skin glue, rabbit glue and fish glue. A careful analysis of the gas chromatograms so obtained has led to the distinction of the different proteinaceous binders in terms of different chromatographic profiles. Some of the pyrolysis products have been identified by library search. PMID:8759333

  17. Triple sorbent thermal desorption/gas chromatography/mass spectrometry determination of vapor phase organic contaminants

    SciTech Connect

    Ma, C.Y.; Skeen, J.T.; Dindal, A.B.; Higgins, C.E.; Jenkins, R.A.

    1994-12-31

    A thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS) method has been evaluated for the determination of volatile organic compounds (VOCs) in vapor phase samples using Carbosieve S-III/Carbotrap/Carbotrap C triple sorbent traps (TST), similar to those available from a commercial source. The analysis was carried out with a Hewlett-Packard 5985A or 5995 GC/MS system with a modified injector to adapt an in-house manufactured short-path desorber for transferring desorbate directly onto a cryofocusing loop for subsequent GC/MS analysis. Vapor phase standards generated from 26 compounds were used for method validation, including alkanes, alkyl alcohols, alkyl ketones, and alkyl nitriles, a group of representative compounds that have previously been identified in a target airborne matrix. The method was validated based on the satisfactory results in terms of reproducibility, recovery rate, stability, and linearity. A relative standard deviation of 0.55 to 24.3% was obtained for the entire TD process (generation of gas phase standards, spiking the standards on and desorbing from TST) over a concentration range of 20 to 500 ng/trap. Linear correlation coefficients for the calibration curves as determined ranged from 0.81 to 0.99 and limits of detection ranged from 3 to 76 ng. For a majority of standards, recoveries of greater than 90% were observed. For three selected standards spiked on TSTs, minimal loss (10 to 22%) was observed after storing the spiked traps in a 4 C refrigerator for 29 days. The only chromatographic artifact observed was a 5% conversion of isopropanol to acetone. The validated method has been successfully applied to the determination of VOCs collected from various emission sources in a diversified concentration range.

  18. APPLICATIONS OF INFORMATION THEORY AND PATTERN RECOGNITION TO GAS CHROMATOGRAPHY-MASS SPECTROMETRIC ANALYSIS OF TOXIC ORGANIC COMPOUNDS IN AMBIENT AIR

    EPA Science Inventory

    The number of information channels contained in the gas chromatographic, mass spectrometric, and combined gas chromatography-mass spectrometric analysis of 78 toxic organic compounds has been determined. The toxic compounds are those routinely monitored in ambient air samples usi...

  19. Whole Microorganisms Studied by Pyrolysis-Gas Chromatography-Mass Spectrometry: Significance for Extraterrestrial Life Detection Experiments 1

    PubMed Central

    Simmonds, Peter G.

    1970-01-01

    Pyrolysis-gas chromatography-mass spectrometric studies of two microorganisms, Micrococcus luteus and Bacillus subtilis var. niger, indicate that the majority of thermal fragments originate from the principal classes of bio-organic matter found in living systems such as protein and carbohydrate. Furthermore, there is a close qualitative similarity between the type of pyrolysis products found in microorganisms and the pyrolysates of other biological materials. Conversely, there is very little correlation between microbial pyrolysates and comparable pyrolysis studies of meteoritic and fossil organic matter. These observations will aid in the interpretation of a soil organic analysis experiment to be performed on the surface of Mars in 1975. The science payload of this landed mission will include a combined pyrolysis-gas chromatography-mass spectrometry instrument as well as several direct biology experiments which are designed to search for extraterrestrial life. PMID:16349890

  20. Determination of herbicides by solid phase extraction gas chromatography-mass spectrometry in drinking waters.

    PubMed

    Bruzzoniti, M C; Sarzanini, C; Costantino, G; Fungi, M

    2006-09-25

    A solid phase extraction (SPE) method has been optimized for the gas chromatography-mass spectrometry (GC-MS) simultaneous determination of herbicides belonging to the following different families: carbamate (molinate), atrazines (atrazine, propazine, simazine, ametryne, cyanazine, terbutylazine, deethylterbutylazine, deethylatrazine), dinitroaniline (trifluralin, pendimethalin), chloroacetamide (alachlor, metolachlor). Different solid substrates have been compared (C18, cyano, styrene-divinylbenzene, phenyl, graphitic carbon). The type of conditioning and elution solvent, its volume, and the sample flow rate have been considered as variables affecting the recovery yields of the herbicides. The optimized experimental conditions are C18 phase conditioned with 3 mL acetone, loaded with 1L water sample at 5 mL min(-1), and eluted with 3 mL acetone. Good recoveries (included between 79% and 99%) and R.S.D. (included between 2% and 12%) have been obtained for all analytes, except for deethylatrazine whose recovery was 46+/-7%. The recovery of deethylatrazine increases up to 94+/-17% if a non-porous graphitic carbon is coupled to the C18 phase, keeping the other parameters constant as optimized. The optimized method has been successfully checked for the identification and quantitation of the selected herbicides in raw and drinking water samples, with quantitation limits as low as 0.01 microg L(-1), fully in agreement with the current legislation. The method is easily routinable. After development, the method is currently routinely applied for the analysis of herbicides in waters and, up today, more than one thousand samples have been analysed at the "Laboratorio della Societ Metropolitana Acque di Torino" (Laboratory of the Municipal Waterworks of Turin) in charge of the control of drinking water quality in Torino. PMID:17723718

  1. Urine Mescaline Screening With a Biochip Array Immunoassay and Quantification by Gas Chromatography-Mass Spectrometry.

    PubMed

    Battal, Dilek; Barnes, Allan J; Castaneto, Marisol S; Martin, Thomas M; Klette, Kevin L; Huestis, Marilyn A

    2015-12-01

    Mescaline, the primary psychoactive chemical in peyote cactus, has been consumed for thousands of years in ancient religious ceremonies. The US military wanted to determine if mescaline intake was a problem for personnel readiness. Twenty thousand seventeen urine specimens negative for cannabinoids, cocaine, opiates, and amphetamines were tested for mescaline with the Randox Drugs of Abuse V (DOA-V) biochip array immunoassay at the manufacturer's recommended cutoff of 6 mcg/L. A sensitive and specific method for mescaline quantification in urine was developed and fully validated. Extracted analytes were derivatized with pentafluoropropionic anhydride and pentafluoropropanol and quantified by gas chromatography-mass spectrometry (GC/MS) with electron impact ionization. Standard curves, using linear least squares regression with 1/x weighting, were linear from 1 to 250 mcg/L with coefficients of determination >0.994. Intra- and inter-assay imprecision was <4.4 coefficient of variation (%CV), with accuracies >90.4%. Mean extraction efficiencies were >92.0% across the linear range. This fully validated method was applied for the confirmation of urinary mescaline in 526 presumptive-positive specimens and 198 randomly selected presumptive-negative specimens at the manufacturer's 6 mcg/L cutoff. No specimen confirmed positive at the GC/MS limit of quantification of 1 mcg/L. Results indicated that during this time frame, there was insufficient mescaline drug use in the military to warrant routine screening in the drug testing program. However, mescaline stability, although assessed, could have contributed to lower prevalence. We also present a validated GC/MS method for mescaline quantification in urine for reliable confirmation of suspected mescaline intake. PMID:25992796

  2. [Simultaneous determination of five hypertoxic rodenticides in serum by gas chromatography-mass spectrometry].

    PubMed

    Huang, Huiqiu; Huang, Xun; Yu, Jingsun

    2015-03-01

    A fast analytical method based on gas chromatography-mass spectrometry (GC-MS) was established for the simultaneous determination of tetramine, fluoroacetamide, sodium fluoroacetate, gliftor I and gliftor II in serum. At pH 2.0, sodium fluoroacetate was derivatizated at room temperature for 5 min by using N,N-diethyl-p-phenylenediamine as the derivatization reagent and N, N'-dicyclohexylcarbodiimide as the catalyst. The derivative and other rodenticides were extracted with ethyl acetate and concentrated with nitrogen at 50 C, then determined by GC-MS in selected ion monitoring (SIM) mode, and quantified with matrix-match standard solutions. The analysis was carried out on an ionic liquid chromatographic capillary column (SLB-IL59, 30 m x 0.25 mm x 0.20 m, maximum temperature 300 C) at a flow rate of 1.0 mL/min, and the five rodenticides were successfully separated in 15 min when temperature programming was used. The results showed that the calibration curves were linear in the range of 0.01-1.0 mg/L, except for fluoroacetamide (0.02-2.0 mg/L) and tetramine (0.02-10 mg/L), with correlation coefficients (R2) greater than 0.995, and the limits of detection (LODs) were 0.001-0.002 mg/L (S/N = 3). The recoveries were 84.0%-110.0% at three different spiked levels, and the relative standard deviations (RSDs) were 2.9%-7.5% (n = 6). The method is simple, accurate, highly sensitive and suitable for the detection of the five hypertoxic rodenticides in serum for toxicological purposes. PMID:26182477

  3. Quantitation of opioids in whole blood by electron impact-gas chromatography-mass spectrometry.

    PubMed

    Tiscione, Nicholas B; Shan, Xiaoqin; Alford, Ilene; Yeatman, Dustin Tate

    2011-03-01

    Opioids are frequently encountered in Forensic Toxicology casework. A PubMed literature search was conducted to find a method using electron impact-gas chromatography-mass spectrometry to examine whole blood specimens. A previously published method was identified, and an updated version was provided by the State of North Carolina Office of the Chief Medical Examiner. This procedure was used as a starting point for development and validation of a refined procedure to be used in the Palm Beach County Sheriff's Office Forensic Toxicology laboratory for routine analysis of antemortem forensic toxicology case samples. Materials and instrumentation common to most forensic toxicology laboratories were utilized while obtaining detection limits from 1 to 10 ng/mL and quantitation limits of 2.5 to 10 ng/mL using 1 mL of whole blood. Target compounds were chosen based on applicability to the method as well as availability and common use in the United States and include dihydrocodeine, codeine, morphine, hydrocodone, 6-monoacetylmorphine, hydromorphone, oxycodone, and oxymorphone. Each analyte demonstrated two zero-order linear ranges (r(2) > 0.990) over the concentrations evaluated (from 2.5 to 500 ng/mL). The coefficient of variation of replicate analyses was less than 12%. Quantitative accuracy was within 27% at 2.5 ng/mL, 11% at 10 ng/mL, and 8% at 50 ng/mL. The validated method provides a more sensitive procedure for the quantitation of common opioids in blood using standard laboratory equipment and a small amount of sample. PMID:21396229

  4. Systematic analysis of glycerol: colourimetric screening and gas chromatography-mass spectrometric confirmation.

    PubMed

    Sardela, Vincius F; Scalco, Fernanda B; Cavalcante, Karina M; Simoni, Ruth E; Silva, Deyvison R; Pereira, Henrique Marcelo G; de Oliveira, Maria Lcia L Costa; Aquino Neto, Francisco R

    2015-10-01

    Glycerol is a naturally occurring polyol in the human body, essential for several metabolic processes. It is widely used in the food, pharmaceutical, and medical industries and in clinical practice as a plasma volume expander (PVE). Athletes, however, may use glycerol to mask the presence of forbidden substances or to enhance performance, inclusively through hyperhydration achieved by glycerol ingestion with added fluid. These practices are considered doping, and are prohibited by the World Anti-Doping Agency (WADA). Therefore, glycerol was introduced in the prohibited list. Doping through glycerol ingestion can readily be identified by detection of elevated glycerol concentrations in urine. In this paper, a protocol for the fast detection of glycerol in urine is proposed. It consists of a previous visual colourimetric screening, followed by a quantitative/qualitative confirmation analysis by mass spectrometry. The screening procedure involves a reaction in which polyhydric alcohols are oxidized by periodate to formic acid and formaldehyde, which is detected by the addition of a fuchsin solution. For the subsequent qualitative/quantitative confirmation analysis, a gas chromatography-mass spectrometry based approach with a non-deuterated internal standard and a drying step of only 10 min is proposed. The linear correlation was demonstrated within WADAs threshold range. The calculated RSD were 2.1% for within-day precision and 2.8% for between-day precision. The uncertainty estimation was calculated, and a value of 2.7% was obtained. The procedure may also be used for the analysis of other polyols in urine, as for example the PVE mannitol. PMID:26112364

  5. Triple sorbent thermal desorption/gas chromatography/mass spectrometry determination of vapor phase organic contaminants

    SciTech Connect

    Ma, C.Y.; Skeen, J.T.; Dindal, A.B.; Higgins, C.E.; Jenkins, R.A.

    1994-05-01

    A thermal desorption/ps chromatography/mass spectrometry (TD/GC/MS) has been evaluated for the determination of volatile organic compounds (VOCS) in vapor phase samples using Carbosieve S-III/Carbotrap/Carotrap C triple sorbent traps (TST) similar to those available from a commercial source. The analysis was carried out with a Hewlett-Packard 5985A or 5995 GC/MS system with a modified injector to adapt an inhouse manufactured short-path desorber for transferring desorbate directly onto a cryofocusing loop for subsequent GC/MS analysis. Vapor phase standards generated from twenty six compounds were used for method validation, including alkanes, alkyl alcohols, alkyl ketones, and alkyl nitrites, a group of representative compounds that have previously been identified in a target airborne matrix. The method was validated based on the satisfactory results in terms of reproducibility, recovery rate, stability, and linearity. A relative, standard deviation of 0.55 to 24.3 % was obtained for the entire TD process (generation of gas phase standards, spiking the standards on and desorbing from TST) over a concentration range of 20 to 500 ng/trap. Linear correlation coefficients for the calibration curves as determined ranged from 0.81 to 0.99 and limits of detection ranged from 3 to 76 ng. For a majority of standards, recoveries of greater than 90% were observed. For three selected standards spiked on TSTS, minimal loss (10 to 22%) was observed after storing the spiked in, a 4{degree}C refrigerator for 29 days. The only chromatographable artifact observed was a 5% conversion of isopropanol to acetone. The validated method been successfully applied, to the determination of VOCs collected from various emission sources in a diversified concentration range.

  6. Determination of organoarsenic warfare agents in sediment samples from Skagerrak by gas chromatography-mass spectrometry.

    PubMed

    Trnes, John Aasulf; Opstad, Aase Mari; Johnsen, Bjrn Arne

    2006-03-01

    In 1945 the Norwegian authorities gave permission to scuttle ships loaded with captured chemical ammunition on board in an area approximately 14x4 km in size, 25 nautical miles south-east of Arendal. An investigation was carried out in 2002 to inspect four wrecks by using a remote-operated vehicle with video cameras. The Norwegian Defence Research Establishment (Forsvarets forskningsinstitutt, FFI) carried out the project on behalf of the Norwegian Pollution Control Authority (SFT). Sediment samples were collected at eight positions around each wreck. One of the wrecks was broken up into several smaller parts. Here sediments were collected at one additional position close to one of the parts. From each position, at least two sediment cores were taken up to the surface. One of the cores from each position was sliced into three parts that were immediately frozen. The other whole cores were frozen on board the ship and transported back to the laboratory in a freezer. In total, sediment samples from 33 different locations were collected and analysed for organoarsenic warfare agents and some of their decomposition products by gas chromatography-mass spectrometry (GC-MS) after derivatisation with 1-propanethiol. Most of the identified organoarsenic compounds found in the sediment samples are parts of the arsine oil mixture produced by Germany during World War II. The compounds were found both close to the wreck and at a somewhat longer distance from the wrecks. The highest concentrations were found in a sediment sample collected close to a bomb seen on the seabed. The organoarsenic warfare agents adamsite or lewisite were not found in any of the samples. Lewisite is not reported to have been produced during World War II, but was nevertheless looked for in the samples. PMID:15993928

  7. Supervised pattern recognition procedures for discrimination of whiskeys from gas chromatography/mass spectrometry congener analysis.

    PubMed

    Gonzlez-Arjona, Domingo; Lpez-Prez, Germn; Gonzlez-Gallero, Vctor; Gonzlez, A Gustavo

    2006-03-22

    The volatile congener analysis of 52 commercialized whiskeys (24 samples of single malt Scotch whiskey, 18 samples of bourbon whiskey, and 10 samples of Irish whiskey) was carried out by gas chromatography/mass spectrometry after liquid-liquid extraction with dichloromethane. Pattern recognition procedures were applied for discrimination of different whiskey categories. Multivariate data analysis includes linear discriminant analysis (LDA), k nearest neighbors (KNN), soft independent modeling of class analogy (SIMCA), procrustes discriminant analysis (PDA), and artificial neural networks techniques involving multilayer perceptrons (MLP) and probabilistic neural networks (PNN). Classification rules were validated by considering the number of false positives (FPs) and false negatives (FNs) of each class associated to the prediction set. Artificial neural networks led to the best results because of their intrinsic nonlinear features. Both techniques, MLP and PNN, gave zero FPs and zero FNs for all of the categories. KNN is a nonparametric method that also provides zero FPs and FNs for every class but only when selecting K = 3 neighbors. PDA produced good results also (zero FPs and FNs always) but only by selecting nine principal components for class modeling. LDA shows a lesser classification performance, because of the building of linear frontiers between classes that does not apply in many real situations. LDA led to one FP for bourbons and one FN for scotches. The worse results were obtained with SIMCA, which gave a higher number of FPs (five for both scotches and bourbons) and FNs (six for scotchs and two for bourbons). The possible cause of these findings is the strong influence of class inhomogeneities on the SIMCA performance. It is remarkable that in any case, all of the methodologies lead to zero FPs and FNs for the Irish whiskeys. PMID:16536565

  8. Improved method for rapid detection of phthalates in bottled water by gas chromatography-mass spectrometry.

    PubMed

    Otero, Paz; Saha, Sushanta Kumar; Moane, Siobhan; Barron, John; Clancy, Gerard; Murray, Patrick

    2015-08-01

    An improved gas chromatography-mass spectrometry (GC-MS) method for simple, rapid and precise quantification of phthalates in drinking water is presented. This method was validated for bis (2-n-butoxyethyl) phthalate (DBEP), bis (2-n-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), di-butyl phthalate (DBP), diethyl phthalate (DEP), dihexyl phthalate (DHP), dimethyl phthalate (DMP), di-n-octyl phthalate (DNOP) and dinonyl phthalate (DINP). Linearity of 0.9984>r(2)>0.9975 in the range of 0.075-4.8?g/mL for the selected phthalates was obtained. Accuracy values were in the range of 93-114% and RSD% for the analysis of 1.2?g/mL of each phthalate was below 2.3% (n=9). This new method design has significantly improved the detection in terms of rapidity, specificity, repeatability and accuracy compared to available methods. The procedure has been applied to the analyses of three different brands of commercially available bottled mineral water and the corresponding plastic bottles. Phthalates were extracted with dichloromethane and re-constituted in cyclohexane prior to GC-MS analysis. When the validated GC-MS method was applied to the quantification of the selected phthalates in the samples, only DBP (up to 0.06750.0018?g/mL) and DEHP (up to 1.68480.1631?g/mL) were found. Furthermore, we provide specific data about the concentration of DBP and DEHP in bottled water attributable to migration of phthalates from respective plastic bottles. PMID:26134297

  9. Nitrate Reduction in a Groundwater Microcosm Determined by 15N Gas Chromatography-Mass Spectrometry

    PubMed Central

    Bengtsson, Gran; Annadotter, Helne

    1989-01-01

    Aerobic and anaerobic groundwater continuous-flow microcosms were designed to study nitrate reduction by the indigenous bacteria in intact saturated soil cores from a sandy aquifer with a concentration of 3.8 mg of NO3?-N liter?1. Traces of 15NO3? were added to filter-sterilized groundwater by using a Darcy flux of 4 cm day?1. Both assimilatory and dissimilatory reduction rates were estimated from analyses of 15N2, 15N2O, 15NH4+, and 15N-labeled protein amino acids by capillary gas chromatography-mass spectrometry. N2 and N2O were separated on a megabore fused-silica column and quantified by electron impact-selected ion monitoring. NO3? and NH4+ were analyzed as pentafluorobenzoyl amides by multiple-ion monitoring and protein amino acids as their N-heptafluorobutyryl isobutyl ester derivatives by negative ion-chemical ionization. The numbers of bacteria and their [methyl-3H]thymidine incorporation rates were simultaneously measured. Nitrate was completely reduced in the microcosms at a rate of about 250 ng g?1 day?1. Of this nitrate, 80 to 90% was converted by aerobic denitrification to N2, whereas only 35% was denitrified in the anaerobic microcosm, where more than 50% of NO3? was reduced to NH4+. Assimilatory reduction was recorded only in the aerobic microcosm, where N appeared in alanine in the cells. The nitrate reduction rates estimated for the aquifer material were low in comparison with rates in eutrophic lakes and coastal sediments but sufficiently high to remove nitrate from an uncontaminated aquifer of the kind examined in less than 1 month. PMID:16348048

  10. Chemometric Profile of Root Extracts of Rhodiola imbricata Edgew. with Hyphenated Gas Chromatography Mass Spectrometric Technique

    PubMed Central

    Tayade, Amol B.; Dhar, Priyanka; Kumar, Jatinder; Sharma, Manu; Chauhan, Rajinder S.; Chaurasia, Om P.; Srivastava, Ravi B.

    2013-01-01

    Rhodiola imbricata Edgew. (Rose root or Arctic root or Golden root or Shrolo), belonging to the family Crassulaceae, is an important food crop and medicinal plant in the Indian trans-Himalayan cold desert. Chemometric profile of the n-hexane, chloroform, dichloroethane, ethyl acetate, methanol, and 60% ethanol root extracts of R. imbricata were performed by hyphenated gas chromatography mass spectrometry (GC/MS) technique. GC/MS analysis was carried out using Thermo Finnigan PolarisQ Ion Trap GC/MS MS system comprising of an AS2000 liquid autosampler. Interpretation on mass spectrum of GC/MS was done using the NIST/EPA/NIH Mass Spectral Database, with NIST MS search program v.2.0g. Chemometric profile of root extracts revealed the presence of 63 phyto-chemotypes, among them, 1-pentacosanol; stigmast-5-en-3-ol, (3?,24S); 1-teracosanol; 1-henteracontanol; 17-pentatriacontene; 13-tetradecen-1-ol acetate; methyl tri-butyl ammonium chloride; bis(2-ethylhexyl) phthalate; 7,8-dimethylbenzocyclooctene; ethyl linoleate; 3-methoxy-5-methylphenol; hexadecanoic acid; camphor; 1,3-dimethoxybenzene; thujone; 1,3-benzenediol, 5-pentadecyl; benzenemethanol, 3-hydroxy, 5-methoxy; cholest-4-ene-3,6-dione; dodecanoic acid, 3-hydroxy; octadecane, 1-chloro; ethanone, 1-(4-hydroxyphenyl); ?-tocopherol; ascaridole; campesterol; 1-dotriacontane; heptadecane, 9-hexyl were found to be present in major amount. Eventually, in the present study we have found phytosterols, terpenoids, fatty acids, fatty acid esters, alkyl halides, phenols, alcohols, ethers, alkanes, and alkenes as the major group of phyto-chemotypes in the different root extracts of R. imbricata. All these compounds identified by GC/MS analysis were further investigated for their biological activities and it was found that they possess a diverse range of positive pharmacological actions. In future, isolation of individual phyto-chemotypes and subjecting them to biological activity will definitely prove fruitful results in designing a novel drug. PMID:23326358

  11. A gas chromatography-mass spectrometry method for the quantitation of clobenzorex.

    PubMed

    Cody, J T; Valtier, S

    1999-01-01

    Drugs metabolized to amphetamine or methamphetamine are potentially significant concerns in the interpretation of amphetamine-positive urine drug-testing results. One of these compounds, clobenzorex, is an anorectic drug that is available in many countries. Clobenzorex (2-chlorobenzylamphetamine) is metabolized to amphetamine by the body and excreted in the urine. Following administration, the parent compound was detectable for a shorter time than the metabolite amphetamine, which could be detected for days. Because of the potential complication posed to the interpretation of amphetamin-positive drug tests following administration of this drug, the viability of a current amphetamine procedure using liquid-liquid extraction and conversion to the heptafluorobutyryl derivative followed by gas chromatography-mass spectrometry (GC-MS) analysis was evaluated for identification and quantitation of clobenzorex. Qualitative identification of the drug was relatively straightforward. Quantitative analysis proved to be a far more challenging process. Several compounds were evaluated for use as the internal standard in this method, including methamphetamine-d11, fenfluramine, benzphetamine, and diphenylamine. Results using these compounds proved to be less than satisfactory because of poor reproducibility of the quantitative values. Because of its similar chromatographic properties to the parent drug, the compound 3-chlorobenzylamphetamine (3-Cl-clobenzorex) was evaluated in this study as the internal standard for the quantitation of clobenzorex. Precision studies showed 3-Cl-clobenzorex to produce accurate and reliable quantitative results (within-run relative standard deviations [RSDs] < 6.1%, between-run RSDs < 6.0%). The limits of detection and quantitation for this assay were determined to be 1 ng/mL for clobenzorex. PMID:10595847

  12. Determination of Synthetic Cathinones in Urine Using Gas Chromatography-Mass Spectrometry Techniques.

    PubMed

    Hong, Wei-Yin; Ko, Ya-Chun; Lin, Mei-Chih; Wang, Po-Yu; Chen, Yu-Pen; Chiueh, Lih-Ching; Shih, Daniel Yang-Chih; Chou, Hsiu-Kuan; Cheng, Hwei-Fang

    2016-01-01

    In recent years, the abuse of synthetic cathinones has increased considerably. This study proposes a method, based on gas chromatography/mass spectrometry (GC-MS), to analyze and quantify six synthetic cathinones in urine samples: mephedrone (4-MMC), methylone (bk-MDMA), butylone, ethylone, pentylone and methylenedioxypyrovalerone (MDPV). In our procedure, the urine samples undergo solid-phase extraction (SPE) and derivatization prior to injection into the GC-MS device. Separation is performed using a HP-5MS capillary column. The use of selective ion monitoring (SIM mode) makes it is good sensitivity in this method, and the entire analysis process is within 18 min. In addition, the proposed method maintains linearity in the calibration curve from 50 to 2,000 ng/mL (r(2) > 0.995). The limit of detection of this method is 5 ng/mL, with the exception of MDPV (20 ng/mL); the limit of quantification is 20 ng/mL, with the exception of MDPV (50 ng/mL). In testing, the extraction performance of SPE was between 82.34 and 104.46%. Precision and accuracy results were satisfactory <15%. The proposed method was applied to six real urine samples, one of which was found to contain 4-MMC and bk-MDMA. Our results demonstrate the efficacy of the proposed method in the identification of synthetic cathinones in urine, with regard to the limits of detection and quantification. This method is highly repeatable and accurate. PMID:26410364

  13. [Simultaneous determination of 8 polybrominated biphenyls in human serum using gas chromatography-mass spectrometry].

    PubMed

    Liu, Xiao; Li, Jingguang; Huang, Feifei; Wu, Yongning

    2012-05-01

    A comprehensive analytical method based on gas chromatography-mass spectrometry (GC-MS) has been developed for the simultaneous determination of 8 polybrominated biphenyl congeners (PBBs: BB-15, 18, 52, 101, 153, 180, 194 and 206) in human serum. After the protein was removed, the sample was cleaned-up by an Oasis HLB solid-phase extraction (SPE) cartridge, then purified further by a two-layer cartridge containing activated silica gel and a mixture of silica gel and sulfuric acid, in which elution solvent was optimized. The eluent was evaporated to about 100 microL by a gentle nitrogen stream for GC-MS analysis. The separation was performed on a DB-5ms column (15 m x 0.25 mm x 0.1 microm) and the qualitative and quantitative analyses were carried out in electron impact (EI) selected ion monitoring (SIM) mode, in which isotope was used as internal standard. The limits of detection (LODs, 3.14 times of standard deviation) and the limits of quantification (LOQs, 10 times of standard deviation) were 0.002-0.029 ng/mL and 0.008-0.092 ng/mL respectively for the 8 PBBs. The average recoveries for all PBBs at three spiked levels were 74.24%-119.49% with the relative standard deviations in the range of 1.23%-12.02%. The method was verified by accurate analysis of BB-153 in organic contaminant standard reference materials (SRM) 1957 and 1958. This method is simple, rapid, accurate, precise and fit for the determination of PBBs in human serum. PMID:22934409

  14. Comparison of the structures of humic substances from aquatic and terrestrial sources by pyrolysis gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Wilson, M. A.; Philp, R. P.; Gillam, A. H.; Gilbert, T. D.; Tate, K. R.

    1983-03-01

    Four humic extracts isolated from terrestrial, mahne, plankton and freshwater sources have been investigated by pyrolysis-gas chromatography-mass spectrometry. The results show that substantial quantities of phenols (some not derived from lignin), pyrroles and nitrites (derived from proteins, nucleic acids or porphyrins) are decomposition products. Small amounts of furans (derived from carbohydrates) and unsaturated ketones (derived from polycarboxylic aliphatic acids) are also present. The results illustrate how parent material, transport factors and biological activity affect the composition of humic extracts.

  15. Identification of New Metabolites of Bacterial Transformation of Indole by Gas Chromatography-Mass Spectrometry and High Performance Liquid Chromatography

    PubMed Central

    Arora, Pankaj Kumar

    2014-01-01

    Arthrobacter sp. SPG transformed indole completely in the presence of an additional carbon source. High performance liquid chromatography and gas chromatography-mass spectrometry detected indole-3-acetic acid, indole-3-glyoxylic acid, and indole-3-aldehyde as biotransformation products. This is the first report of the formation of indole-3-acetic acid, indole-3-glyoxylic acid, and indole-3-aldehyde from indole by any bacterium. PMID:25548566

  16. Gas chromatography mass spectrometry computer analysis of volatile halogenated hydrocarbons in man and his environment--A multimedia environmental study.

    PubMed

    Barkley, J; Bunch, J; Bursey, J T; Castillo, N; Cooper, S D; Davis, J M; Erickson, M D; Harris, B S; Kirkpatrick, M; Michael, L C; Parks, S P; Pellizzari, E D; Ray, M; Smith, D; Tomer, K B; Wagner, R; Zweidinger, R A

    1980-04-01

    As part of a study to make a comparative analysis of selected halogenated compounds in man and the environmental media, a quantitative gas chromatography mass spectrometric analysis of the levels of the halogenated compounds found in the breath, blood and urine of an exposed population (Old Love Canal area, Niagara, New York) and their immediate environment (air and water) was undertaken. In addition, levels of halogenated hydrocarbons in air samples taken in the general Buffalo, Niagara Falls area were determined. PMID:7448328

  17. Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

    NASA Technical Reports Server (NTRS)

    Van De Meent, D.; Brown, S. C.; Philp, R. P.; Simoneit, B. R. T.

    1980-01-01

    A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.

  18. Detecting Organic Compounds in Martian Soil Analogues Using Gas Chromatography Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Glavin, D. P.; Buch, A.; Mahaffy, P. R.

    2004-01-01

    One of the primary objectives of the 1976 Viking missions was to determine whether organic compounds, possibly of biological origin, were present in the Martian surface soils. The Viking gas chromatography mass spectrometry (GCMS) instruments found no evidence for any organic compounds of Martian origin above a few parts per billion in the upper 10 cm of surface soil [l], suggesting the absence of a widely distributed Martian biota. However, Benner et d. have suggested that significant amounts of non-volatile organic compounds, possibly including oxidation products of bioorganic molecules (e.g. carboxylic acids) would not have been detected by the Viking GCMS [2]. Moreover, other key organic compounds important to biology, such as amino acids and nucleobases, would also likely have been missed by the Viking GCMS as these compounds require chemical derivatization to be stable in a GC column [3]. Recent pyrolysis experiments with a Mars soil analogue that had been innoculated with Escherichia coli bacteria have shown that amino acid decomposition products (amines) and nucleobases are among the most abundant products generated after pyrolysis of the bacterial cells [4,5]. At the part per billion level (Viking GCMS detection limit), these pyrolysis products generated from several million bacterial cells per gram of Martian soil would not have been detected by the Viking GCMS instruments [4]. Analytical protocols are under development for upcoming in situ lander opportunities to target several important biological compounds including amino acids and nucleobases. For example, extraction and chemical derivatization techniques [3] are being adapted for space flight use to transform reactive or fragile molecules that would not have been detected by the Viking GCMS instruments, into species that are sufficiently volatile to be detected by GCMS. Recent experiments carried out at NASA Goddard have shown that using this derivatization technique all of the targeted compounds mentioned above can be separated on a GC column and detected by MS at sub-picomole (< 10(exp -l2 mole) levels. With these methods, the detection limit for amino acids, carboxylic acids and nucleobases is several orders of magnitude more sensitive than the Viking GCMS instruments for these compounds. Preliminary results using this analytical technique on a variety of Martian soil analogues will be presented.

  19. Plasma metabolomic profiling of dairy cows affected with ketosis using gas chromatography/mass spectrometry

    PubMed Central

    2013-01-01

    Background Ketosis is an important problem for dairy cows` production performance. However, it is still little known about plasma metabolomics details of dairy ketosis. Results A gas chromatography/mass spectrometry (GC/MS) technique was used to investigate plasma metabolic differences in cows that had clinical ketosis (CK, n=22), subclinical ketosis (SK, n=32), or were clinically normal controls (NC, n=22). The endogenous plasma metabolome was measured by chemical derivatization followed by GC/MS, which led to the detection of 267 variables. A two-sample t-test of 30, 32, and 13 metabolites showed statistically significant differences between SK and NC, CK and NC, and CK and SK, respectively. Orthogonal signal correction-partial least-square discriminant analysis (OPLS-DA) revealed that the metabolic patterns of both CK and SK were mostly similar, with the exception of a few differences. The development of CK and SK involved disturbances in many metabolic pathways, mainly including fatty acid metabolism, amino acid metabolism, glycolysis, gluconeogenesis, and the pentose phosphate pathway. A diagnostic model arbitrary two groups was constructed using OPLS-DA and receiveroperator characteristic curves (ROC). Multivariate statistical diagnostics yielded the 19 potential biomarkers for SK and NC, 31 for CK and NC, and 8 for CK and SK with area under the curve (AUC) values. Our results showed the potential biomarkers from CK, SK, and NC, including carbohydrates, fatty acids, amino acids, even sitosterol and vitamin E isomers, etc. 2-piperidinecarboxylic acid and cis-9-hexadecenoic acid were closely associated with metabolic perturbations in ketosis as Glc, BHBA and NEFA for dealing with metabolic disturbances of ketosis in clinical practice. However, further research is needed to explain changes of 2,3,4-trihydroxybutyric acid, 3,4-dihydroxybutyric acid, ?-aminobutyric acid, methylmalonic acid, sitosterol and ?-tocopherol in CK and SK, and to reveal differences between CK and SK. Conclusion Our study shows that some new biomarkers of ketosis from plasma may find new metabolic changes to have clinically new utility and significance in diagnosis, prognosis, and prevention of ketosis in the future. PMID:24070026

  20. Analytical strategies for characterizing organic paint media using gas chromatography/mass spectrometry.

    PubMed

    Colombini, Maria Perla; Andreotti, Alessia; Bonaduce, Ilaria; Modugno, Francesca; Ribechini, Erika

    2010-06-15

    Throughout history, artists have experimented with a variety of organic-based natural materials, using them as paint binders, varnishes, and ingredients for mordants in gildings. Artists often use many layers of paint to produce particular effects. How we see a painting is thus the final result of how this complex, highly heterogeneous, multimaterial, and multilayered structure interacts with light. The chemical characterization of the organic substances in paint materials is of great importance for artwork conservation because the organic components of the paint layers are particularly subject to degradation. In addition, understanding the organic content and makeup of paint materials allows us to differentiate between the painting techniques that have been used over history. Applying gas chromatography/mass spectrometry (GC/MS) analysis to microsamples of paint layers is widely recognized as the best approach for identifying organic materials, such as proteins, drying oils, waxes, terpenic resins, and polysaccharide gums. The method provides essential information for reconstructing artistic techniques, assessing the best conditions for long-term preservation, and planning restoration. In this Account, we summarize the more common approaches adopted in the study of the organic components of paint materials. Our progress in developing GC/MS analytical procedures in the field of cultural heritage is presented, focusing on problems that arise from (i) the presence of mixtures of many chemically complex and degraded materials, (ii) the interference of inorganic species, (iii) the small size of the samples, and (iv) the risk of contamination. We outline some critical aspects of the analytical strategy, such as the need to optimize specific wet-chemical sample pretreatments in order to separate the various components, hydrolyze macromolecular analytes, clean-up inorganic ions, and derivatize polar molecules for subsequent GC/MS separation and identification. We also discuss how to interpret the chromatographic data so as to be able to identify the materials. This identification is based on the presence of specific biomarkers (chemotaxonomy), on the evaluation of the overall chromatographic profile, or on the quantitative analysis of significant compounds. GC/MS-based analytical procedures have for 20 years provided important contributions to conservation science, but challenges and opportunities still coexist in the field of organic-based paint materials. We give selected examples and provide case studies showing how a better understanding of the chemical composition of organic paint materials and of their degradation pathways contribute to a better knowledge our cultural heritage, and to its preservation for future generations. PMID:20180544

  1. EPA Method 525.3 - Determination of Semivolatile Organic Chemicals in Drinking Water by Solid Phase Extraction and Capillary Column Gas Chromatography/Mass Spectrometry (GC/MS)

    EPA Science Inventory

    Method 525.3 is an analytical method that uses solid phase extraction (SPE) and gas chromatography/mass spectrometry (GC/MS) for the identification and quantitation of 125 selected semi-volatile organic chemicals in drinking water.

  2. The use of stable isotopes and gas chromatography/mass spectrometry in the identification of steroid metabolites in the equine

    SciTech Connect

    Houghton, E.; Dumasia, M.C.; Teale, P.; Smith, S.J.; Cox, J.; Marshall, D.; Gower, D.B. )

    1990-10-01

    Stable isotope gas chromatography/mass spectrometry has been used successfully in the elucidation of structures of urinary steroid metabolites in the horse and in the identification of metabolites isolated from in vivo perfusion and in vitro incubation studies using equine tissue preparations. Deuterium-labeled steroids, testosterone, dehydroepiandrosterone, and 5-androstene-3 beta,17 beta-diol have been synthesized by base-catalyzed isotope exchange methods and the products characterized by gas chromatography/mass spectrometry. (16,16(-2)H2)Dehydroepiandrosterone (plus radiolabeled dehydroepiandrosterone) was perfused into a testicular artery of a pony stallion and was shown to be metabolized into 2H2-labeled testosterone, 4-androstenedione, isomers of 5-androstene-3,17-diol, 19-hydroxytestosterone, and 19-hydroxy-4-androstenedione. In further studies, equine testicular minces have been incubated with 2H2-labeled and radiolabeled dehydroepiandrosterone and 5-androstene-3 beta, 17 beta-diol. The metabolites, whose identity was confirmed by stable isotope gas chromatography/mass spectrometry, proved the interconversion of the two substrates, as well as formation of testosterone and 4-androstenedione. The aromatization of dehydroepiandrosterone was also confirmed, together with the formation of an isomer of 5(10)-estrene-3,17-diol from both substrates showing 19-demethylation without concomitant aromatization. In studies of the feto-placental unit, the allantochorion was shown to aromatize (2H5)testosterone to (2H4)estradiol, the loss of one 2H from the substrate being consistent with aromatization of the A ring. The formation of 6-hydroxyestradiol was also confirmed in this study. The same technique has been valuable in determining the structure of two metabolites of nandrolone isolated from horse urine.

  3. Thermal desorption-gas chromatography-mass spectrometry method to determine phthalate and organophosphate esters from air samples.

    PubMed

    Aragón, M; Borrull, F; Marcé, R M

    2013-08-16

    A method based on thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) has been developed to determine four organophosphate esters, seven phthalate esters, and bis(2-ethylhexyl) adipate in the gas phase from harbour and urban air samples. The method involves the sampling of 1.5L of air in a Tenax TA sorbent tube followed by thermal desorption (using a Tenax TA cryogenic trap) coupled to gas chromatography-mass spectrometry. The repeatability of the method expressed as %RSD (n=3) is less than 15% and the MQLs are between 0.007μgm(-3) (DMP, TBP, BBP, TPP and DnOP) and 6.7μgm(-3) (DEHP). The method was successfully applied in two areas (urban and harbour) testing two and three points in each one, respectively. Some of these compounds were found in both urban and harbour samples. Di-(2-ethylhexyl)phthalate was the most abundant compound found in both areas at concentration levels between 6.7μgm(-3) and 136.4μgm(-3). This study demonstrates that thermal desorption is an efficient method for the determination of these semi-volatile compounds in the gas phase fraction of air samples. PMID:23859797

  4. Application of capillary gas chromatography mass spectrometry/computer techniques to synoptic survey of organic material in bed sediment

    USGS Publications Warehouse

    Steinheimer, T.R.; Pereira, W.E.; Johnson, S.M.

    1981-01-01

    A bed sediment sample taken from an area impacted by heavy industrial activity was analyzed for organic compounds of environmental significance. Extraction was effected on a Soxhlet apparatus using a freeze-dried sample. The Soxhlet extract was fractionated by silica gel micro-column adsorption chromatography. Separation and identification of the organic compounds was accomplished by capillary gas chromatography/mass spectrometry techniques. More than 50 compounds were identified; these include saturated hydrocarbons, olefins, aromatic hydrocarbons, alkylated polycyclic aromatic hydrocarbons, and oxygenated compounds such as aldehydes and ketones. The role of bed sediments as a source or sink for organic pollutants is discussed. ?? 1981.

  5. [Analysis of oxygenates from fischer-Tropsch synthesis oil using column liquid chromatography and gas chromatography-mass spectrography].

    PubMed

    Fan, Gaixian; Xu, Yuanyuan; Li, Ying; Li, Ying; Xiang, Hongwei; Li, Yongwang

    2007-11-01

    A liquid chromatographic column filled with silica gel of 100 - 200 mesh was used to separate cold trap oil from Fischer-Tropsch synthesis with dimethylsulfoxide (DMSO) as eluent. With this pretreatment method, the cold trap oil was separated into two major classes, namely, hydrocarbons and oxygenates. Minor components were also enriched and determined, and small peaks adjacent to big peaks and tailings were also well solved. The oxygenates were then analyzed with gas chromatography-mass spectrometry (GC-MS), and 139 components were identified. PMID:18257312

  6. Quantitative determination of trimethylamine in urine by solid-phase microextraction and gas chromatography-mass spectrometry.

    PubMed

    Mills, G A; Walker, V; Mughal, H

    1999-02-19

    Trimethylaminuria (fish odour syndrome) is diagnosed from an increase in urinary excretion of trimethylamine with decreased trimethylamine oxide. We report a new quantitative stable isotope dilution gas chromatography-mass spectrometry procedure for the analysis of these metabolites using solid-phase microextraction (SPME). Both polydimethylsiloxane and mixed Carboxen-polydimethylsiloxane SPME fibres were found to be suitable for the headspace extraction of TMA. This new sampling technique could have wide application for the analysis of volatile and semi-volatile compounds by metabolic screening laboratories. PMID:10080656

  7. Sensitive determination of fluoride in biological samples by gas chromatography-mass spectrometry after derivatization with 2-(bromomethyl)naphthalene.

    PubMed

    Kwon, Sun-Myung; Shin, Ho-Sang

    2014-12-10

    A gas chromatography-mass spectrometric method was developed in this study in order to determine fluoride in plasma and urine after derivatization with 2-(bromomethyl)naphthalene. 2-Fluoronaphthalene was chosen as the internal standard. The derivatization of fluoride was performed in the biological sample and the best reaction conditions (10.0 mg mL(-1) of 2-(bromomethyl)naphthalene, 1.0 mg mL(-1) of 15-crown-5-ether as a phase transfer catalyst, pH of 7.0, reaction temperature of 70C, and heating time of 70 min) were established. The organic derivative was extracted with dichloromethane and then measured by a gas chromatography-mass spectrometry. Under the established condition, the detection limits were 11 ?g L(-1) and 7 ?g L(-1) by using 0.2 mL of plasma or urine, respectively. The accuracy was in a range of 100.8-107.6%, and the precision of the assay was less than 4.3% in plasma or urine. Fluoride was detected in a concentration range of 0.12-0.53 mg L(-1) in six urine samples after intake of natural mineral water containing 0.7 mg L(-1) of fluoride. PMID:25441893

  8. Chromatographic fingerprint analysis of metabolites in natural and artificial agarwood using gas chromatography-mass spectrometry combined with chemometric methods.

    PubMed

    Gao, Xiaoxia; Xie, Mingrong; Liu, Shaofeng; Guo, Xiaoling; Chen, Xiaoying; Zhong, Zhaojian; Wang, Lei; Zhang, Weimin

    2014-09-15

    Agarwood is a resinous material formed in wounded Aquilaria sinensis in China, which is widely used as an effective traditional Chinese medicine (TCM). This study is aimed to use gas chromatography-mass spectrometry combined with chemometric methods to create reliable criteria for accurate identification of natural agarwood and artificial agarwood, as well as for quality evaluation of artificial agarwood. Natural agarwood and artificial agarwood (stimulated by formic acid or formic acid plus fungal inoculation) were used as standards and controls for the gas chromatography-mass spectrometry (GC-MS) and multivariate analysis. The identification criteria developed were applied to commercial agarwood. A reliable criteria including correlation coefficient of GC-MS fingerprint of natural agarwood and 22 markers of metabolism in natural and artificial agarwood was constructed. Compared with chemically stimulated agarwood (formic acid) and in terms of the 22 markers, artificial agarwood obtained by formic acid stimulation and fungal inoculation were much closer to natural agarwood. The study demonstrates that the chemical components of artificial agarwood obtained by comprehensive stimulated method (formic acid plus fungal inoculation) are much closer to the natural agarwood than those obtained by chemically stimulated method (formic acid), as times goes by. A reliable criteria containing correlation coefficient of GC-MS fingerprint of natural agarwood and 22 metabolism markers can be used to evaluate the quality of the agarwood. As an application case, three samples were identified as natural agarwood from the 25 commercial agarwood by using the evaluation method. PMID:25129412

  9. Studies of long chain lipids in insects by high temperature gas chromatography and high temperature gas chromatography-mass spectrometry.

    PubMed

    Sutton, Paul A; Wilde, Michael J; Martin, Stephen J; Cva?ka, Josef; Vrkoslav, Vladimr; Rowland, Steven J

    2013-07-01

    The organic compounds occurring naturally on the cuticles (surfaces) of insects are important for insect communication, help to act as protective water barriers and are useful in chemical taxonomy. Typically the cuticular lipids are only studied by gas chromatography-mass spectrometry (GC-MS) of hexane or pentane extracts, so the normal limitations of GC-MS makes it perhaps unsurprising that compounds with more than about 35 carbon atoms have only rarely been reported. Here we show by high temperature (HT) GC and HTGC-MS of extracts of eleven species of insects from nine genera, that longer chain compounds are actually common. Wax esters and triacylglycerides are virtually ubiquitous in such extracts, but long chain (>C35) hydrocarbons also sometimes occur. Whilst the latter have occasionally been reported previously from mass spectrometry studies, the use of the HTGC combination with MS allowed even some isobaric isomers to be separated and thus more complete lipid distributions to be monitored. Since the physical properties of cuticular compounds depend on this composition of the mixtures, such differences may influence the water loss rates of the insects, amongst other effects. In addition, the high molecular weight compound profiles may allow species to be more easily differentiated, one from another. It would be interesting to apply these methods to examination of the cuticular lipids of insects on a more routine basis, ideally in combination with MALDI-TOF-MS and imaging methods. PMID:23726079

  10. Detection of clenbuterol residues in bovine liver, muscle, retina and urine using gas chromatography/mass spectrometry.

    PubMed

    Blanchflower, W J; Hewitt, S A; Cannavan, A; Elliott, C T; Kennedy, D G

    1993-06-01

    A gas chromatographic/mass spectrometric method is described for the detection of clenbuterol residues in liver, muscle, urine and retina. Tissue samples are first digested using protease and any clenbuterol present is extracted using a simple liquid/liquid extraction procedure. The dried extracts are then derivatized using methylboronic acid and the derivates are subjected to gas chromatography/mass spectrometry on a magnetic sector instrument. The detection limit of the assay is 0.05 ng g-1 clenbuterol in liver, muscle or urine a 10 g sample size, and 4 ng g-1 in retina using a 0.5 g sample size. The assay is made very specific by using selected ion monitoring of three ions at a resolution of 3500 and by ion ratio measurements. The precision and reproducibility of the assay are enhanced by the use of a deuterated internal standard, with a typical coefficient of variation of 3%. PMID:8329461

  11. Quantitative determination of dimethyl fumarate in silica gel by solid-phase microextraction/gas chromatography/mass spectrometry and ultrasound-assisted extraction/gas chromatography/mass spectrometry.

    PubMed

    Bocchini, Paola; Pinelli, Francesca; Pozzi, Romina; Ghetti, Federica; Galletti, Guido C

    2015-06-01

    Dimethyl fumarate (DMF) is a chemical compound which has been added to silica gel bags used for preserving leather products during shipment. DMF has recently been singled out due to its ability to induce a number of medical problems in people which touch products contaminated by it. Its use as a biocide has been recently made illegal in Europe. Two different extraction techniques, namely ultrasound-assisted extraction (UAE) and solid-phase microextraction (SPME), both coupled with gas chromatography/mass spectrometry were applied to the quantitative determination of DMF in silica gel. Linearity of the methods, reproducibility and detection limits were determined. The two methods were applied to the quantification of DMF in thirty-four silica gel samples used as anti-mould agents in different leather products sold in Italy, and the obtained results were statistically compared. PMID:25939646

  12. Analysis of odour compounds from scented consumer products using gas chromatography-mass spectrometry and gas chromatography-olfactometry.

    PubMed

    Bartsch, Jennifer; Uhde, Erik; Salthammer, Tunga

    2016-01-21

    Scented consumer products are being bought in increasing amounts and gaining more popularity. There is, however, relatively little information available about their ingredients, emissions and allergenic potential. Frequently, a mixture of different fragrance substances and not solely an individual substance contributes to the overall desired smell. The aim of this study was to investigate the odorous volatile organic compounds (OVOCs) in consumer products containing fragrances. Over 44 products were selected: various scented candles, printing products with different scent types and other products types particularly meant to be used indoors. Measurements were carried out in a desiccator. Air samples were collected on thermal desorption tubes to determine the released fragrance substances by means of gas chromatography-mass spectrometry (GC-MS). Moreover, gas chromatography-olfactometry (GC-O) was used to obtain sensory data and to ensure no important odorant was overlooked. Using both methods it was possible to distinguish between odour active and inactive compounds and subsequently to identify almost 300 different odorants across all scented products. Besides the advantage of differentiation, as the human nose is a very sensitive detector, GC-O was found to be a useful tool for detecting traces and chosen target compounds. One focus in this study lay on the 26 EU-regulated fragrance allergens to prove their relevance in scented consumer goods. In total, 18 of them were identified, with at least one substance being present in almost every product. Benzyl alcohol, cinnamaldehyde, citronellol, eugenol, linalool and limonene were the prevalently detected allergens. Particularly linalool and limonene were observed in over 50% of the products. In addition, eugenol appeared to be one of the most frequently detected compounds in trace-level concentrations in the candle emissions. PMID:26724768

  13. The analysis of tire rubber traces collected after braking incidents using Pyrolysis-GasChromatography/Mass Spectrometry.

    PubMed

    Sarkissian, Garry

    2007-09-01

    Automobile tire marks can routinely be found at the scenes of crime, particularly hit-and-run accidents and are left on road surfaces because of sudden braking or the wheels spinning. The tire marks are left due to the friction between the tire rubber and the solid road surface, and do not always demonstrate the tire tread pattern. However, the tire mark will contain traces of the tire. In this study, Pyrolysis Gas Chromatography/Mass Spectrometry was used to analyze 12 tires from different manufacturer's and their traces collected after braking incidents. Tire marks were left on a conglomerate road surface with sudden braking. The samples were pyrolysed without removal of contaminant in a micro-furnace type pyrolyser. Quantitative and qualitative analysis were performed on all the samples. All 12 samples were distinguished from each other. Each of the tire traces were identified as coming from there original source. PMID:17767653

  14. Gas chromatography-mass spectrometry of JWH-018 metabolites in urine samples with direct comparison to analytical standards.

    PubMed

    Emerson, Beth; Durham, Bill; Gidden, Jennifer; Lay, Jackson O

    2013-06-10

    JWH-018 (1-pentyl-3-(1-naphthoyl)indole) is one of numerous potential aminoalkylindoles contained in products marketed as 'K2' or 'Spice'. Investigation of the urinary metabolites from consumption of these compounds is important because they are banned in the United States and many European countries. An efficient extraction procedure and gas chromatography-mass spectrometry (GC-MS) method were developed for detection of 'K2' metabolites in urine from individuals suspected of using these products. Analytical standards were used to elucidate the structure-specific mass spectral fragmentations and retention properties to confirm proposed identifications and support quantitative studies. A procedure for the synthesis of one of these metabolites (5-hydroxypentyl JWH-018) was also developed. Results are comparable to existing LC-MS/MS methods, with the same primary metabolites detected. The specific metabolite hydrolysis products include 4-hydroxpentyl, 5-hydroxypentyl, and N-pentanoic acid derivatives. PMID:23683902

  15. Fatty acid composition of wild mushroom species of order Agaricales--examination by gas chromatography-mass spectrometry and chemometrics.

    PubMed

    Marekov, Ilko; Momchilova, Svetlana; Grung, Bjrn; Nikolova-Damyanova, Boryana

    2012-12-01

    Applying gas chromatography-mass spectrometry of 4,4-dimethyloxazoline fatty acid derivatives, the fatty acid composition of 15 mushroom species belonging to 9 genera and 5 families of order Agaricales growing in Bulgaria is determined. The structure of 31 fatty acids (not all present in each species) is unambiguously elucidated, with linoleic, oleic and palmitic acids being the main components (ranging between 70.9% (Marasmius oreades) and 91.2% (Endoptychum agaricoides)). A group of three hexadecenoic positionally isomeric fatty acids, 6-, 9- and 11-16:1, appeared to be characteristic components of the examined species. By applying chemometrics it was possible to show that the fatty acid composition closely reflects the classification of the species. PMID:23168239

  16. Fourier transform-infrared spectroscopy and Gas chromatography-mass spectroscopy: Reliable techniques for analysis of Parthenium mediated vermicompost

    NASA Astrophysics Data System (ADS)

    Rajiv, P.; Rajeshwari, Sivaraj; Venckatesh, Rajendran

    2013-12-01

    Fourier transform infrared spectroscopy (FT-IR) and Gas chromatography-mass spectroscopy have been carried out to investigate the chemical composition of Parthenium mediated vermicompost. Four different concentrations of Parthenium and cow dung mixtures were vermicomposted using the earthworms (Eudrilus eugeniae). FT-IR spectra reveal the absence of Parthenin toxin (sesquiterpene lactone) and phenols in vermicompost which was obtained from high concentration of cow dung mixed treatments. GC-MS analysis shows no phenolic compounds and predominant level of intermediate metabolites such as 4,8,12,16-Tetramethylheptadecan-4-olide (7.61%), 2-Pentadecanone, 6,10,14-trimethyl- (5.29%) and Methyl 16-methyl-heptadecanoate (4.69%) during the vermicomposting process. Spectral results indicated that Parthenin toxin and phenols can be eradicated via vermicomposting if mixed with appropriate quantity of cow dung.

  17. Fourier transform-infrared spectroscopy and Gas chromatography-mass spectroscopy: reliable techniques for analysis of Parthenium mediated vermicompost.

    PubMed

    Rajiv, P; Rajeshwari, Sivaraj; Venckatesh, Rajendran

    2013-12-01

    Fourier transform infrared spectroscopy (FT-IR) and Gas chromatography-mass spectroscopy have been carried out to investigate the chemical composition of Parthenium mediated vermicompost. Four different concentrations of Parthenium and cow dung mixtures were vermicomposted using the earthworms (Eudrilus eugeniae). FT-IR spectra reveal the absence of Parthenin toxin (sesquiterpene lactone) and phenols in vermicompost which was obtained from high concentration of cow dung mixed treatments. GC-MS analysis shows no phenolic compounds and predominant level of intermediate metabolites such as 4,8,12,16-Tetramethylheptadecan-4-olide (7.61%), 2-Pentadecanone, 6,10,14-trimethyl- (5.29%) and Methyl 16-methyl-heptadecanoate (4.69%) during the vermicomposting process. Spectral results indicated that Parthenin toxin and phenols can be eradicated via vermicomposting if mixed with appropriate quantity of cow dung. PMID:23998948

  18. Pyrolysis-gas chromatography/mass spectrometry analyses of biological particulates collected during recent space shuttle missions

    NASA Technical Reports Server (NTRS)

    Matney, M. L.; Limero, T. F.; James, J. T.

    1994-01-01

    Biological particulates collected on air filters during shuttle missions (STS-40 and STS-42) were identified using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). A method was developed for identifying the atmospheric particles and their sources through the analysis of standard materials and the selection of "marker" compounds specific to the particle type. Pyrolysis spectra of biological standards were compared with those of airborne particles collected during two space shuttle missions; marker compounds present in the shuttle particle spectra were matched with those of the standards to identify the source of particles. Particles of 0,5--1-mm diameter and weighing as little as 40 micrograms could be identified using this technique. The Py-GC/MS method identified rat food and soilless plant-growth media as two sources of particles collected from the shuttle atmosphere during flight.

  19. Accelerated solvent extraction and gas chromatography/mass spectrometry for determination of polycyclic aromatic hydrocarbons in smoked food samples.

    PubMed

    Wang, G; Lee, A S; Lewis, M; Kamath, B; Archer, R K

    1999-03-01

    Accelerated solvent extraction (ASE) is a new sample extraction method offering a number of advantages such as low pe -extraction cost, reduced solvent and time consumption, and simplified extraction protocols. In this study, the ASE method was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from biological samples. For recovery studies, fish tissues and ground pork were used as sample matrices. Sample aliquots fortified with 16 PAHs were extracted by ASE, and the extracts were treated with sulfuric acid and Florisil, followed by gas chromatography-mass spectrometry analysis. The PAH recoveries by the ASE method were found to be comparable with or better than those by Soxhlet extraction. The extraction and quantitation method was then applied to the determination of PAHs in several smoked meat samples obtained from a local market. Up to 12 PAHs were found to be present at concentrations ranging from 3 to 52 ng/g wet sample. PMID:10552416

  20. Dual low thermal mass gas chromatography-mass spectrometry for fast dual-column separation of pesticides in complex sample.

    PubMed

    Sasamoto, Kikuo; Ochiai, Nobuo; Kanda, Hirooki

    2007-07-31

    A method is described for fast dual-column separation of pesticides by use of dual low thermal mass gas chromatography-mass spectrometry (dual LTM-GC-MS) with different temperature programming. The method can provide two total ion chromatograms with different separation on DB-5 and DB-17 in a single run, which allows improved identification capability, even with short analysis time (<17 min). Also simultaneous detection with MS and elemental selective detector, e.g. pulsed flame photometric detection (PFPD) was evaluated for fast dual-column separation of 82 pesticide mixtures including 27 phosphorus pesticides. Dual LTM-GC-MS/PFPD was applied to analysis of pesticides in a brewed green tea sample with dual stir bar sorptive extraction method (dual SBSE). PMID:19071809

  1. [Rapid determination of alkaloids in tobacco using gas chromatography-mass spectrometry with full scan-selected ion monitoring mode].

    PubMed

    Wang, Baoxing; Yang, Shihua; Hou, Ying; Zeng, Xiaoying; Wu, Yi; Xu, Guowang

    2008-05-01

    Simultaneous full scan-selected ion monitoring mode (Scan-SIM) is a new improvement method of data acquisition of gas chromatography-mass spectrometry (GC-MS). A method of determing alkaloids in tobacco was established by GC-MS with Scan-SIM. Nicotine, nornicotine, anabasine and anatabine were determined with scan mode, and myosmine, nicotyrine, 2,3'-bipyridyl and cotinine were determined with SIM mode. The average recoveries of alkaloids ranged from 94.8% to 98.8%, and the relative standard deviations were less than 6.0% (n = 5). Therefore, it is a simple, rapid, accurate method. Tobacco samples picked in different years were determined using this method, and the results were satisfactory. PMID:18724666

  2. Ultra trace determination of fluorobenzoic acids in reservoir and ground water using isotope dilution gas chromatography mass spectrometry.

    PubMed

    Mller, Karsten; Seubert, Andreas

    2014-06-01

    The accurate ultra-trace analysis of six fluorobenzoic acids (FBAs) via isotope dilution gas chromatography mass spectrometry through their deuterated analogues is described. North Sea reservoir and ground water samples were spiked with six deuterated FBAs (dFBAs), enriched using solid-phase extraction (SPE) and analysed using GC/MS after derivatisation with BF 3 MeOH. All FBAs were enriched and determined simultaneously. SPE allowed a 250-fold enrichment of the acids if 100 mL of sample volume was used. The method enables the determination of FBAs down to the range of 8-37 ng L (-1) with recoveries between 66 % and 85 %. It uses low amounts of chemicals and is adaptable to larger and smaller sample volumes. PMID:24620719

  3. Rapid identification of pork for halal authentication using the electronic nose and gas chromatography mass spectrometer with headspace analyzer.

    PubMed

    Nurjuliana, M; Che Man, Y B; Mat Hashim, D; Mohamed, A K S

    2011-08-01

    The volatile compounds of pork, other meats and meat products were studied using an electronic nose and gas chromatography mass spectrometer with headspace analyzer (GCMS-HS) for halal verification. The zNose was successfully employed for identification and differentiation of pork and pork sausages from beef, mutton and chicken meats and sausages which were achieved using a visual odor pattern called VaporPrint, derived from the frequency of the surface acoustic wave (SAW) detector of the electronic nose. GCMS-HS was employed to separate and analyze the headspace gasses from samples into peaks corresponding to individual compounds for the purpose of identification. Principal component analysis (PCA) was applied for data interpretation. Analysis by PCA was able to cluster and discriminate pork from other types of meats and sausages. It was shown that PCA could provide a good separation of the samples with 67% of the total variance accounted by PC1. PMID:21420795

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Biocatalytic Lactone Generation in Genetically Engineered Escherichia coli and Identification of Products by Gas Chromatography-Mass Spectroscopy

    NASA Astrophysics Data System (ADS)

    Slawson, Chad; Stewart, Jon; Potter, Robert

    2001-11-01

    Genetically altered Escherichia coli are used as biocatalysts to produce optically pure lactones from a variety of cyclic ketones as a biotechnology experiment for a biochemistry laboratory. The genetically engineered E. coli bacteria express large amounts of the enzyme cyclohexanone monooxygenase and are therefor capable of converting a variety of ketones into optically pure lactones. Separation by organic extraction and analysis by thin layer chromatography and gas chromatography-mass spectroscopy allows for the direct identification of products. Yield calculations and evaluation of the cost effectiveness of various substrates give students an opportunity to make recommendations and model industrial decision-making. Evaluation of the synthetic process for its environmental impact allows students to consider problems of cost versus environmental concerns. Use of bacterial biocatalysts offers chemistry students an opportunity to work with microorganisms and directly see the utility of genetically altered bacteria for synthetic chemistry.

  6. The identification of synthetic organic pigments in modern paints and modern paintings using pyrolysis-gas chromatography-mass spectrometry.

    PubMed

    Russell, Joanna; Singer, Brian W; Perry, Justin J; Bacon, Anne

    2011-05-01

    A collection of more than 70 synthetic organic pigments were analysed using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). We report on the analysis of diketo-pyrrolo-pyrrole, isoindolinone and perylene pigments which are classes not previously reported as being analysed by this technique. We also report on a number of azo pigments (2-naphthol, naphthol AS, arylide, diarylide, benzimidazolone and disazo condensation pigments) and phthalocyanine pigments, the Py-GC-MS analysis of which has not been previously reported. The members of each class were found to fragment in a consistent way and the pyrolysis products are reported. The technique was successfully applied to the analysis of paints used by the artist Francis Bacon (1909-1992), to simultaneously identify synthetic organic pigments and synthetic binding media in two samples of paint taken from Bacon's studio and micro-samples taken from three of his paintings and one painting attributed to him. PMID:21416165

  7. Use of gas chromatography-mass spectrometry/solid phase microextraction for the identification of MVOCs from moldy building materials.

    PubMed

    Wady, Loay; Bunte, Annicka; Pehrson, Christina; Larsson, Lennart

    2003-03-01

    Gas chromatography-mass spectrometry/solid phase microextraction (GC-MS/SPME) was applied to identify microbial volatile organic compounds (MVOCs) in water-damaged, mold-infested building materials (gypsum board papers (n=2), mineral wool, and masonite) and in cultivated molds (Aspergillus penicillioides, Stachybotrys chartarum, and Chaetomium globosum). Three SPME fibers (65-microm PDMS-DVB, 75-microm Carboxen-PDMS, and 70-microm Carbowax-stableflex) designed for automated injection were used of which the latter showed best performance. A number of previously reported MVOCs were detected both in the building materials and the cultivated molds. In addition, methyl benzoate was identified both in the S. chartarum and A. penicillioides cultures and in the building materials. SPME combined with GC-MS may be a useful method for the determination of MVOCs emitted from mold-infested building materials. PMID:12531501

  8. A gas chromatography-mass spectrometry-based metabolomic approach for the characterization of goat milk compared with cow milk.

    PubMed

    Scano, Paola; Murgia, Antonio; Pirisi, Filippo M; Caboni, Pierluigi

    2014-10-01

    In this work, the polar metabolite pool of commercial caprine milk was studied by gas chromatography-mass spectrometry and multivariate statistical data analysis. Experimental data were compared with those of cow milk and the discriminant analysis correctly classified milk. By the same means, differences due to heat treatments (UHT or pasteurization) on milk samples were also investigated. Results of the 2 discriminant analyses were combined, with the aim of finding the discriminant metabolites unique for each class and shared by 2 classes. Valine and glycine were specific to goat milk, talose and malic acid to cow milk, and hydroxyglutaric acid to pasteurized samples. Glucose and fructose were shared by cow milk and UHT-treated samples, whereas ribose was shared by pasteurized and goat milk. Other discriminant variables were not attributed to specific metabolites. Furthermore, with the aim to reduce food fraud, the issue of adulteration of caprine milk by addition of cheaper bovine milk has been also addressed. To this goal, mixtures of goat and cow milk were prepared by adding the latter in a range from 0 to 100% (vol/vol) and studied by multivariate regression analysis. The error in the level of cow milk detectable was approximately 5%. These overall results demonstrated that, through the combined approach of gas chromatography-mass spectrometry and multivariate statistical data analysis, we were able to discriminate between milk typologies on the basis of their polar metabolite profiles and to propose a new analytical method to easily discover food fraud and to protect goat milk uniqueness. The use of appropriate visualization tools improved the interpretation of multivariate model results. PMID:25108860

  9. A low thermal mass fast gas chromatograph and its implementation in fast gas chromatography mass spectrometry with supersonic molecular beams.

    PubMed

    Fialkov, Alexander B; Moragn, Mati; Amirav, Aviv

    2011-12-30

    A new type of low thermal mass (LTM) fast gas chromatograph (GC) was designed and operated in combination with gas chromatography mass spectrometry (GC-MS) with supersonic molecular beams (SMB), including GC-MS-MS with SMB, thereby providing a novel combination with unique capabilities. The LTM fast GC is based on a short capillary column inserted inside a stainless steel tube that is resistively heated. It is located and mounted outside the standard GC oven on its available top detector port, while the capillary column is connected as usual to the standard GC injector and supersonic molecular beam interface transfer line. This new type of fast GC-MS with SMB enables less than 1 min full range temperature programming and cooling down analysis cycle time. The operation of the fast GC-MS with SMB was explored and 1 min full analysis cycle time of a mixture of 16 hydrocarbons in the C(10)H(22) up to C(44)H(90) range was achieved. The use of 35 mL/min high column flow rate enabled the elution of C(44)H(90) in less than 45 s while the SMB interface enabled splitless acceptance of this high flow rate and the provision of dominant molecular ions. A novel compound 9-benzylazidanthracene was analyzed for its purity and a synthetic chemistry process was monitored for the optimization of the chemical reaction yield. Biodiesel was analyzed in jet fuel (by both GC-MS and GC-MS-MS) in under 1 min as 5 ppm fatty acid methyl esters. Authentic iprodion and cypermethrin pesticides were analyzed in grapes extract in both full scan mode and fast GC-MS-MS mode in under 1 min cycle time and explosive mixture including TATP, TNT and RDX was analyzed in under 1 min combined with exhibiting dominant molecular ion for TATP. Fast GC-MS with SMB is based on trading GC separation for speed of analysis while enhancing the separation power of the MS via the enhancement of the molecular ion in the electron ionization of cold molecules in the SMB. This paper further discusses several features of fast GC and fast GC-MS and the various trade-offs involved in having powerful and practical fast GC-MS. PMID:22119674

  10. Dehydration of Methylcyclohexanol Isomers in the Undergraduate Organic Laboratory and Product Analysis by Gas Chromatography-Mass Spectroscopy (GC-MS)

    ERIC Educational Resources Information Center

    Clennan, Malgorzata M.; Clennan, Edward L.

    2011-01-01

    Dehydrations of "cis"- and "trans"-2-methylcyclohexanol mixtures were carried out with 60% sulfuric acid at 78-80 [degrees]C as a function of time and the products were identified by gas chromatography-mass spectroscopy (GC-MS) analysis. The compounds identified in the reaction mixtures include alkenes, 1-, 3-, and 4-methylcyclohexenes and…

  11. Determination of off-flavor compounds, 2-methylisoborneol and geosmin, in salmon fillets using stir bar sorptive extractionthermal desorption coupled with gas chromatographymass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A sensitive and solvent-less method for the determination of musty and earthy off-flavor compounds, 2-methylisoborneol (MIB) and geosmin (GSM), in salmon tissue was developed using stir bar sorptive extraction -thermal desorption coupled with gas chromatography -mass spectrometry (SBSE -TD -GCMS). M...

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

    ERIC Educational Resources Information Center

    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…

  13. Lipid fatty acid profile analyses in liver and serum in rats with nonalcoholic steatohepatitis using improved gas chromatography-mass spectrometry methodology

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fatty acids (FA) are essential components of lipids and exhibit important biological functions. The analyses of FAs are routinely carried out by gas chromatography-mass spectrometry, after multi-step sample preparation. In this study, several key experimental factors were carefully examined, validat...

  14. Analysis of Whiskey by Dispersive Liquid-Liquid Microextraction Coupled with Gas Chromatography/Mass Spectrometry: An Upper Division Analytical Chemistry Experiment Guided by Green Chemistry

    ERIC Educational Resources Information Center

    Owens, Janel E.; Zimmerman, Laura B.; Gardner, Michael A.; Lowe, Luis E.

    2016-01-01

    Analysis of whiskey samples prepared by a green microextraction technique, dispersive liquid-liquid microextraction (DLLME), before analysis by a qualitative gas chromatography-mass spectrometry (GC/MS) method, is described as a laboratory experiment for an upper division instrumental methods of analysis laboratory course. Here, aroma compounds in…

  15. METHOD 530 DETERMINATION OF SELECT SEMIVOLATILE ORGANIC CHEMICALS IN DRINKING WATER BY SOLID PHASE EXTRACTION AND GAS CHROMATOGRAPHY/ MASS SPECTROMETRY (GC/MS)

    EPA Science Inventory

    1.1. This is a gas chromatography/mass spectrometry (GC/MS) method for the determination of selected semivolatile organic compounds in drinking waters. Accuracy and precision data have been generated in reagent water, and in finished ground and surface waters for the compounds li...

  16. DETERMINATION OF A BOUND MUSK XYLENE METABOLITE IN CARP HEMOGLOBIN AS A BIOMARKER OF EXPOSURE BY GAS CHROMATOGRAPHY MASS SPECTROMETRY USING SELECTED ION MONITORING

    EPA Science Inventory

    Musk xylene (MX) is widely used as a fragrance ingredient in commercial toiletries. Identification and quantification of a bound 4-amino-MX (AMX) metabolite was carried out by gas chromatography-mass spectrometry (GC/MS), with selected ion monitoring (SIM). Detection of AMX occur...

  17. Thermal ExtractionTwo-Dimensional Gas ChromatographyMass Spectrometry with Heart-Cutting for Nitrogen Heterocyclics in Biomass Burning Aerosols

    EPA Science Inventory

    A thermal extraction-two-dimensional gas chromatography-mass spectrometry (TE-GC-MS) method (with heart-cutting) is developed for quantitatively assessing nitrogen (N-bearing organic species (e.g., pyrrole, pyridine, nitriles, and amines) in aerosols emitted from agricultural fir...

  18. AUTOMATED GEL-PERMEATION SYSTEM FOR REMOVAL OF LIPIDS IN GAS CHROMATOGRAPHY/MASS SPECTROMETRIC ANALYSIS OF FATTY TISSUES FOR XENOBIOTIC CHEMICALS

    EPA Science Inventory

    The interference of natural lipids in gas chromatography/mass spectrometric analysis of xenobiotic chemicals in fatty tissue can be substantially reduced using gel-permeation chromatographic removal of the lipids. This paper presents an inexpensive controller which can be used wi...

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

    ERIC Educational Resources Information Center

    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

  20. Dehydration of Methylcyclohexanol Isomers in the Undergraduate Organic Laboratory and Product Analysis by Gas Chromatography-Mass Spectroscopy (GC-MS)

    ERIC Educational Resources Information Center

    Clennan, Malgorzata M.; Clennan, Edward L.

    2011-01-01

    Dehydrations of "cis"- and "trans"-2-methylcyclohexanol mixtures were carried out with 60% sulfuric acid at 78-80 [degrees]C as a function of time and the products were identified by gas chromatography-mass spectroscopy (GC-MS) analysis. The compounds identified in the reaction mixtures include alkenes, 1-, 3-, and 4-methylcyclohexenes and

  1. Analysis of Whiskey by Dispersive Liquid-Liquid Microextraction Coupled with Gas Chromatography/Mass Spectrometry: An Upper Division Analytical Chemistry Experiment Guided by Green Chemistry

    ERIC Educational Resources Information Center

    Owens, Janel E.; Zimmerman, Laura B.; Gardner, Michael A.; Lowe, Luis E.

    2016-01-01

    Analysis of whiskey samples prepared by a green microextraction technique, dispersive liquid-liquid microextraction (DLLME), before analysis by a qualitative gas chromatography-mass spectrometry (GC/MS) method, is described as a laboratory experiment for an upper division instrumental methods of analysis laboratory course. Here, aroma compounds in

  2. Fluoroacetylation/fluoroethylesterification as a derivatization approach for gas chromatography-mass spectrometry in metabolomics: preliminary study of lymphohyperplastic diseases.

    PubMed

    Karamani, Anna A; Fiamegos, Yiannis Ch; Vartholomatos, George; Stalikas, Constantine D

    2013-08-01

    Metabolic fingerprinting in combination with gas chromatography and multivariate analysis is being extensively employed for the improved understanding of biological changes induced by endogenous or exogenous factors. Chemical derivatization increases the sensitivity and specificity of gas chromatography-mass spectrometry (GC-MS) for polar or thermally labile biological compounds, which bear derivatizable groups. Thus, there is a constant demand for simple methods of derivatization and separation that satisfy the need for metabolite analysis, identifying as many chemical classes of compounds as possible. In this study, an optimized protocol of extraction and derivatization is established as a generally applicable method for the analysis of a wide range of classes of metabolites in urine, whole blood and saliva. Compounds of biological relevance bearing hydroxyl- carboxyl- and amino-groups are derivatized using single-step fluoroacetylation/fluoroethylesterification after proper optimization of the protocol. Subsequently, the developed derivatization procedure is engaged in finding blood metabolic biomarkers, induced by lymphohyperplastic disease, through the metabolomic fingerprinting approach, the multivariate modeling (hierarchical cluster analysis) and GC-MS. Our preliminary, GC-MS-based metabolomic fingerprinting study underlines the contribution of certain metabolites to the discrimination of patients with lymphohyperplastic diseases. PMID:23806352

  3. [Determination of monoethylglycinexylidide concentration in serum using solid phase extraction and capillary gas chromatography-mass spectrometry].

    PubMed

    Wang, Zhenxia; Zhang, Ruiming; Cao, Wei; Ouyang, Xiaohui; Zhao, Haiping; Dong, Peide; Meng, Xingkai

    2008-05-01

    A novel method for the determination of monoethylglycinexylidide (MEGX) (lidocaine metabolin) in serum using solid phase extraction (SPE) and capillary gas chromatography-mass spectrometry (GC-MS) was established. The serum sample was extracted with a CN-SPE column. An HP-5MS capillary column (15 m x 0.25 mm x 0.1 microm) was used. The initial temperature of the column was set at 100 degrees C, held for 1 min, then raised to 200 degrees C at 40 degrees C/min, and held at 200 degrees C for 0.5 min. The sample size was 2 microL, and the split ratio was set at 1 : 1. The carrier gas was high purity helium with a flow rate of 1.0 mL/min. The monitoring ions for the determination were m/z 58 for MEGX and m/z 86 for procaine (internal standard). The calibration curve of MEGX had good linear relationship in the range of 1.562 - 25 ng/mL ( r = 0.998 1). The limit of detection was 0.5 ng/mL. The extraction recovery ranged from 80.1% to 85.7%. The method advanced the quantitative analysis of MEGX in serum by combining rapid and efficient SPE with specific and sensitive quantitation by GC-MS. PMID:18724665

  4. Gas chromatography-mass spectrometric determination of fatty acids in seed oil of winged bean (Psophocarpus tetragonolobus (L.) DC).

    PubMed

    Higuchi, M; Terao, J; Iwai, K

    1982-10-01

    Fatty acids of winged bean seed oil were examined by gas chromatography-mass spectrometry of their pyrrolidide derivatives. Oleic and linoleic acids were determined to be the major unsaturated fatty acids in the oil. Long chain saturated fatty acids, such as behenic and lignoceric acids, were found in relatively high amounts as compared with other edible seed oils. The fatty acids that could not be separated by gas liquid chromatography were identified as linolenic acid and arachidic acid respectively on mass spectrometric analysis. Parinaric acid, previously reported by Cerny et al., was not detected and this supposed fraction was instead found to be eiconsenoic acid. Erucic acid, suspected of having an adverse effect on myocardial lesions in rats, was detected but only in small quantity. The identifications of these unsaturated fatty acids were further confirmed by deducing the location of the double bonds in their moieties. From these findings, winged bean seed oil can be suggested as being a food source of favorable quality. PMID:7161648

  5. Development of thermal desorption gas chromatography/mass spectrometry as a rapid method for ambient particulate characterization

    NASA Astrophysics Data System (ADS)

    Sheya, Sue Anne N.

    A direct thermal desorption gas chromatography/mass spectrometry (TD GC/MS) method for air particulate matter (PM) analysis of volatile and semivolatile organic compounds was investigated. This technique uses a specially designed microdesorption GC inlet utilizing an inductively heated ferromagnetic foil with a Curie point temperature suitable for desorption, which can accommodate microgram amounts of material deposited on a thin strip of quartz fiber filter. Liquid or solid samples can be rapidly desorbed within 10 s at 315C, followed by 30--40 min of chromatography time. The results obtained by this technique were found to be statistically equivalent to those obtained by the conventional solvent extraction gas chromatography/mass spectrometry (SX GC/MS) method for analysis of aromatic and n alkane standards, single source soot particles, and PM 10 filter samples. Correlations between injecting an extract, desorbing an extract, and desorbing particles averaged R = 0.94, with a three way correlation averaging R = 0.97. High volume sampling conducted at 12 spatially distributed sites located along the US/Mexican border of the El Paso/Juarez metroplex supplied 24h PM 10 filters for an investigation combining thermal desorption with a rapid online chemical derivatization procedure, and multivariate methods of source attribution using principal component and canonical correlation analysis of the resultant chemical markers. Four major combustion related PM emission sources were revealed at these sites: automotive, waste burning, biomass burning and meat cooking. A second investigation conducted in the same area used mediumvolume sampling to collect 2 h timeresolved PM 10 receptor samples for TD GC/MS analysis. Additionally, 2 h samples for inorganic analysis, multichannel particle size distribution measurements, and meteorological data were collected enabling generation of circadian PM multicharacterization profiles. Factor analysis based receptor modeling using principal component analysis of the mixed characterization data resulted in the deconvolution of temporally overlapping PM events, trends and gradients. Results of the temporally resolved PM receptor sampling profiles confirmed the results of the spatially distributed PM receptor sampling in that the major sources were attributed to automotive traffic, biomass and waste combustion. However, in the time resolved data, urban dust events---in particular a large evening PM peak---were seen to play a more prominent role.

  6. Comparison of the limulus amebocyte lysate test and gas chromatography-mass spectrometry for measuring lipopolysaccharides (endotoxins) in airborne dust from poultry-processing industries.

    PubMed Central

    Sonesson, A; Larsson, L; Schtz, A; Hagmar, L; Hallberg, T

    1990-01-01

    The lipopolysaccharide (endotoxin) content in airborne dust samples from three different poultry slaughterhouses was determined with both the chromogenic Limulus amebocyte lysate assay and gas chromatography-mass spectrometry analysis of lipopolysaccharide-derived 3-hydroxy fatty acids. Gram-negative cell walls were also measured by using two-dimensional gas chromatography/electron-capture analysis of diaminopimelic acid originating from the peptidoglycan. The correlation between the results of the Limulus assay and those of gas chromatography-mass spectrometry for determination of the lipopolysaccharide content in the dust samples was poor, whereas a good correlation was obtained between lipopolysaccharide and diaminopimelic acid concentrations with the gas chromatographic methods. The results suggest that it is predominantly cell-wall-dissociated lipopolysaccharides that are measured with the Limulus assay, whereas the gas chromatographic methods allow determination of total concentrations of lipopolysaccharide, including Limulus-inactive lipopolysaccharide, gram-negative cells, and cellular debris. PMID:2187411

  7. Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry.

    PubMed

    Hilkert; Douthitt; Schlter; Brand

    1999-07-01

    Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd. PMID:10407302

  8. SPECIATION OF SUBSURFACE CONTAMINANTS BY CONE PENETROMETRY GAS CHROMATOGRAPHY/MASS SPECTROMETRY. (R826184)

    EPA Science Inventory

    A thermal extraction cone penetrometry gas chroma tography/mass spectrometry system (TECP GC/MS) has been developed to detect subsurface contaminants in situ. The TECP can collect soil-bound organics up to depths of 30 m. In contrast to traditional cone penetrometer sample collec...

  9. PRECOLUMN SAMPLE ENRICHMENT DEVICE FOR ANALYSIS OF AMBIENT VOLATILE ORGANICS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY

    EPA Science Inventory

    Gas chromatographic-mass spectrometric (GC/MS) identification of air pollutants generally requires a preconcentration step to provide sufficient sample for analysis. Cryogenic trapping is often used to enrich the sample since nitrogen and oxygen are not condensed. It does, howeve...

  10. Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Freeman, K. H.; Ricci, M. P.; Studley, S. A.; Hayes, J. M.

    1995-01-01

    Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

  11. A phytochemical study of the quinolizidine alkaloids from Genista tenera by gas chromatography-mass spectrometry.

    PubMed

    Martins, Alice; Wink, Michael; Tei, Andreas; Brum-Bousquet, Michle; Tillequin, Franois; Rauter, Amlia-Pilar

    2005-01-01

    Gas chromatography coupled with mass spectrometry has been used to analyse the alkaloids present in the aerial parts of Genista tenera. Anagyrine, cytisine, N-formylcytisine, N-methylcytisine and lupanine were the major compounds, the last two alkaloids being known for their hypoglycaemic activity. Dehydrocytisine, 5,6-dehydrolupanine, rhombifoline, aphylline and thermopsine were the minor alkaloids. The characterisation of the constituents was based on comparison of their Kovats retention indexes and electron impact-mass spectrometric data recorded on-line with those of reference compounds and literature data. PMID:16042152

  12. Gas chromatography-mass spectrometry of carbonyl compounds in cigarette mainstream smoke after derivatization with 2,4-dinitrophenylhydrazine.

    PubMed

    Dong, Ji-Zhou; Moldoveanu, Serban C

    2004-02-20

    An improved gas chromatography-mass spectrometry (GC-MS) method was described for the analysis of carbonyl compounds in cigarette mainstream smoke (CMS) after 2,4-dinitrophenylhydrazine (DNPH) derivatization. Besides formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, methyl ethyl ketone, butyraldehyde, and crotonaldehyde that are routinely analyzed in cigarette smoke, this technique separates and allows the analysis of several C4, C5 and C6 isomeric carbonyl compounds. Differentiation could be made between the linear and branched carbon chain components. In cigarette smoke, the branched chain carbonyls are found at higher level than the linear chain carbonyls. Also, several trace carbonyl compounds such as methoxyacetaldehyde were found for the first time in cigarette smoke. For the analysis, cigarette smoke was collected using DNPH-treated pads, which is a simpler procedure compared to conventional impinger collection. Thermal decomposition of DNPH-carbonyl compounds was minimized by the optimization of the GC conditions. The linear range of the method was significantly improved by using a standard mixture of DNPH-carbonyl compounds instead of individual compounds for calibration. The minimum detectable quantity for the carbonyls ranged from 1.4 to 5.6 microg/cigarette. PMID:14971480

  13. Fuzzy C-means clustering for chromatographic fingerprints analysis: A gas chromatography-mass spectrometry case study.

    PubMed

    Parastar, Hadi; Bazrafshan, Alisina

    2016-03-18

    Fuzzy C-means clustering (FCM) is proposed as a promising method for the clustering of chromatographic fingerprints of complex samples, such as essential oils. As an example, secondary metabolites of 14 citrus leaves samples are extracted and analyzed by gas chromatography-mass spectrometry (GC-MS). The obtained chromatographic fingerprints are divided to desired number of chromatographic regions. Owing to the fact that chromatographic problems, such as elution time shift and peak overlap can significantly affect the clustering results, therefore, each chromatographic region is analyzed using multivariate curve resolution-alternating least squares (MCR-ALS) to address these problems. Then, the resolved elution profiles are used to make a new data matrix based on peak areas of pure components to cluster by FCM. The FCM clustering parameters (i.e., fuzziness coefficient and number of cluster) are optimized by two different methods of partial least squares (PLS) as a conventional method and minimization of FCM objective function as our new idea. The results showed that minimization of FCM objective function is an easier and better way to optimize FCM clustering parameters. Then, the optimized FCM clustering algorithm is used to cluster samples and variables to figure out the similarities and dissimilarities among samples and to find discriminant secondary metabolites in each cluster (chemotype). Finally, the FCM clustering results are compared with those of principal component analysis (PCA), hierarchical cluster analysis (HCA) and Kohonon maps. The results confirmed the outperformance of FCM over the frequently used clustering algorithms. PMID:26916594

  14. Determination of polycyclic aromatic hydrocarbons in fresh milk by hollow fiber liquid-phase microextraction-gas chromatography mass spectrometry.

    PubMed

    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 g/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 g/L based on a signal-to-noise ratio of 3:1. Average relative recoveries for the determination of PAHs studied at 100 g/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. PMID:22776739

  15. Headspace-trap gas chromatography-mass spectrometry for determination of sulphur mustard and related compounds in soil.

    PubMed

    Røen, Bent T; Unneberg, Erik; Tørnes, John Aa; Lundanes, Elsa

    2010-04-01

    Methods for trace determination of sulphur mustard (HD) and some related cyclic sulphur compounds in soil samples have been developed using headspace-trap in combination with gas chromatography-mass spectrometry (GC-MS). Two quite different types of soil were employed in the method optimisation (sandy loam and silty clay loam). Prior to analysis, water saturated with sodium chloride was added to the samples, at a water to soil ratio of 1:1. A detection limit of 3 ng/g was achieved for HD, while the cyclic sulphur compounds 1,4-thioxane, 1,3-dithiolane and 1,4-dithiane could be detected at 0.2-0.7 ng/g. The methods were validated in the concentration range from the limit of quantification (LOQ) to hundred times LOQ. The within assay precision at fifty times LOQ was 6.9-7.3% relative standard deviation (RSD) for determination of the cyclic sulphur compounds, and 15% RSD for determination of HD. Recoveries were in the range of 43-60% from the two soil types. As the technique requires very little sample preparation, the total time for sample handling and analysis was less than 1h. The technique was successfully employed for the determination of cyclic sulphur compounds in a sediment sample from an old dumping site for chemical munitions, known to contain HD degradation products. PMID:20189185

  16. Mammalian fatty acid synthase activity from crude tissue lysates tracing C-labeled substrates using gas chromatography-mass spectrometry.

    PubMed

    Rudolph, Michael C; Karl Maluf, N; Wellberg, Elizabeth A; Johnson, Chris A; Murphy, Robert C; Anderson, Steve M

    2012-09-15

    Fatty acid synthase (FASN or FAS, EC 2.3.1.85) is the sole mammalian enzyme to synthesize fatty acids de novo from acetyl- and malonyl-coenzyme A (CoA) esters. This article describes a new method that directly quantifies uniformly labeled (C??-labeled palmitate ([C??]palmitate) by tracing [C?]acetyl-CoA and [C?]malonyl-CoA using an in vitro FASN assay. This method used gas chromatography-mass spectrometry (GC-MS) to detect [C??]palmitate carboxylate anions (m/z 271) of pentafluorobenzyl (PFB) derivatives and was highly sensitive at femtomole quantities. Uniformly incorporated [C??]palmitate was the primary product of both recombinant and crude tissue lysate FASN. Quantification of FASN protein within crude tissue lysates ensured equal FASN amounts, preserved steady-state kinetics, and enabled calculation of FASN-specific activity. FASN activity determined by [C??]palmitate synthesis was consistent with values obtained from ?-nicotinamide adenine dinucleotide 2'-phosphate (NADPH) oxidation assays. Analysis of FASN activity from tissue extracts was not hampered by contaminating enzymes or preexisting fatty acids. Crude mammary gland and liver lysates had significantly different activities at 82 and 65 nmol min? mg?, respectively, suggesting that tissue-specific activity levels differ in a manner unrelated to FASN amount. GC-MS quantification of [C??]palmitate synthesis permits sensitive evaluation of FASN activity from tissues of varied physiological states and of purified FASN activity in the presence of modifying proteins, enzymes, or drugs. PMID:22728958

  17. Applications of Hadamard transform-gas chromatography/mass spectrometry for the detection of hexamethyldisiloxane in a wafer cleanroom.

    PubMed

    Cheng, Yuan-Kai; Lin, Cheng-Huang; Kuo, Samuel; Yang, Jonathan; Hsiung, Szu-Yuan; Wang, Jia-Lin

    2012-01-13

    The Hadamard transform-gas chromatography/mass spectrometry (HT-GC/MS) technique was successfully employed for the detection of hexamethyldisiloxane (HMDSO, C(6)H(18)OSi(2)) at the sub-nL/L level in a semiconductor wafer cleanroom. Indoor air samples were collected from the room, according to EPA Method TO-17 using a Tedlar bag where the air samples were allowed to pass through an absorption tube for 24 h. The condensed components were then heated and simultaneously injected into a GC column through a Hadamard-injector, which was operated in accordance with the Hadamard codes. Compared to the single injection used in most GC/MS systems, the signal-to-noise (S/N) ratios were substantially improved after the inverse Hadamard transformation of the encoded chromatogram. Under optimized conditions, when cyclic S-matrix orders of 255, 1023 and 2047 were used, the S/N ratios of the HMDSO signals were substantially improved by 7.4-, 15.1- and 20.1-fold, respectively. These improvements are in good agreement with theoretically calculated values (8.0-, 16.0- and 22.6-fold, respectively). We found that when the HT-GC/MS technique was applied, HMDSO could be detected at the 0.1 nL/L level. PMID:22192564

  18. Metabolite profiling of sucrose effect on the metabolism of Melissa officinalis by gas chromatography-mass spectrometry.

    PubMed

    Kim, Sooah; Shin, Min Hye; Hossain, Md Aktar; Yun, Eun Ju; Lee, Hojoung; Kim, Kyoung Heon

    2011-04-01

    The effect of sugar on plant metabolism, which is known to be similar to hormone-like signaling, was metabolomically studied using Melissa officinalis (lemon balm). The metabolite profiles of M. officinalis treated with sucrose were analyzed by gas chromatography-mass spectrometry (GC-MS) and principal component analysis (PCA). A total of 64 metabolites from various chemical classes including alcohols, amines, amino acids, fatty acids, inorganic acids, organic acids, phosphates, and sugars were identified by GC-MS. Three groups treated with different sucrose concentrations were clearly separated by PCA of their metabolite profiles, indicating changes in the levels of many metabolites depending on the sucrose concentration. Metabolite profiling revealed that treatment with a higher sucrose level caused an increase in the levels of metabolites such as sugars, sugar alcohols, and sugar phosphates, which are related to the glycolytic pathway of M. officinalis. Furthermore, proline and succinic acid, which are associated with the proline-linked pentose phosphate pathway, the shikimic acid pathway, and the biosynthesis of phenylpropanoids, also increased with increasing sucrose concentration. Therefore, these metabolic changes induced by sucrose ultimately led to the increased production of flavonoids such as caffeic acid via the biosynthetic pathway of phenylpropanoids. This study demonstrated that the abundance changes in some primary and secondary metabolites were somewhat interlocked with each other in response to sucrose. PMID:21301821

  19. [Simultaneous determination of nine pharmaceuticals personal care products in waters by solid phase extraction-gas chromatography-mass spectrometry].

    PubMed

    Jia, Yanyan; Tan, Jianhua; Xu, Chen; Tang, Jiajun; Wang, Yingli; Xie, Qilai

    2014-03-01

    An analytical method has been developed and validated for the simultaneous determination of nine pharmaceuticals and personal care products (PPCPs) in water samples, including salicylic acid, naproxen, ibuprofen, paracetamol, clofibric acid, triclosan, diclofenac, ketoprofen, bisphenol A. The qualification and quantification of the target compounds were performed by gas chromatography-mass spectrometry in selected ion monitoring mode (GC-MS-SIM). The water samples were concentrated and purified through Oasis HLB cartridges after the pH value of the water was adjusted to 3, then derivatized with trimethyl sulfonium hydroxide (TMSH) at room temperature, and determined by GC-MS-SIM using 2,4,5-fenoprop as internal standard. The conditions for sample pretreatment (e. g. solid phase extraction and derivatization) were studied. Under the optimized conditions, the recoveries were ranged from 50.7% to 115.4% with the relative standard deviations lower than 10%. The limits of detection were in the range of 0.03-0.30 microg/L and the limits of quantification were in the range of 0.15-1.50 microg/L. The method has been successfully applied to monitor the occurrence of the PPCPs residues in agricultural irrigation water in Dongguan, Guangdong Province. The four compounds were detected at maximum mass concentration range of 0.176-0.998 microg/L. It proved that this analytical method is sensitive, reliable and acceptable. PMID:24984466

  20. A rapid and simple procedure for the determination of ephedrine alkaloids in dietary supplements by gas chromatography-mass spectrometry.

    PubMed

    Marchei, Emilia; Pellegrini, Manuela; Pacifici, Roberta; Zuccaro, Piergiorgio; Pichini, Simona

    2006-08-28

    A simple method for the determination of ephedrine alkaloids: ephedrine (EF), pseudoephedrine (PE), norpseudoephedrine (NPE), norephedrine (NE) and methylpseudoephedrine (MPE) in dietary supplements by gas chromatography-mass spectrometry is described. After the addition of 3,4-methylenedioxypropylamphetamine as internal standard, a liquid-liquid extraction procedure in alkaline conditions with chloroform/isopropanol (9:1, v/v) was applied to the samples prior to analysis. Chromatography was performed on a fused capillary column and analytes, derivatized with pentafluoropropionic anhydride, were determined in the selected-ion-monitoring (SIM) mode. The method was validated in the range 0.3-10 microg/mg for EP, 0.06-2.5 microg/mg for PE and NPE and 0.04-1 microg/mg NE and MPE. Mean recovery ranged between 65.7 and 81.3% for the different analytes in dietary supplements. The quantification limits were 0.3 microg/mg for EP, 0.06 microg/mg for PE, 0.04 microg/mg for NPE, NE and MPE. The method was applied to analysis of various dietary supplements containing Ma-huang (Ephedra Sinica) and Sida Cordifolia plant extracts promoted for aiding weight control and boosting sports performance and energy. PMID:16580167

  1. Determining the Levels of Volatile Organic Pollutants in Urban Air Using a Gas Chromatography-Mass Spectrometry Method

    PubMed Central

    Nicoara, Simona; Tonidandel, Loris; Traldi, Pietro; Watson, Jonathan; Morgan, Geraint; Popa, Ovidiu

    2009-01-01

    The paper presents the application of a method based on coupled gas chromatography-mass spectrometry, using an isotopically labelled internal standard for the quantitative analysis of benzene (B), toluene (T), ethyl benzene (E), and o-, m-, p-xylenes (X). Their atmospheric concentrations were determined based on short-term sampling, in different sites of Cluj-Napoca, a highly populated urban centre in N-W Romania, with numerous and diversified road vehicles with internal combustion engines. The method is relatively inexpensive and simple and shows good precision and linearity in the ranges of 760 ?g/m3 (B), 1390 ?g/m3 (T), 750 ?g/m3 (E), 1070 ?g/m3 (X-m,p), and 20130 ?g/m3 (X-o). The limits of quantitation/detection of the method LOQ/LOD are of 10/5 ?g/m3 (Xo), 5/3 ?g/m3 (B, E, X-m,p), and of 3/1 ?g/m3 (T), respectively. PMID:20168976

  2. Comparison of gas chromatography/mass spectrometry and immunoassay techniques on concentrations of atrazine in storm runoff

    USGS Publications Warehouse

    Lydy, M.J.; Carter, D.S.; Crawford, C.G.

    1996-01-01

    Gas chromatography/mass spectrometry (GC/MS) and enzyme linked immunosorbent assay (ELISA) techniques were used to measure concentrations of dissolved atrazine in 149 surface-water samples. Samples were collected during May 1992-September 1993 near the mouth of the White River (Indiana) and in two small tributaries of the river. GC/MS was performed on a Hewlett- Packard 5971A with electron impact ionization and selected ion monitoring of filtered water samples extracted by C-18 solid phase extraction: ELISA was performed with a magnetic-particle-based assay with photometric analysis. ELISA results compared reasonably well to GC/MS measurements at concentrations below the Maximum Contaminant Level for drinking water set by the U.S. Environmental Protection Agency (3.0 ??g/L), but a systematic negative bias was observed at higher concentrations. When higher concentration samples were diluted into the linear range of calibration, the relation improved. A slight positive bias was seen in all of the ELISA data compared to the GC/MS results, and the bias could be partially explained by correcting the ELISA data for cross reactivity with other triazine herbicides. The highest concentrations of atrazine were found during the first major runoff event after the atrazine was applied. Concentrations decreased throughout the rest of the sampling period even though large runoff events occurred during this time, indicating that most atrazine loading to surface waters in the study area occurs within a few weeks after application.

  3. Direct detection of Mycobacterium tuberculosis in sputum using combined solid phase extraction-gas chromatography-mass spectrometry.

    PubMed

    Dang, Ngoc A; Mouro, Marta; Kuijper, Sjoukje; Walters, Elisabetta; Janssen, Hans-Gerd; Kolk, Arend H J

    2015-04-01

    Recently, thermally-assisted hydrolysis and methylation followed by gas chromatography-mass spectrometry (THM-GC-MS) in combination with chemometrics has been used to develop a 20-compound model for fast differentiation of Mycobacterium tuberculosis (MTB) from Non-tuberculous mycobacteria (NTM) in bacterial cultures. This model provided better than 95% accuracy. In our current work a hexane/methanol/water extraction followed by a solid phase extraction (SPE) clean-up procedure was developed for use before THM-GC-MS, to make the test suitable for the identification of mycobacteria in sputum. The 20 biomarker model had to be adapted since many compounds were also found in the sputum of non-tuberculosis patients. An algorithm was established based on tuberculostearic acid, hexacosanoic acid and mycoserosates. The detection limit of the method was approximately 110(4) bacteria/mL sputum. Sputum specimens from 32 patients from South Africa who were suspected of having tuberculosis were blindly tested using the new method. Eight of the nine culture-positive sputum specimens were detected by the new SPE-THM-GC-MS method, resulting in a sensitivity of 89%. The specimen that was missed by the new method was also microscopy negative. The specificity of the test was 100%; all 23 microscopy- and culture-negative specimens were correctly identified as negative by SPE-THM-GC-MS. PMID:25728368

  4. Wavelet- and Fourier-transform-based spectrum similarity approaches to compound identification in gas chromatography/mass spectrometry.

    PubMed

    Koo, Imhoi; Zhang, Xiang; Kim, Seongho

    2011-07-15

    The high-throughput gas chromatography/mass spectrometry (GC/MS) technology offers a powerful means of analyzing a large number of chemical and biological samples. One of the important analyses of GC/MS data is compound identification. In this work, novel spectral similarity measures based on the discrete wavelet and Fourier transforms were proposed. The proposed methods are composite similarities that are composed of weighted intensities and wavelet/Fourier coefficients using cosine correlation. The performance of the proposed approaches along with the existing similarity measures was evaluated using the NIST Chemistry WebBook mass database maintained by the National Institute of Standards and Technology (NIST) as a library of reference spectra and repetitive mass spectral data as query spectra. The analysis results showed that the identification accuracies of the wavelet- and Fourier-transform-based methods were improved by 2.02% and 1.95%, respectively, compared to that of the weighted dot product (cosine correlation) and by 3.01% and 3.08%, respectively, compared to that of the composite similarity measure. The improved identification accuracy demonstrates that the proposed approaches outperformed the existing similarity measures in the literature. PMID:21651237

  5. Wavelet and Fourier Transforms-based Spectrum Similarity Approaches to Compound Identification in Gas Chromatography Mass Spectrometry

    PubMed Central

    Koo, Imhoi; Zhang, Xiang; Kim, Seongho

    2011-01-01

    The high-throughput gas chromatography-mass spectrometry (GC-MS) technology offers a powerful means of analyzing a large number of chemical and biological samples. One of the important analyses of GC-MS data is compound identification. In this work, novel spectral similarity measures based on the discrete wavelet and Fourier transforms were proposed. The proposed methods are composite similarities that are composed of weighted intensities and wavelet/Fourier coefficients using cosine correlation. The performance of the proposed approaches along with the existing similarity measures was evaluated using the NIST Chemistry WebBook mass database maintained by the National Institute of Standards and Technology (NIST) as a library of reference spectra and repetitive mass spectral data as query spectra. The analysis results showed that the identification accuracies of the wavelet/Fourier transform-based methods were improved by 2.02% and 1.95%, respectively, comparing the weighted dot product (cosine correlation) and by 3.01% and 3.08%, respectively, comparing to the composite similarity measure. The improved identification accuracy demonstrates that the proposed approaches outperformed the existing similarity measures in the literature. PMID:21651237

  6. Gas Chromatography-Mass Spectrometry Analysis of Ulva fasciata (Green Seaweed) Extract and Evaluation of Its Cytoprotective and Antigenotoxic Effects.

    PubMed

    Rodeiro, Idania; Olguín, Sitlali; Santes, Rebeca; Herrera, José A; Pérez, Carlos L; Mangas, Raisa; Hernández, Yasnay; Fernández, Gisselle; Hernández, Ivones; Hernández-Ojeda, Sandra; Camacho-Carranza, Rafael; Valencia-Olvera, Ana; Espinosa-Aguirre, Jesús Javier

    2015-01-01

    The chemical composition and biological properties of Ulva fasciata aqueous-ethanolic extract were examined. Five components were identified in one fraction prepared from the extract by gas chromatography-mass spectrometry, and palmitic acid and its ethyl ester accounted for 76% of the total identified components. Furthermore, we assessed the extract's antioxidant properties by using the DPPH, ABTS, and lipid peroxidation assays and found that the extract had a moderate scavenging effect. In an experiment involving preexposition and coexposition of the extract (1-500 µg/mL) and benzo[a]pyrene (BP), the extract was found to be nontoxic to C9 cells in culture and to inhibit the cytotoxicity induced by BP. As BP is biotransformed by CYP1A and CYP2B subfamilies, we explored the possible interaction of the extract with these enzymes. The extract (25-50 µg/mL) inhibited CYP1A1 activity in rat liver microsomes. Analysis of the inhibition kinetics revealed a mixed-type inhibitory effect on CYP1A1 supersome. The effects of the extract on BP-induced DNA damage and hepatic CYP activity in mice were also investigated. Micronuclei induction by BP and liver CYP1A1/2 activities significantly decreased in animals treated with the extract. The results suggest that Ulva fasciata aqueous-ethanolic extract inhibits BP bioactivation and it may be a potential chemopreventive agent. PMID:26612994

  7. Determination of aromatic hydrocarbons in bituminous emulsion sealants using headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    PubMed

    Tang, Bing; Isacsson, Ulf

    2006-12-22

    The possibility of quantitative determination of aromatic hydrocarbons in bituminous emulsion sealants was investigated using headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS). The target analytes studied were benzene, toluene, ethylbenzene, p-, m-, and o-xylene (BTEX) as well as 1,3,5- and 1,2,4-trimethylbenzene. Experimental factors influencing HS-SPME efficiency were studied (sample-headspace equilibration time, extraction time and sample matrix effects). A HS-SPME method using surrogate matrix was developed. The detection limit was estimated as approximately 0.1 ppmw for the target analytes investigated. Good linearity was observed (R(2)>0.997) for all calibration curves obtained. The repeatability of the method (RSD, relative standard deviation) was found less than 10%. The accuracy of the method given by recovery of spiked samples was between 99 and 116%. The HS-SPME method developed was applied to two commercially available bituminous emulsion sealants. External calibration and standard addition approaches were investigated, and statistical paired t-test was performed. The contents of target aromatic hydrocarbons in the sealants studied varied from approximately 0.4 to 150 ppmw. The method developed shows potential as a tool for the determination of aromatic hydrocarbons in emulsified bituminous materials. PMID:17069821

  8. Direct detection of Mycobacterium tuberculosis in sputum: A validation study using solid phase extraction-gas chromatography-mass spectrometry.

    PubMed

    Mouro, Marta P B; Kuijper, Sjoukje; Dang, Ngoc A; Walters, Elisabetta; Janssen, Hans-Gerd; Kolk, Arend H J

    2016-02-15

    Tuberculosis (TB) remains a worldwide health problem, especially in developing countries. Correct identification of Mycobacterium tuberculosis (MTB) infection is extremely important for providing appropriate treatment and care to patients. Here we describe a solid phase extraction-gas chromatography-mass spectrometry method (SPE-THM-GC-MS) for the detection of five biomarkers for M. tuberculosis. The method for classification is developed and validated through the analysis of 112 sputum samples from patients suspected of having TB. Twenty of twenty-five MTB culture-positive sputum samples were correctly classified as positive by our improved SPE-THM-GC-MS method. Eighty-five of eighty-seven MTB culture-negative samples were also negative by SPE-THM-GC-MS. The overall sensitivity of the new SPE-THM-GC-MS method is 80% (20/25) and the specificity is 98% (85/87) compared with culture. The method proved to be reliable and, although complex in principle, easy to operate due to the high degree of automation. PMID:26807702

  9. Plasma Metabolite Profiling and Chemometric Analyses of Lung Cancer along with Three Controls through Gas Chromatography-Mass Spectrometry

    PubMed Central

    Musharraf, Syed Ghulam; Mazhar, Shumaila; Choudhary, Muhammad Iqbal; Rizi, Nadeem; Atta-ur-Rahman

    2015-01-01

    Lung cancer has been the most common death causing cancer in the world for several decades. This study is focused on the metabolite profiling of plasma from lung cancer (LC) patients with three control groups including healthy non-smoker (NS), smokers (S) and chronic obstructive pulmonary disease patients (COPD) samples using gas chromatography-mass spectrometry (GC-MS) in order to identify the comparative and distinguishing metabolite pattern for lung cancer. Metabolites obtained were identified through National Institute of Standards and Technology (NIST) mass spectral (Wiley registry) and Fiehn Retention Time Lock (RTL) libraries. Mass Profiler Professional (MPP) Software was used for the alignment and for all the statistical analysis. 32 out of 1,877 aligned metabolites were significantly distinguished among three controls and lung cancer using p-value ? 0.001. Partial Least Square Discriminant Analysis (PLSDA) model was generated using statistically significant metabolites which on external validation provide high sensitivity (100%) and specificity (78.6%). Elevated level of fatty acids, glucose and acids were observed in lung cancer in comparison with control groups apparently due to enhanced glycolysis, gluconeogenesis, lipogenesis and acidosis, indicating the metabolic signature for lung cancer. PMID:25712604

  10. Determination of chloro-s-triazines including didealkylatrazine using solid-phase extraction coupled with gas chromatography-mass spectrometry.

    PubMed

    Jiang, Hua; Adams, Craig D; Koffskey, Wayne

    2005-02-01

    Chloro-s-triazines are a class of compounds comprising atrazine, simazine, propazine, cyanazine and their chlorinated metabolites. The US Environmental Protection Agency (EPA) has determined that selected chloro-s-triazines--atrazine, simazine, propazine, deethylatrazine, deisopropylatrazine, and didealkylatrazine--have a common mode of toxicity related to endocrine disruption. In this paper, a dual-resin solid-phase extraction (SPE) gas chromatography-mass spectrometry (GC-MS) method is reported that provides for each of these chloro-s-triazines including the polar metabolite, didealkylatrazine. The method utilizes deuterated internal standards for quantitation and terbuthylazine as a recovery standard. The limit-of-detection was 0.01 microg/L for simazine, deethylatrazine, deisopropylatrazine and didealkylatrazine, and 0.02 microg/L for atrazine and propazine in surface water. Mean recoveries for 0.5 and 3.0 microg/L spikes for atrazine, simazine, propazine, deethylatrazine, deisopropylatrazine and didealkylatrazine were 94, 104, 103, 110, 108 and 102%, respectively, in surface water. The method was also validated by matrix spikes into fourteen different raw and treated natural surface waters. This method is useful for monitoring "total chloro-s-triazines" in both raw and treated drinking waters. PMID:15739890

  11. Simultaneous determination of cannabidiol, cannabinol, and delta9-tetrahydrocannabinol in human hair by gas chromatography-mass spectrometry.

    PubMed

    Kim, Jin Young; Suh, Sung Ill; In, Moon Kyo; Paeng, Ki-Jung; Chung, Bong Chul

    2005-09-01

    An analytical method was developed for evaluating the cannabidiol (CBD), cannabinol (CBN), and delta9-tetrahydrocannabinol (delta9-THC) level in human hair using gas chromatography-mass spectrometry (GC-MS). Hair samples (50 mg) were washed with isopropyl alcohol and cut into small fragments (< 1 mm). After adding a deuterated internal standard, the hair samples were incubated in 1.0 M NaOH for 10 min at 95 degrees C. The analytes from the resulting hydrolyzed samples were extracted using a mixture of n-hexane-ethyl acetate (75:25, v/v). The extracts were then evaporated, derivatized, and injected into the GC-MS. The recovery ranges of CBD, CBN, and delta9-THC at three concentration levels were 37.9-94.5% with good correlation coefficients (r2 >0.9989). The intra-day precision and accuracy ranged from -9.4% to 17.7%, and the inter-day precision and accuracy ranged from -15.5% to 14.5%, respectively. The limits of detection (LOD) for CBD, CBN, and delta9-THC were 0.005, 0.002, and 0.006 ng/mg, respectively. The applicability of this method of analyzing the hair samples from cannabis abusers was demonstrated. PMID:16212242

  12. Gas Chromatography-Mass Spectrometry Analysis of Ulva fasciata (Green Seaweed) Extract and Evaluation of Its Cytoprotective and Antigenotoxic Effects

    PubMed Central

    Rodeiro, Idania; Olguín, Sitlali; Santes, Rebeca; Herrera, José A.; Pérez, Carlos L.; Mangas, Raisa; Hernández, Yasnay; Fernández, Gisselle; Hernández, Ivones; Hernández-Ojeda, Sandra; Camacho-Carranza, Rafael; Valencia-Olvera, Ana; Espinosa-Aguirre, Jesús Javier

    2015-01-01

    The chemical composition and biological properties of Ulva fasciata aqueous-ethanolic extract were examined. Five components were identified in one fraction prepared from the extract by gas chromatography-mass spectrometry, and palmitic acid and its ethyl ester accounted for 76% of the total identified components. Furthermore, we assessed the extract's antioxidant properties by using the DPPH, ABTS, and lipid peroxidation assays and found that the extract had a moderate scavenging effect. In an experiment involving preexposition and coexposition of the extract (1–500 µg/mL) and benzo[a]pyrene (BP), the extract was found to be nontoxic to C9 cells in culture and to inhibit the cytotoxicity induced by BP. As BP is biotransformed by CYP1A and CYP2B subfamilies, we explored the possible interaction of the extract with these enzymes. The extract (25–50 µg/mL) inhibited CYP1A1 activity in rat liver microsomes. Analysis of the inhibition kinetics revealed a mixed-type inhibitory effect on CYP1A1 supersome. The effects of the extract on BP-induced DNA damage and hepatic CYP activity in mice were also investigated. Micronuclei induction by BP and liver CYP1A1/2 activities significantly decreased in animals treated with the extract. The results suggest that Ulva fasciata aqueous-ethanolic extract inhibits BP bioactivation and it may be a potential chemopreventive agent. PMID:26612994

  13. Determination of Sucrose in Honey with Derivatization/Solid-Phase Microextraction and Gas-Chromatography/Mass Spectrometry.

    PubMed

    Wang, Haijing; Geppert, Helmut; Fischer, Thomas; Wieprecht, Wolfgang; Mller, Detlev

    2015-10-01

    A new method for the determination of sucrose in honey with derivatization solid-phase microextraction and gas chromatography/mass spectrometry (D-SPME-GC/MS) was developed. The method incorporates a sample derivatization with acetic anhydride using N-methylimidazole as the catalyst and the subsequent enrichment of the analyte in a Polyacrylate-SPME fiber. Results show that 100 L N-methylimidazole and 800 L acetic anhydride were sufficient to complete the acetylation for sucrose in 100 L aqueous sample at room temperature. For SPME, an enrichment time of 30 min was sufficient. SPME was performed by immersing the fiber into the solution with additional vibration. Then, the analyte was desorbed for 5 min at 280C in the GC/MS injection port with splitless mode. The present method exhibits good linearity at a concentration range of 0.3-8% of sucrose in honey with excellent regression (R = 0.9993). The method has been successfully applied to the control of sucrose adulteration in honey. PMID:25911451

  14. Detection and identification of carprofen and its in vivo metabolites in greyhound urine by capillary gas chromatography-mass spectrometry.

    PubMed

    Dumasia, M C; Ginn, A; Hyde, W; Peterson, J; Houghton, E

    2003-05-25

    Rimadyl (carprofen) was administered orally to the racing greyhound at a dose of 2.2 mg kg(-1). Following both alkaline and enzymatic hydrolysis, postadministration urine samples were extracted by mixed mode solid-phase extraction (SPE) cartridges to identify target analyte(s) for forensic screening and confirmatory analysis methods. The acidic isolates were derivatised as trimethylsilyl ethers (TMS) and analysed by gas chromatography-mass spectrometry (GC-MS). Carprofen and five phase I metabolites were identified. Positive ion electron ionisation (EI(+)) mass spectra of the TMS derivatives of carprofen and its metabolites show a diagnostic base peak at M(+)*. -117 corresponding to the loss of COO-Si-(CH(3))(3) group as a radical. GC-MS with positive ion ammonia chemical ionisation (CI(+)) of the compounds provided both derivatised molecular mass and some structural information. Deutromethylation-TMS derivatisation was used to distinguish between aromatic and aliphatic oxidations of carprofen. The drug is rapidly absorbed, extensively metabolised and excreted as phase II conjugates in urine. Carprofen, three aromatic hydroxy and a minor N-hydroxy metabolite were detected for up to 48 h. For samples collected between 2 and 8 h after administration, the concentration of total carprofen ranged between 200 and 490 ng ml(-1). The major metabolite, alpha-hydroxycarprofen was detected for over 72 h and therefore can also be used as a marker for the forensic screening of carprofen in greyhound urine. PMID:12705970

  15. [Determination of musk ketone in aquatic products by gas chromatography-mass spectrometry with dispersive solid phase extraction].

    PubMed

    Ding, Liping; Guo, Jing; Chen, Zhitao; Zhao, Jianhui; Zheng, Ling; Cai, Wei

    2013-05-01

    A dispersive solid phase extraction coupled with gas chromatography-mass spectrometry (GC-MS) method was established for the determination of trace amounts of musk ketone in aquatic products. The target analyte in the samples was extracted with acetonitrile containing 1% acetic acid, cleaned-up with the mixture of N-propyl-ethylenediamine (PSA), C18 and graphitized carbon (GCB), and analyzed by GC-MS under selected ion monitoring (SIM) mode and quantified by the external standard method. The orthogonal experiment was carried out to optimize the pre-treatment conditions. Under the optimal conditions, good linear relationship was obtained in the range of 1 - 50 microg/L for musk ketone with correlation coefficient not less than 0.999, and the limits of detection (S/N = 3) was 0.30 microg/kg. The recoveries of musk ketone in the prawn and tilapia blank samples at three spiked levels of 1.0, 2.0 and 10.0 microg/kg ranged from 91.8% to 110.6% with RSDs in the range of 2.6% - 8.4%. The method is simple, rapid and accurate, and can be used for the routine analysis of musk ketone in aquatic products. PMID:24010352

  16. Monitoring human exposure to ethylene oxide by the determination of hemoglobin adducts using gas chromatography-mass spectrometry

    SciTech Connect

    Farmer, P.B.; Bailey, E.; Gorf, S.M.; Toernqvist, M.O.; Osterman-Golkar, S.; Kautiainen, A.; Lewis-Enright, D.P.

    1986-04-01

    Globin samples from ethylene oxide-exposed workers and non-exposed referrents were analyzed by two methods: (i) gas chromatography-mass spectrometry determination of Nt-(2-hydroxyethyl)histidine as its methyl ester heptafluorobutyryl derivative, after hydrolysis of the protein and isolation of the alkylated amino acid by ion exchange chromatography. The internal standard, Nt-(2-hydroxy-d4-ethyl)histidine, was added to the protein before hydrolysis. (ii) Determination of N-(2-hydroxyethyl)valine after derivatization of the protein by a modified Edman procedure, extraction and g.c.-m.s. determination of alkylated N-terminal valine in the form of its pentafluorophenylthiohydantoin derivative. The internal standard used was in this case a globin with a known content of hydroxy-d4-ethylated amino acids. The two methods gave consistent results, especially at high levels of alkylated products. The average content of hydroxyethylhistidine was 0.6 nmol/g higher than the content of hydroxyethylvaline. Higher levels of background alkylation (of unknown origin) were recorded with the histidine method as compared with the valine method, suggesting that the latter assay should show greater sensitivity for low level ethylene oxide exposure monitoring.

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

    PubMed Central

    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. PMID:24592162

  18. [Pyrolysis of the Lysimachia foenum-graecum Hance extract by online pyrolysis-gas chromatography-mass spectrometry].

    PubMed

    Yang, Yekun; Miao, Enming; Geng, Yongqin; Wei, Yuling; Xu, Jicang; Li, Xuemei; Ding, Zhongtao; Zhou, Jun

    2014-05-01

    In order to study the pyrolytic properties of Lysimachia foenum-graecum Hance extract, it was pyrolysed and detected by online pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). The pyrolytic experimental conditions were designed to simulate the real combustion conditions inside a burning cigarette. The sample was heated at 30 degrees C/s from 300 to 900 degrees C (held for 5 s) under the flow of 9% oxygen in nitrogen. The pyrolytic components and volatile components were compared. The results showed that 64 pyrolytic components were detected, with 88.27% of the total peak area, including linoleic acid ethyl ester (10.33%), hexadecanoic acid, ethyl ester (9.12%), 9,12,15-octadecatrienoic acid, (Z,Z,Z) - (8.03%), 2-furan-carboxaldehyde, 5-(hydroxymethyl) - (6.02%), neophytadiene (5.12%), heptadecanoic acid, ethyl ester (4.50%), acetic acid, phenyl ester (3.51%), 5-methoxy-2, 2-di-methylindan-1-one (2.73%). The number of pyrolytic components was more than that of the volatile components, and 20 components were identified in both pyrolytic components and volatile components, including higher fatty acids and their esters, neophytadiene, 2-furancarboxaldehyde, (hydroxymethyl)-, and 2 (5H)-furanone, 3-hydroxy-4, 5-dimethyl-. The on-line pyrolysis was similar to the real cigarette combustion conditions. The method is a simple, rapid and good qualitative method for the pyrolysis. PMID:25185319

  19. Determination of carbon number distributions of complex phthalates by gas chromatography-mass spectrometry with ammonia chemical ionization.

    PubMed

    Di Sanzo, Frank P; Lim, Peniel J; Han, Wenning W

    2015-01-01

    An assay method for phthalate esters with a complex mixture of isomer of varying carbon numbers, such as di-isononyl phthalate (DINP) and di-isodecyl phthalate (DIDP), using gas chromatography-mass spectrometry (GC-MS) positive chemical ionization (PCI) with 5% ammonia in methane is described. GC-MS-PCI-NH3, unlike GC-MS electron ionization (EI) (GC-MS-EI) that produces generally m/z 149 ion as the main base peak and low intensity M(+) peaks, produces higher intensity (M + 1) ions that allow the determination of total (R + R') carbon number distributions based on the various R and R' alkyl groups of the di-esters moiety. The technique allows distinguishing among the various commercial DINP and DIDP plasticizers. The carbon number distributions are determined in the acceptable range of <0.1 mole percent to >85 mole percent (m/m). Several examples of analysis made on commercial DINP and DIDP are presented. The use of only 5% instead of 100% ammonia simplifies use of GC-MS-PCI-NH3 but still produces sufficient M + 1 ion intensities that are appropriate for the assay. In addition, use of low concentrations of ammonia mitigates potential safety aspects related to use of ammonia and provides less corrosion for the instrument hardware. PMID:26240191

  20. Dual dispersive liquid-liquid microextraction for determination of phenylpropenes in oils by gas chromatography-mass spectrometry.

    PubMed

    Tsai, Chia-Ju; Li, Jih-Heng; Feng, Chia-Hsien

    2015-09-01

    A novel, simple and quick sample preparation method was developed and used for pre-concentration and extraction of six phenylpropenes, including anethole, estragole, eugenol, methyl eugenol, safrole and myristicin, from oil samples by dual dispersive liquid-liquid microextraction. Gas chromatography-mass spectrometry was used for determination and separation of compounds. Several experimental parameters affecting extraction efficiency were evaluated and optimized, including forward-extractant type and volume, surfactant type and concentration, water volume, and back-extractant type and volume. For all analytes (10-1000ng/mL), the limits of detection (S/N?3) ranged from 1.0 to 3.0ng/mL; the limits of quantification (S/N?10) ranged from 2.5 to 10.0ng/mL; and enrichment factors ranged from 3.2 to 37.1 times. Within-run and between-run relative standard deviations (n=6) were less than 2.61% and less than 4.33%, respectively. Linearity was excellent with determination coefficients (r(2)) above 0.9977. The experiments showed that the proposed method is a simple, effective, and environmentally friendly method of analyzing phenylpropenes in oil samples. PMID:26253833

  1. A rapid and simple procedure for the determination of synephrine in dietary supplements by gas chromatography-mass spectrometry.

    PubMed

    Marchei, Emilia; Pichini, Simona; Pacifici, Roberta; Pellegrini, Manuela; Zuccaro, Piergiorgio

    2006-06-16

    A simple and rapid procedure based on gas chromatography-mass spectrometry (GC-MS) is described for determination of synephrine, active principle of Citrus aurantium plant, in solid and liquid dietary supplements. After the addition of 3,4-methylenedioxypropylamphetamine as internal standard (I.S.), a liquid-liquid extraction procedure in alkaline conditions with chloroform/isopropanol (9:1, v/v) was applied to the samples prior to analysis. Chromatography was performed on a fused capillary column and synephrine and I.S., derivatized with pentafluoropropionic anhydride, were determined in the selected-ion-monitoring (SIM) mode. The method was validated in the range 0.1-50 microg/mg or microg/mL synephrine. Mean recovery ranged between 89.3% and 90.5% in both solid and liquid dietary supplements. The quantification limit was 0.1 microg/mg or microg/ml. The method was applied to analysis of various dietary supplements promoted for aiding weight control containing, among other constituents such as ephedrine alkaloids and methylxanthines, Citrus aurantium. Amount of synephrine present in such products ranged from 3.1 microg/mg solid product to 480.2 microg/mL liquid product. PMID:16698212

  2. A Gas Chromatography-Mass Spectrometry Based Study on Urine Metabolomics in Rats Chronically Poisoned with Hydrogen Sulfide

    PubMed Central

    Deng, Mingjie; Zhang, Meiling; Sun, Fa; Ma, Jianshe; Hu, Lufeng; Yang, Xuezhi; Lin, Guanyang; Wang, Xianqin

    2015-01-01

    Gas chromatography-mass spectrometry (GS-MS) in combination with multivariate statistical analysis was applied to explore the metabolic variability in urine of chronically hydrogen sulfide- (H2S-) poisoned rats relative to control ones. The changes in endogenous metabolites were studied by partial least squares-discriminate analysis (PLS-DA) and independent-samples t-test. The metabolic patterns of H2S-poisoned group are separated from the control, suggesting that the metabolic profiles of H2S-poisoned rats were markedly different from the controls. Moreover, compared to the control group, the level of alanine, d-ribose, tetradecanoic acid, L-aspartic acid, pentanedioic acid, cholesterol, acetate, and oleic acid in rat urine of the poisoning group decreased, while the level of glycine, d-mannose, arabinofuranose, and propanoic acid increased. These metabolites are related to amino acid metabolism as well as energy and lipid metabolism in vivo. Studying metabolomics using GC-MS allows for a comprehensive overview of the metabolism of the living body. This technique can be employed to decipher the mechanism of chronic H2S poisoning, thus promoting the use of metabolomics in clinical toxicology. PMID:25954748

  3. Innovative microwave-assisted oximation and silylation procedures for metabolomic analysis of plasma samples using gas chromatography-mass spectrometry.

    PubMed

    Hong, Zhanying; Lin, Zebin; Liu, Yue; Tan, Guangguo; Lou, Ziyang; Zhu, Zhenyu; Chai, Yifeng; Fan, Guorong; Zhang, Junping; Zhang, Liming

    2012-09-01

    Analysis of plasma metabolomic samples by gas chromatography-mass spectrometry always requires comprehensive pretreatment including oximation and silylation. Although heating block (HB) is a commonly used method, it is time consuming. This study describes an extremely time-effective microwave-assisted (MA) oximation and silylation approach for metabolomic study of plasma samples. The Box-Behnken design was employed to optimize the MA conditions by means of oximation at 65 W for 100 s and then silylation through 180 s incubation with 230 W microwave irradiation. The results showed that microwave irradiation decreased the sample preparation time from approximately 180 min to 5 min without loss of information for the metabolites in plasma samples. Both the HB method and the developed MA method were applied in plasma metabolomic study of sulfur mustard intoxication. Partial least-squares discriminant analysis (PLS-DA) was used to globally understand the metabolic changes, and multi-criteria assessment was used to select the most significant and reliable variables as potential biomarkers. The data obtained by the MA method were in good correlation with the HB method. Compared with HB method, the newly developed MA oximation and silylation of plasma metabolome samples was more efficient and time-effective and may prove to be an attractive alternative for high-throughput sample preparation in plasma metabolomics. PMID:22841665

  4. [Matrix effects in analysis of three beta-agonist residues in pig edible tissues using gas chromatography-mass spectrometry].

    PubMed

    Bian, Kui; Lin, Tao; Liu, Min; Yang, Jianwen; Wang, Zongnan; He, Limin

    2014-02-01

    A gas chromatography-mass spectrometry (GC-MS) method was established for the determination of the residues of three beta-agonists (clenbuterol, salbutamol and ractopamine) in pig edible tissues. The matrix effects (MEs) in the analysis of the three compounds with the developed method were determined. The influences of matrix state and its weight on MEs were evaluated statistically. The analytes in pig liver and muscle and their corresponding freeze-dried powders were derivatized with N,O-bis(trimethylsilyl) trifluoroacetamide. Then the derivatives were determined in selected ion monitoring mode and the intensities of MEs of the three beta-agonists were obtained. Significant matrix enhancement was observed for the three analytes, and especially, the ME of ractopamine was more than 1000%. The results of analysis of variance (ANOVA) demonstrated that MEs were significantly different for the three analytes in two matrices among different matrix weights (P < 0.05), and MEs of the three analytes increased from 1 g to 5 g with the increase of matrix weight. MEs for the three analytes were not significantly different between fresh pig tissues and its freeze-dried powder matrices (P > 0.05), indicating that the freeze-dried powder matrices might be used to conveniently prepare the matrix-matched calibration solution, which could efficiently compensate the MEs of the beta-agonists in GC-MS analysis. PMID:24822451

  5. Quantitative ester analysis in cachaca and distilled spirits by gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Nascimento, Eduardo S P; Cardoso, Daniel R; Franco, Douglas W

    2008-07-23

    An analytical procedure for the separation and quantification of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, isoamyl octanoate, and ethyl laurate in cachaca, rum, and whisky by direct injection gas chromatography-mass spectrometry was developed. The analytical method is simple, selective, and appropriated for the determination of esters in distilled spirits. The limit of detection ranged from 29 (ethyl hexanoate) to 530 (ethyl acetate) microg L(-1), whereas the standard deviation for repeatability was between 0.774% (ethyl hexanoate) and 5.05% (isoamyl octanoate). Relative standard deviation values for accuracy vary from 90.3 to 98.5% for ethyl butyrate and ethyl acetate, respectively. Ethyl acetate was shown to be the major ester in cachaca (median content of 22.6 mg 100 mL(-1) anhydrous alcohol), followed by ethyl lactate (median content of 8.32 mg 100 mL(-1) anhydrous alcohol). Cachaca produced in copper and hybrid alembic present a higher content of ethyl acetate and ethyl lactate than those produced in a stainless-steel column, whereas cachaca produced by distillation in a stainless-steel column present a higher content of ethyl octanoate, ethyl decanoate, and ethyl laurate. As expected, ethyl acetate is the major ester in whiskey and rum, followed by ethyl lactate for samples of rum. Nevertheless, whiskey samples exhibit ethyl lactate at contents lower or at the same order of magnitude of the fatty esters. PMID:18570431

  6. Analysis of Trace Quaternary Ammonium Compounds (QACs) in Vegetables Using Ultrasonic-Assisted Extraction and Gas Chromatography-Mass Spectrometry.

    PubMed

    Xiang, Lei; Wang, Xiong-Ke; Li, Yan-Wen; Huang, Xian-Pei; Wu, Xiao-Lian; Zhao, Hai-Ming; Li, Hui; Cai, Quan-Ying; Mo, Ce-Hui

    2015-08-01

    A reliable, sensitive, and cost-effective method was developed for determining three quaternary ammonium compounds (QACs) including dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, and didodecyldimethylammonium chloride in various vegetables using ultrasonic-assisted extraction and gas chromatography-mass spectrometry. The variety and acidity of extraction solvents, extraction times, and cleanup efficiency of sorbents were estimated to obtain an optimized procedure for extraction of the QACs in nine vegetable matrices. Excellent linearities (R(2) > 0.992) were obtained for the analytes in the nine matrices. The limits of detection and quantitation were 0.7-6.0 and 2.3-20.0 ?g/kg (dry weight, dw) in various matrices, respectively. The recoveries in the nine matrices ranged from 70.5% to 108.0% with relative standard deviations below 18.0%. The developed method was applied to determine the QACs in 27 vegetable samples collected from Guangzhou in southern China, showing very high detection frequency with a concentration of 23-180 ?g/kg (dw). PMID:26165915

  7. Rapid determination of nineteen chlorophenols in wood, paper, cardboard, fruits, and fruit juices by gas chromatography/mass spectrometry.

    PubMed

    Diserens, J M

    2001-01-01

    Although the use of pentachlorophenol (PCP) is prohibited in most countries, it is still widely found in the wood of pallets, containers, crates and in cardboard, paper, etc. Such material may contain not only PCP but other chlorophenols as well. Wooden crates and cardboard boxes are often used to store and transport fresh fruits. Consequently, chlorophenols present in the wood may contaminate the stored fruits by migration. To ascertain that packaging, storage material, and fruit raw materials are free from chlorophenol residues, we developed a rapid and sensitive method for the detection of 19 chlorophenols by gas chromatography/mass spectrometry (GC/MS). The test portions are directly extracted and acetylated in a solution of sodium carbonate in the presence of acetic anhydride and hexane. The hexane layer is analyzed, without further purification, by GC/MS in the selective-ion monitoring mode. The method allows the analysis of >40 samples/day with detection limits of <20 microg/kg for chlorophenols in wood, cardboard, and paper, and <2 microg/kg for chlorophenols in fruits. Typical recoveries of all chlorophenols were 94% from paper, 115% from cardboard, 51% from wood (depending on the size of the chips or shavings), and 93% from fruit puree. PMID:11417649

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

    PubMed

    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. PMID:24592162

  9. [Determination of 17 pyrethroid pesticide residues in vegetables by gas chromatography-mass spectrometry with negative chemical ionization].

    PubMed

    Shen, Weijian; Cao, Xiaowen; Liu, Yijun; Zhang, Rui; Fan, Xin; Zhao, Zengyun; Shen, Chongyu; Wu, Bin

    2012-11-01

    A method was established for the determination of 17 pyrethroid pesticide residues in vegetables using QuEChERS (quick, easy, cheap, effective, rugged and safe) clean-up method and gas chromatography-mass spectrometry (GC-MS) with negative chemical ionization (NCI). The pyrethroid pesticides in the sample were extracted with acetonitrile. After QuEChERS clean-up with a mixture of primary secondary amine and graphitized carbon black packings, the extract was analyzed by GC-NCI-MS in selected ion monitoring (SIM) mode. An isotope internal standard of cypermethrin was employed to the quantification. The limits of quantification ranged from 0.02 to 5 microg/kg. The recoveries of the pyrethroid pesticides spiked in three different matrixes (peas, broccoli and Chinese onion green) at four spiked levels of 10, 20, 30 and 100 microg/kg were from 71.0% to 139.0%, and the relative standard deviations were less than 12.8%. This method can be used as a conclusive evidence method of the 17 pyrethroid pesticide residues in vegetables. PMID:23451521

  10. Development of Sensitive and Specific Analysis of Vildagliptin in Pharmaceutical Formulation by Gas Chromatography-Mass Spectrometry

    PubMed Central

    Uaktrk, Ebru

    2015-01-01

    A sensitive and selective gas chromatography-mass spectrometry (GC-MS) method was developed and fully validated for the determination of vildagliptin (VIL) in pharmaceutical formulation. Prior to GC-MS analysis, VIL was efficiently derivatized with MSTFA/NH4I/?-mercaptoethanol at 60C for 30?min. The obtained O-TMS derivative of VIL was detected by selected ion monitoring mode using the diagnostic ions m/z 223 and 252. Nandrolone was chosen as internal standard. The GC-MS method was fully validated by the following validation parameters: limit of detection (LOD) and quantitation (LOQ), linearity, precision, accuracy, specificity, stability, robustness, and ruggedness. LOD and LOQ were found to be 1.5 and 3.5?ng?mL?1, respectively. The GC-MS method is linear in the range of 3.5300?ng?mL?1. The intra- and interday precision values were less than ?3.62%. The intra- and interday accuracy values were found in the range of ?0.262.06%. Finally, the GC-MS method was successfully applied to determine VIL in pharmaceutical formulation. PMID:26682085

  11. Effect of piperine on pharmacokinetics of sodium valproate in plasma samples of rats using gas chromatography-mass spectrometry method

    PubMed Central

    Parveen, Bushra; Pillai, K. K.; Tamboli, E. T.; Ahmad, Sayeed

    2015-01-01

    Piperine (PIP) is used as anticonvulsant in traditional Chinese medicine. Co-administration of low-dose sodium valproate with PIP has been regarded to have potential anticonvulsant activity. Aim: This study was intended to investigate the effect of PIP on the pharmacokinetics of sodium valproate (SVP) in the plasma samples of rats using gas chromatography-mass spectrometry (GC-MS) method. Materials and Methods: The plasma samples obtained after oral administration of SVP, 150 mg/kg and SVP, 150 mg/kg + PIP, and 5 mg/kg to male Wistar rats were used to quantify the concentrations in plasma using GC-MS method. Results: A simple and accurate method developed in-house was applied for the analysis of plasma samples of Wistar rats after oral administration of SVP and PIP + sodium valproate, respectively. The pharmacokinetic parameters reported 14.8-fold increase in plasma concentration (maximum observed concentration in the concentration-time profile), 4.6-fold increase in area under the curve and slightly prolonged time to reach that concentration (1 h) of SVP in presence of PIP. Conclusion: The study reaffirms the bioenhancing effect of PIP suggesting possibility of dose reduction of SVP while co-adminstering with PIP. PMID:26681892

  12. Identifying acetylated lignin units in non-wood fibers using pyrolysis-gas chromatography/mass spectrometry.

    PubMed

    del Río, José C; Gutiérrez, Ana; Martínez, Angel T

    2004-01-01

    A series of non-wood plant fibers, namely kenaf, jute, sisal and abaca, have been analyzed upon pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of the whole material. The pyrolysis products mainly arise from the carbohydrate and lignin moieties of the fibers. The lignin-derived phenols belonged to the p-hydroxyphenylpropanoid (H), guaiacylpropanoid (G) and syringylpropanoid (S) structures, and showed a high S/G ratio of between 2.0 and 5.4, the highest corresponding to kenaf. Among the lignin-derived phenols released, small amounts of sinapyl and coniferyl acetates (in both cis- and trans-forms) were identified for the first time upon Py-GC/MS of lignocellulosic materials. Acetylation of the sinapyl and coniferyl alcohols was at the gamma-position of the side chain. The release of these alcohols derived from intact acetylated lignin units upon pyrolysis seems to indicate that the native lignin in the fibers selected for this study is at least partially acetylated. Sinapyl (and coniferyl) acetates have recently been suggested to be authentic lignin precursors involved in the polymerization of lignin along with the normal sinapyl and coniferyl alcohols. Py-GC/MS will offer a convenient and rapid tool for analyzing naturally acetylated lignins, as well as to screen plant materials for the presence of acetylated units in lignin. PMID:15164346

  13. Measurement of volatile plant compounds in field ambient air by thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Cai, Xiao-Ming; Xu, Xiu-Xiu; Bian, Lei; Luo, Zong-Xiu; Chen, Zong-Mao

    2015-12-01

    Determination of volatile plant compounds in field ambient air is important to understand chemical communication between plants and insects and will aid the development of semiochemicals from plants for pest control. In this study, a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method was developed to measure ultra-trace levels of volatile plant compounds in field ambient air. The desorption parameters of TD, including sorbent tube material, tube desorption temperature, desorption time, and cold trap temperature, were selected and optimized. In GC-MS analysis, the selected ion monitoring mode was used for enhanced sensitivity and selectivity. This method was sufficiently sensitive to detect part-per-trillion levels of volatile plant compounds in field ambient air. Laboratory and field evaluation revealed that the method presented high precision and accuracy. Field studies indicated that the background odor of tea plantations contained some common volatile plant compounds, such as (Z)-3-hexenol, methyl salicylate, and (E)-ocimene, at concentrations ranging from 1 to 3400ngm(-3). In addition, the background odor in summer was more abundant in quality and quantity than in autumn. Relative to previous methods, the TD-GC-MS method is more sensitive, permitting accurate qualitative and quantitative measurements of volatile plant compounds in field ambient air. PMID:26493981

  14. Alternative method for gas chromatography-mass spectrometry analysis of short-chain fatty acids in faecal samples.

    PubMed

    García-Villalba, Rocio; Giménez-Bastida, Juan A; García-Conesa, Maria T; Tomás-Barberán, Francisco A; Espín, Juan Carlos; Larrosa, Mar

    2012-06-01

    Short-chain fatty acids are the major end products of bacterial metabolism in the large bowel. They derive mostly from the bacterial breakdown of carbohydrates and are known to have positive health benefits. Due to the biological relevance of these compounds it is important to develop efficient, cheap, fast, and sensitive analytical methods that enable the identification and quantification of the short-chain fatty acids in a large number of biological samples. In this study, a gas chromatography-mass spectrometry method was developed and validated for the analysis of short-chain fatty acids in faecal samples. These volatile compounds were extracted with ethyl acetate and 4-methyl valeric acid was used as an internal standard. No further cleanup, concentration, and derivatization steps were needed and the extract was directly injected onto the column. Recoveries ranged between 65 and 105%, and no matrix effects were observed. The proposed method has wide linear ranges, good inter- and intraday variability values (below 2.6 and 5.6%, respectively) and limits of detection between 0.49 μM (0.29 μg/g) and 4.31 μM (3.8 μg/g). The applicability of this analytical method was successfully tested in faecal samples from rats and humans. PMID:22674825

  15. Alternative method for gas chromatography-mass spectrometry analysis of short-chain fatty acids in faecal samples.

    PubMed

    García-Villalba, Rocio; Giménez-Bastida, Juan A; García-Conesa, Maria T; Tomás-Barberán, Francisco A; Carlos Espín, Juan; Larrosa, Mar

    2012-08-01

    Short-chain fatty acids are the major end products of bacterial metabolism in the large bowel. They derive mostly from the bacterial breakdown of carbohydrates and are known to have positive health benefits. Due to the biological relevance of these compounds it is important to develop efficient, cheap, fast, and sensitive analytical methods that enable the identification and quantification of the short-chain fatty acids in a large number of biological samples. In this study, a gas chromatography-mass spectrometry method was developed and validated for the analysis of short-chain fatty acids in faecal samples. These volatile compounds were extracted with ethyl acetate and 4-methyl valeric acid was used as an internal standard. No further cleanup, concentration, and derivatization steps were needed and the extract was directly injected onto the column. Recoveries ranged between 65 and 105%, and no matrix effects were observed. The proposed method has wide linear ranges, good inter- and intraday variability values (below 2.6 and 5.6%, respectively) and limits of detection between 0.49 μM (0.29 μg/g) and 4.31 μM (3.8 μg/g). The applicability of this analytical method was successfully tested in faecal samples from rats and humans. PMID:22865755

  16. Validation of Biomarkers for Distinguishing Mycobacterium tuberculosis from Non-Tuberculous Mycobacteria Using Gas Chromatography?Mass Spectrometry and Chemometrics

    PubMed Central

    Dang, Ngoc A.; Kuijper, Sjoukje; Walters, Elisabetta; Claassens, Mareli; van Soolingen, Dick; Vivo-Truyols, Gabriel; Janssen, Hans-Gerd; Kolk, Arend H. J.

    2013-01-01

    Tuberculosis (TB) remains a major international health problem. Rapid differentiation of Mycobacterium tuberculosis complex (MTB) from non-tuberculous mycobacteria (NTM) is critical for decisions regarding patient management and choice of therapeutic regimen. Recently we developed a 20-compound model to distinguish between MTB and NTM. It is based on thermally assisted hydrolysis and methylation gas chromatography-mass spectrometry and partial least square discriminant analysis. Here we report the validation of this model with two independent sample sets, one consisting of 39 MTB and 17 NTM isolates from the Netherlands, the other comprising 103 isolates (91 MTB and 12 NTM) from Stellenbosch, Cape Town, South Africa. All the MTB strains in the 56 Dutch samples were correctly identified and the model had a sensitivity of 100% and a specificity of 94%. For the South African samples the model had a sensitivity of 88% and specificity of 100%. Based on our model, we have developed a new decision-tree that allows the differentiation of MTB from NTM with 100% accuracy. Encouraged by these findings we will proceed with the development of a simple, rapid, affordable, high-throughput test to identify MTB directly in sputum. PMID:24146846

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

    PubMed

    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. PMID:26718189

  18. Mass spectral studies on vinylic degradation products of sulfur mustards under gas chromatography/mass spectrometry conditions.

    PubMed

    Sai Sachin, L; Karthikraj, R; Kalyan Kumar, K; Sony, T; Prasada Raju, N; Prabhakar, S

    2015-01-01

    Sulfur mustards are a class of vesicant chemical warfare agents that rapidly degrade in environmental samples. The most feasible degradation products of sulfur mustards are chloroethyl vinylic compounds and divinylic compounds, which are formed by the elimination of one and two HCl molecules from sulfur mustards, respectively. The detection and characterization of these degradation products in environmental samples are an important proof for the verification of sulfur mustard usage. In this study, we synthesized a set of sulfur mustard degradation products, i.e., divinylic compounds (1-7) and chloroethyl vinylic compounds (8-14), and characterized using gas chromatography/mass spectrometry (GC/MS) under electron ionization (EI) and chemical ionization (CI) (methane) conditions. The EI mass spectra of the studied compounds mainly included the fragment ions that resulted from homolytic cleavages with or without hydrogen migrations. The divinylic compounds (1-7) showed [M-SH](+) ions, whereas the chloroethylvinyl compounds (8-14) showed [M-Cl](+) and [M-CH2CH2Cl](+) ions. Methane/CI mass spectra showed [M+H](+) ions and provided molecular weight information. The GC retention index (RI) values were also calculated for the studied compounds. The EI and CI mass spectral data together with RI values are extremely useful for off-site analysis for the verification of the chemical weapons convention and also to participate in official Organization for the Prohibition of Chemical Weapons proficiency tests. PMID:26764309

  19. Simultaneous Determination of Tramadol and Its Metabolite in Human Urine by the Gas Chromatography-Mass Spectrometry Method.

    PubMed

    Yilmaz, Bilal; Erdem, Ali Fuat

    2015-08-01

    A sensitive and efficient method was developed for determination of tramadol and its metabolite (O-desmethyltramadol) in human urine by gas chromatography-mass spectrometry. Tramadol, O-desmethyltramadol and medazepam (internal standard) were extracted from human urine with a mixture of ethylacetate and diethylether mixture (1 : 1, v/v) at basic pH with liquid-liquid extraction. The calibration curves were linear (r = 0.99) over tramadol and O-desmethyltramadol concentrations ranging from 10 to 200 ng/mL and 7.5 to 300 ng/mL, respectively. The method had an accuracy of >95% and intra- and interday precision (relative standard deviation %) of ≤4.93 and ≤4.62% for tramadol and O-desmethyltramadol, respectively. The extraction recoveries were found to be 94.1 ± 2.91 and 96.3 ± 3.46% for tramadol and O-desmethyltramadol, respectively. The limit of quantification using 0.5 mL human urine was 10 ng/mL for tramadol and 7.5 ng/mL for O-desmethyltramadol. After oral administration of 100 mg of tramadol hydrochloride to a patient, the urinary excretion was monitored during 24 h. About 15% of the dose was excreted as unchanged tramadol. PMID:25616987

  20. Chemical characterization of automotive polyurethane foam using solid-phase microextraction and gas chromatography-mass spectrometry.

    PubMed

    Parsons, Norah S; Lam, Michael H W; Hamilton, Sheilah E

    2013-01-01

    Solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used in this study to identify volatile organic compounds (VOCs) emitted from heated automotive polyurethane (PU) foam collected from 17 different automobiles located in Yuen Long, HK SAR. The samples (0.05 g each) underwent incubation inside 5-mL glass vials for 30 min, and the VOCs were then collected from the headspace with a polydimethylsiloxane fiber by insertion for 30 min. The VOCs were then qualitatively identified by GC-MS analysis and were mostly found to be saturated hydrocarbons. However, differences were noted from car to car in the retention time range of 10-23 min. The VOCs collected during this segment of retention time from the PU foams ranged from antioxidants, food preservatives, pesticides, plasticizers, flame retardants to antiseptic agents. The results obtained from this study therefore highlight the usefulness of SPME/GC-MS as a form of chemical characterization in the analysis of PU foams in forensic casework. PMID:22994148

  1. [Characterization of pyrolysis of waste printed circuit boards by high-resolution pyrolysis gas chromatography-mass spectrometry].

    PubMed

    Zhang, Yanhong; Huang, Hong; Xia, Zhengbin; Chen, Huanqin

    2008-07-01

    Thermal degradation of pyrolysis of waste circuit boards was investigated by high-resolution pyrolysis gas chromatography-mass spectrometry (PyGC-MS) and thermogravimetry (TG). In helium atmosphere, the products of FR-4 waste printed circuit board were pyrolyzed at 350, 450, 550, 650, and 750 degrees degrees C, separately, and the pyrolysis products were identified by online MS. The results indicated that the pyrolysis products of the FR-4 waste circuit board were three kinds of substances, such as the low boiling point products, phenol, bisphenol and their related products. Moreover, under 300 degrees degrees C, only observed less pyrolysis products. As the increase of pyrolysis temperature, the relative content of the low boiling point products increased. In the range of 450-650 degrees degrees C, the qualitative analysis and character were similar, and the relative contents of phenol and bisphenol were higher. The influence of pyrolysis temperature on pyrolyzate yields was studied. On the basis of the pyrolyzate profile and the dependence of pyrolyzate yields on pyrolysis temperature, the thermal degradation mechanism of brominated epoxy resin was proposed. PMID:18959254

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

    PubMed

    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 m 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 L 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. PMID:26306572

  3. Ultrasound-assisted hydrolysis and gas chromatography-mass spectrometric determination of phenolic compounds in cranberry products.

    PubMed

    Wang, Chengjun; Zuo, Yuegang

    2011-09-15

    An ultrasound-assisted hydrolysis and gas chromatography-mass spectrometric (GC-MS) method has been developed for determination of phenolics in cranberry products. Prior to GC-MS separation and characterisation, the phenolics in samples were hydrolysed by hydrochloric acid with ultrasound-assistance, extracted with ethyl acetate, and derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)+1% trimethylchlorosilane (TMCS) reagents. The application of ultrasonication significantly accelerated the acidic hydrolysation of the conjugated phenolics. A baseline separation of the 20 phenolics and internal standard was achieved in 25min. Standard calibration curves were linear over the concentration range of 0.0-50?g/mL and detection limits were 0.06-0.70?g/mL. Twenty phenolics were identified in cranberry samples and all of them occurred mainly in conjugated forms. Of those, the benzoic acid, quercetin, and myricetin were most abundant phenolics. The total phenolics were 12.4mg/g in cranberry fruits, 9.1mg/mL in 100% cranberry juice, and 11.1mg/g in cranberry sauces, respectively. PMID:25212170

  4. Determination of fecal sterols by gas chromatography-mass spectrometry with solid-phase extraction and injection-port derivatization.

    PubMed

    Wu, Jingming; Hu, Ruikang; Yue, Junqi; Yang, Zhaoguang; Zhang, Lifeng

    2009-02-13

    Injection-port derivatization combined with solid-phase extraction (SPE) was developed and applied for the first time to determine five types of fecal sterols (coprostanol, cholestanol, epicholestanol, epicoprostanol and cholesterol) with gas chromatography-mass spectrometry (GC-MS). In this method, silylation of fecal sterols was performed with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) at GC injection-port. The factors influential to this technique such as injection-port temperature, purge-off time, derivatization reagent (BSTFA) volume, and the type of organic solvent were investigated. In addition, the conditions of SPE (including the type of SPE cartridge, the type of elution organic solvent) were also studied. After SPE followed by injection-port silylation by GC-MS, good linearity of analytes was achieved in the range of 0.02-10ng/mL with coefficients of determination, R(2)>0.995. Good reproducibility was obtained with relative standard deviation less than 19.6%. The limits of detection ranged from 1.3ng/mL to 15ng/mL (S/N=3) in environmental water samples. Compared with traditional off-line silylation of fecal sterols performed with water bath (60 degrees C, 30min), this injection-port silylation method is much simpler and convenient. The developed method has been successfully applied for the analysis of fecal sterols from real environmental water samples. PMID:19147150

  5. Characterisation and discrimination of various types of lac resin using gas chromatography mass spectrometry techniques with quaternary ammonium reagents.

    PubMed

    Sutherland, K; del Ro, J C

    2014-04-18

    A variety of lac resin samples obtained from artists' suppliers, industrial manufacturers, and museum collections were analysed using gas chromatography mass spectrometry (GCMS) and reactive pyrolysis GCMS with quaternary ammonium reagents. These techniques allowed a detailed chemical characterisation of microgram-sized samples, based on the detection and identification of derivatives of the hydroxy aliphatic and cyclic (sesquiterpene) acids that compose the resin. Differences in composition could be related to the nature of the resin, e.g. wax-containing (unrefined), bleached, or aged samples. Furthermore, differences in the relative abundances of aliphatic hydroxyacids appear to be associated with the biological source of the resin. The diagnostic value of newly characterised lac components, including 8-hydroxyacids, is discussed here for the first time. Identification of derivatised components was aided by AMDIS deconvolution software, and discrimination of samples was enhanced by statistical evaluation of data using principal component analysis. The robustness of the analyses, together with the minimal sample size required, make these very powerful approaches for the characterisation of lac resin in museum objects. The value of such analyses for enhancing the understanding of museum collections is illustrated by two case studies of objects in the collection of the Philadelphia Museum of Art: a restorer's varnish on a painting by Luca Signorelli, and a pictorial inlay in an early nineteenth-century High Chest by George Dyer. PMID:24642395

  6. A possible ethanol-catalyzed rearrangement of vitamin K(1) detected by gas chromatography/mass spectrometry.

    PubMed

    Osman, Abdimajid; Hannestad, Ulf

    2008-12-01

    We studied vitamin K(1)(20), vitamin K(1)(25), and vitamin K(1) epoxide in n-hexane and ethanol solutions by gas chromatography/mass spectrometry (GC/MS) utilizing a DB-5 MS fused-silica capillary column. In ethanol solutions of K(1), we observed an extra peak eluting from the GC column with somewhat longer retention time than K(1)(20). A similar peak following K(1)(25) was also found. These peaks were not found in n-hexane solutions of K(1). A close examination of the mass spectra of these peaks indicated that they were vitamin K(1) variants containing a base peak at m/z 225 characteristic of the methylnaphthoquinone ring with a four-carbon side chain. In addition, they contained the molecular ions of K(1)(20) and K(1)(25), respectively. We conclude that K(1)(20) and K(1)(25), but not K(1) epoxide, might undergo rearrangements in ethanol involving an intramolecular proton transfer and a shift of the beta,gamma-double bond on the phytyl side chain toward the ring. The conjugation of the phytyl double bond with the quinone ring is probably the driving force of the rearrangement. We emphasize, however, that our conclusion is based only on mass spectral analysis and would require further investigation by other spectroscopic methods. PMID:18980252

  7. Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, D. A.; Hayes, J. M.

    1994-01-01

    Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

  8. Determination of dithiocarbamates and milneb residues in foods by gas chromatography-mass spectrometry.

    PubMed

    Nakamura, Munetomo; Noda, Satoko; Kosugi, Masaki; Ishiduka, Noriko; Mizukoshi, Kazushi; Taniguchi, Makoto; Nemoto, Satoru

    2010-01-01

    A highly sensitive gas chromatographic-mass spectrometric (GC-MS) method was developed for dithiocarbamates (DTCs) and milneb in foods. DTCs and milneb were extracted from foods with cysteine-EDTA solution as sodium salts, and methylated with methyl iodide. Methyl derivatives of DTCs and milneb were cleaned up on a neutral alumina mini column and determined by GC-MS. The mean recoveries of DTCs and milneb were in the range of 72-120%, except for methiram. The quantification limits were 0.01 mg/kg (as CS(2)) in foods except tea (0.1 mg/kg as CS(2)). The developed method was applied to 10 compounds (4 dimethyldithiocarbamates, 3 ethylenebisdithiocarbamates, polycarbamates, propineb and milneb). PMID:21071904

  9. Buprenorphine and Norbuprenorphine Determination in Mice Plasma and Brain by Gas ChromatographyMass Spectrometry

    PubMed Central

    Chiadmi, Fouad; Schlatter, Jol

    2014-01-01

    A gas chromatography tandem mass spectrometry method for quantification of buprenorphine (BUP) and norbuprenorphine (NBUP) in brain and plasma samples from mice was developed and validated. Analytes were extracted from the brain or plasma by solid phase extraction and quantified within 20 minutes. Calibration was achieved by linear regression with a 1/x weighting factor and d4-buprenorphine internal standard. All products were linear from 1 to 2000 ng/mL with a correlation of determination >0.99. Assay accuracy and precision of back-calculated standards were within 10%. The lower limit of quantification for both BUP and NBUP from the brain and plasma was 1 ng/mL. This sensitive and specific method can be used for the investigation of BUP mechanism of action and clinical profile. PMID:24653644

  10. Quantitation of ethyl glucuronide in serum & urine by gas chromatography - mass spectrometry

    PubMed Central

    Sharma, Priyamvada; Bharat, Venkatesh; Murthy, Pratima

    2015-01-01

    Background & objectives: Alcohol misuse has now become a serious public health problem and early intervention is important in minimizing the harm. Biochemical markers of recent and high levels of alcohol consumption can play an important role in providing feedback regarding the health consequences of alcohol misuse. Existing markers are not sensitive to recent consumption and in detecting early relapse. Ethyl glucuronide (EtG), a phase-II metabolite of ethanol is a promising marker of recent alcohol use and can be detected in body fluids. In this study an analytical technique for quantitation of EtG in body fluids using solid-phase extraction (SPE) and gas chromatography (GC) with mass spectrometric detection (MS) was developed and validated. Methods: De-proteinization of serum and urine samples was done with perchloric acid and hydrochloric acid, respectively. Serum samples were passed through phospholipids removal cartridges for further clean up. EtG was isolated using amino propyl solid phase extraction columns. Chromatographic separation was achieved by gas chromatography with mass spectrometry. Results: Limit of detection and limit of quantitation were 50 and 150 ng/ml for urine and 80 and 210 ng/ml for serum, respectively. Signal to noise ratio was 3:1, mean absolute recovery was 80-85 per cent. Significant correlation was obtained between breath alcohol and serum EtG levels (r=0.853) and urine EtG and time since last abuse (r = -0.903) in clinical samples. Interpretation & conclusions: In the absence of other standardized techniques to quantitate EtG in biological samples, this GC-MS method was found to have high throughput and was sensitive and specific. PMID:25857498

  11. [Rapid determination of benzene series in seawater by gas chromatography-mass spectrometry with static headspace extraction].

    PubMed

    Bai, Hongyan; Han, Bin; Chen, Junhui; Zheng, Li; Yang, Dongfang; Wang, Xiaoru

    2012-05-01

    A method for the simultaneous determination of 13 benzene series (BTEX) in seawater using gas chromatography-mass spectrometry with static headspace extraction (HS-GC/MS) was developed. To carefully characterize the performance of this method, several factors affecting parameters were studied in detail, such as the type of column, heating procedure, equilibrium temperature, equilibrium time and the volume ratio of gas phase to liquid phase. The optimized conditions were as follows: the polar column of DB-WAX; heating procedure, 40 degrees C kept for 4 min, then raised to 120 degrees C at 10 degrees C/min, to 180 degrees C at 25 degrees C/min; equilibrium temperature, 80 degrees C; equilibrium time, 10 min; and the volume ratio of gas phase to liquid phase, 1:1. Under the optimized conditions, the linear equations were obtained in the concentration range of 0.16-320 microg/L with correlation coefficients greater than 0.999. The limits of detection (S/N = 3) were 0.019-0.033 microg/L. The recoveries at the three spiked levels of 1.6, 16 and 160 microg/L ranged from 81. 25% to 103.73% with the relative standard deviations (RSD, n=6) from 0.3% to 4.4%. The analytical results of the practical seawater samples from Shanghai Huangpu District were satisfactory. The determination of the 13 benzene series can be finished in 12 min. The method is simple, accurate, reliable, efficient and environmental-friendly. PMID:22934410

  12. Determination of plasma mexiletine levels with gas chromatography-mass spectrometry and selected-ion monitoring.

    PubMed

    Minnigh, M B; Alvin, J D; Zemaitis, M A

    1994-12-01

    Mexiletine, 1-(2,6-dimethylphenoxy)-2-aminopropane (Mexitil), is an orally effective agent useful in the treatment of serious ventricular arrhythmias. This paper describes a gas chromatographic-mass spectrophotometric assay with selected-ion monitoring for the measurement of plasma or serum mexiletine levels. The drug and internal standard (p-chlorophenylalanine methyl ester) were extracted from plasma into ethyl acetate-hexane-methanol (60:40:1, v/v). After separation and evaporation of the organic phase, the drug and internal standard were derivatized to their pentafluoropropyl derivatives prior to analysis. The reproducibility of the daily standard curve yielded mean inter- and intra-day coefficients of variability from 0.7 to 11.0%. The coefficients of variability for control plasma samples (0.5 and 1.0 micrograms/ml) ranged from 2.6 to 5.0% and the accuracy of the assay was 106 +/- 6 and 100 +/- 5% for the low and high level controls respectively. The limit of quantitation for the assay was 0.1 micrograms/ml. No interfering peaks were detected in any patient samples. This method can be used as a primary analytical method to measure mexiletine plasma levels or can serve as a convenient back-up method to HPLC procedures when contaminating peaks coelute with mexiletine. PMID:7894684

  13. Integration of Gas Chromatography Mass Spectrometry Methods for Differentiating Ricin Preparation Methods

    SciTech Connect

    Wunschel, David S.; Melville, Angela M.; Ehrhardt, Christopher J.; Colburn, Heather A.; Victry, Kristin D.; Antolick, Kathryn C.; Wahl, Jon H.; Wahl, Karen L.

    2012-05-17

    The investigation of crimes involving chemical or biological agents is infrequent, but presents unique analytical challenges. The protein toxin ricin is encountered more frequently than other agents and is found in the seeds of the castor plant Ricinus communis. Typically, the toxin is extracted from castor seeds utilizing a variety of different recipes that result in varying purity of the toxin. Moreover, these various purification steps can also leave or differentially remove a variety of exogenous and endogenous residual components with the toxin that may indicate the type and number of purification steps involved. We have applied three gas chromatographic - mass spectrometric (GC-MS) based analytical methods to measure the variation in seed carbohydrates and castor oil ricinoleic acid as well as the presence of solvents used for purification. These methods were applied to the same samples prepared using four previously identified toxin preparation methods starting from four varieties of castor seeds. The individual data sets for seed carbohydrate profiles, ricinoleic acid or acetone amount each provided information capable of differentiating different types of toxin preparations across seed types. However, the integration of the data sets using multivariate factor analysis provided a clear distinction of all samples based on the preparation method and independent of the seed source. In particular the abundance of mannose, arabinose, fucose, ricinoleic acid and acetone were shown to be important differentiating factors. These complementary tools provide a more confident determination of the method of toxin preparation.

  14. Simple and rapid analysis of methyldibromo glutaronitrile in cosmetic products by gas chromatography mass spectrometry.

    PubMed

    Pellegrini, Manuela; Boss, Elena; Rotolo, Maria Concetta; Pacifici, Roberta; Pichini, Simona

    2011-12-15

    A simple and rapid gas chromatography (GC) method with mass spectrometry (MS) detection has been developed for the determination of methyldibromo glutaronitrile (MDBGN) in cosmetic products. The presence of this preservative in commercial cosmetic samples is prohibited since 2007 because of its allergenic properties. The analyzed products were opportunely diluted in methanol and MDBGN was separated by fused silica capillary column and detected by electron impact (EI)-MS in positive ionization mode with a total run time of 7 min. The assay was validated in the range 0.005-0.100 mg MDBGN per g of examined product with good determination coefficients (r(2)?0.99) for the calibration curves. At three concentrations spanning the linear dynamic range of the calibration curves, mean recoveries were always higher than 95% for MDBGN in the tested cosmetics. This method was successfully applied to the analysis of cleansing gels, shampoo and solar waters to disclose the eventual presence of MDBGN illegally added in cosmetic products. PMID:21871753

  15. Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

    NASA Technical Reports Server (NTRS)

    Merritt, Dawn A.; Hayes, J. M.; Des Marais, David J.

    1995-01-01

    Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

  16. Methods of analysis-Determination of pesticides in sediment using gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Hladik, Michelle L.; McWayne, Megan M.

    2012-01-01

    A method for the determination of 119 pesticides in environmental sediment samples is described. The method was developed by the U.S. Geological Survey (USGS) in support of the National Water Quality Assessment (NAWQA) Program. The pesticides included in this method were chosen through prior prioritization. Herbicides, insecticides, and fungicides along with degradates are included in this method and span a variety of chemical classes including, but not limited to, chloroacetanilides, organochlorines, organophosphates, pyrethroids, triazines, and triazoles. Sediment samples are extracted by using an accelerated solvent extraction system (ASE, and the compounds of interest are separated from co-extracted matrix interferences (including sulfur) by passing the extracts through high performance liquid chromatography (HPLC) with gel-permeation chromatography (GPC) along with the use of either stacked graphitized carbon and alumina solid-phase extraction (SPE) cartridges or packed Florisil. Chromatographic separation, detection, and quantification of the pesticides from the sediment-sample extracts are done by using gas chromatography with mass spectrometry (GC/MS). Recoveries in test sediment samples fortified at 10 micrograms per kilogram (?g/kg) dry weight ranged from 75 to 102 percent; relative standard deviations ranged from 3 to 13 percent. Method detection limits (MDLs), calculated by using U.S. Environmental Protection Agency procedures (40 CFR 136, Appendix B), ranged from 0.6 to 3.4 ?g/kg dry weight.

  17. Improved sensitivity gas chromatography-mass spectrometry determination of parabens in waters using ionic liquids.

    PubMed

    Cacho, Juan Ignacio; Campillo, Natalia; Vias, Pilar; Hernndez-Crdoba, Manuel

    2016-01-01

    A new procedure for the introduction of ionic liquid samples in gas chromatography (GC) is proposed. This procedure, based on microvial insert thermal desorption, allows the direct analysis of the compounds preconcentrated by ionic liquid based liquid-liquid microextraction (IL-LLME) using the combination of a thermal desorption unit (TDU) and a programmed temperature vaporization injector (PTV). Two different IL-LLME methodologies, one based on the formation of a microdroplet emulsion by dispersive liquid-liquid microextraction (DLLME) and other through ultrasound-assisted emulsification microextraction (USAEME) were studied and evaluated. IL-DLLME proved advantageous and consequently, it was adopted for preconcentration purposes. This easy to apply approach was used for the determination of five parabens (methyl-, ethyl-, propyl-, butyl- and isobutyl paraben) in swimming pool waters, after in situ acetylation. The optimized conditions of TDU/PTV allowed the analytes contained in 20L of the enriched IL to be transferred to the capillary column. Quantification of the samples was carried out against aqueous standards, and quantification limits of between 4.3 and 8.1ngL(-1) were obtained, depending on the compound. Concentrations of between 9 and 47ngL(-1) for some analytes were obtained in the analysis of ten samples. PMID:26695305

  18. Determination of synthetic musk compounds in sewage biosolids by gas chromatography/mass spectrometry.

    PubMed

    Osemwengie, Lantis I

    2006-09-01

    A review of sewage sludge regulations and land application practices by the United States National Research Council (2002) recommended development of improved analytical techniques to adequately identify and quantify new chemical contaminants, such as synthetic musk compounds in Class A sewage sludge (i.e., biosolids). This prompted the development of a rugged analytical method using gas chromatography coupled to mass spectrometry to detect this group of organic pollutants in biosolids. In this paper, the term "biosolids" is used interchangeably with "sewage sludge", which is defined in the regulations and used in the statue (Clean Water Act). Samples of Class A biosolids obtained from sewage treatment plants in Los Angeles, California, the City of Las Vegas, Nevada, and also in the form of a commercial fertilizer, were extracted using pressurized liquid extraction technique, subjected to gel permeation chromatography clean-up, and analyzed by GC/MS using the selected ion monitoring mode. The method developed has the potential to detect synthetic musk compounds in complex matrices, may provide accurate data useful in human health and environmental risk assessment, and may be useful in determining the efficacy of municipal sewage treatment plants for removing synthetic musk compounds. PMID:16951749

  19. Potential biomarkers of smoked fentanyl utilizing pyrolysis gas chromatography-mass spectrometry.

    PubMed

    Nishikawa, Rona K; Bell, Suzanne C; Kraner, James C; Callery, Patrick S

    2009-10-01

    Fentanyl is a potent opioid analgesic that is increasingly becoming a choice drug of abuse. Fentanyl transdermal patches (FTPs) are easily obtained and consumed by smoking the reservoir gel and/or the whole patch. This allows for an increased bioavailability when inhaled. A method using analytical pyrolysis was developed to identify possible biomarkers associated with smoked fentanyl and FTPs. Pyrolysis was carried out under anaerobic and aerobic conditions using helium and air coupled to a gas chromatograph-mass spectrometer. The presence of a trap enhanced recovery and afforded a positive identification of pyrolytic products. Anaerobic and aerobic pyrolysis of fentanyl and FTPs consistently yielded propionanilide as the major pyrolytic product along with pyridine and previously reported metabolites (norfentanyl and despropionyl fentanyl). Analysis of fentanyl resulted in chlorine-containing compounds, presumably formed from the HCl salt of fentanyl. Analysis of FTPs showed significant polymeric and hydrocarbon compounds and products likely derived from the gel matrix. Fentanyl in the FTPs was in the citrate salt form; therefore, the chlorine-containing pyrolytic products obtained with the neat drug were not observed. Based on this application, it may be possible to identify what salt form of the drug was smoked based on pyrolytic products and to target distinguishing metabolic products for future research. PMID:19874647

  20. Determination of Selected Phthalates by Gas Chromatography-Mass Spectrometry in Personal Perfumes.

    PubMed

    Orecchio, Santino; Indelicato, Roberta; Barreca, Salvatore

    2015-01-01

    A simple and fast method is proposed to analyze commercial personal perfumes. Our method includes measurement of phthalates, known to be major sources of endocrine disruptor chemicals (EDC), which originate from the less volatile fraction of perfumes. The quantification of phthalates were carried out directly with no sample preparation required on 30 samples of commercial products using gas chromatography and mass spectrometry (GC-MS) as a detector. The total concentrations of 15 investigated compounds ranged from 17 to 9650 mg/L with an average of 2643 mg/L. The highest total concentration was found in cologne. Diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di(2-ethylhexyl) phthalate (DEHP), and di-n-butyl phthalate (DBP) were detected in appreciable concentrations. Further, it was found that the composition of counterfeit samples varied widely from that of authentic products. The composition of old products was different from that of recent perfumes, which contain less harmful chemicals, attributed to the ban on some phthalates in Europe due their toxicity. It should be noted that older and contaminated products are not equivalent to authentic products when considering quality, safety, and probably effectiveness. Older and nonapproved perfumes contain chemicals that are not allowed for commercial use and may contain toxic impurities. PMID:26262443

  1. Determination of the Levels of Polycyclic Aromatic Hydrocarbons in Toasted Bread Using Gas Chromatography Mass Spectrometry

    PubMed Central

    Al-Rashdan, Amal; Helaleh, Murad I. H.; Nisar, A.; Ibtisam, A.; Al-Ballam, Zainab

    2010-01-01

    Concentration of 16 polycyclic aromatic hydrocarbons (PAHs) in eighteen baked bread samples using gas oven toasting were evaluated in this study. Samples were classified into the following categories: (1) bread baked from white wheat flour, (2) bread baked from brown wheat flour, and (3) sandwich bread baked from white wheat flour. Analysis was performed by GC-MS after Soxhlet extraction of the sample and clean up of the extract. The levels of B[a]P was not detected in ten of eighteen samples. In the rest of the samples, B[a]P are varied from 2.83 to 16.54 ?g/kg. B[a]A, CHR, B[b]FA, B[k] FA, IP, DB[a,h]A, and B[ghi]P concentrations were found to be less than 10.0 ?g/kg. However, B[a]P are not detected in original white and brown wheat flour. The total PAHs were varied in the range 1.0644.24 ?g/kg and 3.08278.66 ?g/kg for H-PAH and L-PAH, respectively. Reproducibility and repeatability of the proposed method was calculated and presented in terms of recovery and relative standard deviations (RSD, %). Recoveries were varied from 72.46% to 99.06% with RSD 0.2815.01% and from 82.39% to 95.01% with RSD 1.9113.01% for repeatability and reproducibility, respectively. Different commercialized samples of toasted bread were collected and analyzed. PMID:20862370

  2. What Experimental Factors Influence the Accuracy of Retention Projections in Gas Chromatography-Mass Spectrometry?

    PubMed Central

    Wilson, Michael B.; Barnes, Brian B.; Boswell, Paul G.

    2014-01-01

    Programmed-temperature gas chromatographic (GC) retention information is difficult to share because it depends on so many experimental factors that vary among laboratories. Though linear retention indexing cannot properly account for experimental differences, retention times can be accurately calculated, or projected, from shared isothermal retention vs. temperature (T) relationships, but only if the temperature program and hold-up time vs. T profile produced by a GC is known with great precision. The effort required to measure these profiles were previously impractical, but we recently showed that they can be easily back-calculated from the programmed-temperature retention times of a set of 25 n-alkanes using open-source software at www.retentionprediction.org/gc. In a multi-lab study, the approach was shown to account for both intentional and unintentional differences in the temperature programs, flow rates, and inlet pressures produced by the GCs. Here, we tested 16 other experimental factors and found that only 5 could reduce accuracy in retention projections: injection history, exposure to very high levels of oxygen at high temperature, a very low transfer line temperature, an overloaded column, and a very short column (? 15 m). We find that the retention projection methodology acts as a hybrid of conventional retention projection and retention indexing, drawing on the advantages of both; it properly accounts for a wide range of experimental conditions while accommodating the effects of experimental factors not properly taken into account in the calculations. Finally, we developed a four-step protocol to efficiently troubleshoot a GC system after it is found to be yielding inaccurate retention projections. PMID:25482038

  3. What experimental factors influence the accuracy of retention projections in gas chromatography-mass spectrometry?

    PubMed

    Wilson, Michael B; Barnes, Brian B; Boswell, Paul G

    2014-12-19

    Programmed-temperature gas chromatographic (GC) retention information is difficult to share because it depends on so many experimental factors that vary among laboratories. Though linear retention indexing cannot properly account for experimental differences, retention times can be accurately calculated, or "projected", from shared isothermal retention vs. temperature (T) relationships, but only if the temperature program and hold-up time vs. T profile produced by a GC is known with great precision. The effort required to measure these profiles were previously impractical, but we recently showed that they can be easily back-calculated from the programmed-temperature retention times of a set of 25 n-alkanes using open-source software at www.retentionprediction.org/gc. In a multi-lab study, the approach was shown to account for both intentional and unintentional differences in the temperature programs, flow rates, and inlet pressures produced by the GCs. Here, we tested 16 other experimental factors and found that only 5 could reduce accuracy in retention projections: injection history, exposure to very high levels of oxygen at high temperature, a very low transfer line temperature, an overloaded column, and a very short column (≤15m). We find that the retention projection methodology acts as a hybrid of conventional retention projection and retention indexing, drawing on the advantages of both; it properly accounts for a wide range of experimental conditions while accommodating the effects of experimental factors not properly taken into account in the calculations. Finally, we developed a four-step protocol to efficiently troubleshoot a GC system after it is found to be yielding inaccurate retention projections. PMID:25482038

  4. Identification and quantification of polyfunctionalized hopanoids by high temperature gas chromatographymass spectrometry

    PubMed Central

    Sessions, Alex L.; Zhang, Lichun; Welander, Paula V.; Doughty, David; Summons, Roger E.; Newman, Dianne K.

    2013-01-01

    Hopanoids are triterpenoids produced mainly by bacteria, are ubiquitous in the environment, and have many important applications as biological markers. A wide variety of related hopanoid structures exists, many of which are polyfunctionalized. These modifications render the hopanoids too involatile for conventional gas chromatography (GC) separation, so require either laborious oxidative cleavage of the functional groups or specialized high temperature (HT) columns. Here we describe the systematic evaluation and optimization of a HT-GC method for the analysis of polyfunctionalized hopanoids and their methylated homologs. Total lipid extracts are derivatized with acetic anhydride and no further treatment or workup is required. We show that acid or base hydrolysis to remove di- and triacylglycerides leads to degradation of several BHP structures. DB-XLB type columns can elute hopanoids up to bacteriohopane-tetrol at 350 C, with baseline separation of all 2-methyl/desmethyl homologs. DB-5HT type columns can additionally elute bacteriohopaneaminotriol and bacteriohopaneaminotetrol, but do not fully separate 2-methyl/desmethyl homologs. The method gave 2- to 7-fold higher recovery of hopanoids than oxidative cleavage and can provide accurate quantification of all analytes including 2-methyl hopanoids. By comparing data from mass spectra with those from a flame ionization detector, we show that the mass spectromet (MS) response factors for different hopanoids using either total ion counts or m/z 191 vary substantially. Similarly, 2-methyl ratios estimated from selected-ion data are lower than those from FID by 1030% for most hopanoids, but higher by ca. 10% for bacteriohopanetetrol. Mass spectra for a broad suite of hopanoids, including 2-methyl homologs, from Rhodopseudomonas palustris are presented, together with the tentative assignment of several new hopanoid degradation products. PMID:24496464

  5. Analysis of chemical profiles of insect adhesion secretions by gas chromatography-mass spectrometry.

    PubMed

    Reitz, Manuela; Gerhardt, Heike; Schmitt, Christian; Betz, Oliver; Albert, Klaus; Lmmerhofer, Michael

    2015-01-01

    This article reports on the chemical analysis of molecular profiles of tarsal secretions of the desert locust Schistocerca gregaria (Forsskl, 1775) by gas chromatography hyphenated with quadrupol mass spectrometry (GC-MS) as well as (1)H-nuclear magnetic resonance ((1)H NMR) spectroscopy. Special focus of this study was to elaborate on sampling methods which enable selective microscale extraction of insect secretions in a spatially controlled manner, in particular tarsal adhesive secretions and secretions located on cuticle surfaces at the tibia. Various solvent sampling procedures and contact solid-phase microextraction (SPME) methods were compared in terms of comprehensiveness and extraction efficiencies as measured by signal intensities in GC-MS. Solvent sampling with water as extraction solvent gave access to the elucidation of chemical profiles of polar compound classes such as amino acids and carbohydrates, but is extremely tedious. Contact SPME on the other hand can be regarded as a simplified and more elegant alternative, in particular for the lipophilic compound fraction. Many proteinogenic amino acids and ornithine as well as carbohydrate monomers arabinose, xylose, glucose, and galactose were detected in tarsal secretions after acid hydrolysis of aqueous extracts. Qualitatively similar but quantitatively significantly different molecular profiles were found for the lipid fraction which contained mainly n-alkanes and internally branched monomethyl-, dimethyl-, and trimethyl-alkanes in the C23-C49 range as well as long chain fatty acids and aldehydes. Especially, hydrocarbons with >C40 carbon numbers have previously been rarely reported for insect secretions. The results suggest that the investigated insect secretions are complex emulsions which allow the attachment of tarsi on various otherwise incompatible materials of smooth and rough surfaces. The solid consistence of the established alkanes at ambient temperatures might contribute to a semi-solid consistence of the adhesive, amalgamating partly opposing functions such as slip resistance, tarsal release, desiccation resistance, and mechanical compliance. The methods developed can be extended to other similar applications of studying compositions of insect secretions of other species. PMID:25479867

  6. Organic compounds present in the natural Amazonian aerosol: Characterization by gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Graham, Bim; Guyon, Pascal; Taylor, Philip E.; Artaxo, Paulo; Maenhaut, Willy; Glovsky, M. Michael; Flagan, Richard C.; Andreae, Meinrat O.

    2003-12-01

    As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign in July 2001, separate day and nighttime aerosol samples were collected at a ground-based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural "background" aerosol. We used a high-volume sampler to separate the aerosol into fine (aerodynamic diameter, AD < 2.5 μm) and coarse (AD > 2.5 μm) size fractions and quantified a range of organic compounds in methanolic extracts of the samples by a gas chromatographic-mass spectrometric technique. The carbon fraction of the compounds could account for an average of 7% of the organic carbon (OC) in both the fine and coarse aerosol fractions. We observed the highest concentrations of sugars, sugar alcohols, and fatty acids in the coarse aerosol samples, which suggests that these compounds are associated with primary biological aerosol particles (PBAP) observed in the forest atmosphere. Of these, trehalose, mannitol, arabitol, and the fatty acids were found to be more prevalent at night, coinciding with a nocturnal increase in PBAP in the 2-10 μm size range (predominantly yeasts and other small fungal spores). In contrast, glucose, fructose, and sucrose showed persistently higher daytime concentrations, coinciding with a daytime increase in large fungal spores, fern spores, pollen grains, and, to a lesser extent, plant fragments (generally >20 μm in diameter), probably driven by lowered relative humidity and enhanced wind speeds/convective activity during the day. For the fine aerosol samples a series of dicarboxylic and hydroxyacids were detected with persistently higher daytime concentrations, suggesting that photochemical production of a secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Anhydrosugars (levoglucosan, mannosan, galactosan), which are specific tracers for biomass burning, were detected only at low levels in the fine aerosol samples. On the basis of the levoglucosan-to-OC emission ratio measured for biomass burning aerosol, we estimate that an average of ˜16% of the OC in the fine aerosol was due to biomass burning during CLAIRE 2001, indicating that the major fraction was associated with biogenic particles.

  7. Development and Application of Pyrolysis Gas Chromatography/Mass Spectrometry for the Analysis of Bound Trinitrotoluene Residues in Soil

    USGS Publications Warehouse

    Weiss, J.M.; Mckay, A.J.; Derito, C.; Watanabe, C.; Thorn, K.A.; Madsen, E.L.

    2004-01-01

    TNT (trinitrotoluene) is a contaminant of global environmental significance, yet determining its environmental fate has posed longstanding challenges. To date, only differential extraction-based approaches have been able to determine the presence of covalently bound, reduced forms of TNT in field soils. Here, we employed thermal elution, pyrolysis, and gas chromatography/mass spectrometry (GC/MS) to distinguish between covalently bound and noncovalently bound reduced forms of TNT in soil. Model soil organic matter-based matrixes were used to develop an assay in which noncovalently bound (monomeric) aminodinitrotoluene (ADNT) and diaminonitrotoluene (DANT) were desorbed from the matrix and analyzed at a lower temperature than covalently bound forms of these same compounds. A thermal desorption technique, evolved gas analysis, was initially employed to differentiate between covalently bound and added 15N-labeled monomeric compounds. A refined thermal elution procedure, termed "double-shot analysis" (DSA), allowed a sample to be sequentially analyzed in two phases. In phase 1, all of an added 15N-labeled monomeric contaminant was eluted from the sample at relatively low temperature. In phase 2 during high-temperature pyrolysis, the remaining covalently bound contaminants were detected. DSA analysis of soil from the Louisiana Army Ammunition Plant (LAAP; ???5000 ppm TNT) revealed the presence of DANT, ADNT, and TNT. After scrutinizing the DSA data and comparing them to results from solvent-extracted and base/acid-hydrolyzed LAAP soil, we concluded that the TNT was a noncovalently bound "carryover" from phase 1. Thus, the pyrolysis-GC/MS technique successfully defined covalently bound pools of ADNT and DANT in the field soil sample.

  8. Full evaporation dynamic headspace and gas chromatography-mass spectrometry for uniform enrichment of odor compounds in aqueous samples.

    PubMed

    Ochiai, Nobuo; Sasamoto, Kikuo; Hoffmann, Andreas; Okanoya, Kazunori

    2012-06-01

    A method for analysis of a wide range of odor compounds in aqueous samples at sub-ng mL? to ?g mL? levels was developed by full evaporation dynamic headspace (FEDHS) and gas chromatography-mass spectrometry (GC-MS). Compared to conventional DHS and headspace solid phase microextraction (HS-SPME), FEDHS provides more uniform enrichment over the entire polarity range for odor compounds in aqueous samples. FEDHS at 80C using 3 L of purge gas allows complete vaporization of 100 ?L of an aqueous sample, and trapping and drying it in an adsorbent packed tube, while providing high recoveries (85-103%) of the 18 model odor compounds (water solubility at 25C: log0.54-5.65 mg L?, vapor pressure at 25C: 0.011-3.2 mm Hg) and leaving most of the low volatile matrix behind. The FEDHS-GC-MS method showed good linearity (r>0.9909) and high sensitivity (limit of detection: 0.21-5.2 ng mL?) for the model compounds even with the scan mode in the conventional MS. The feasibility and benefit of the method was demonstrated with analyses of key odor compounds including hydrophilic and less volatile characteristics in beverages (whiskey and green tea). In a single malt whiskey sample, phenolic compounds including vanillin could be determined in the range of 0.92-5.1 ?g mL? (RSD<7.4%, n=6). For a Japanese green tea sample, 48 compounds including 19 potent odorants were positively identified from only 100 ?L of sample. Heat-induced artifact formation for potent odorants was also examined and the proposed method does not affect the additional formation of thermally generated compounds. Eighteen compounds including 12 potent odorants (e.g. coumarin, furaneol, indole, maltol, and pyrazine congeners) were determined in the range of 0.21-110 ng mL? (RSD<10%, n=6). PMID:22542289

  9. Quantitative analysis of arbutin and hydroquinone in strawberry tree (Arbutus unedo L., Ericaceae) leaves by gas chromatography-mass spectrometry.

    PubMed

    Jurica, Karlo; Kara?onji, Irena Br?i?; egan, Sandra; Opsenica, Duanka Milojkovi?; Kremer, Dario

    2015-09-01

    The phenolic glycoside arbutin and its metabolite with uroantiseptic activity hydroquinone occur naturally in the leaves of various medicinal plants and spices. In this study, an extraction procedure coupled with gas chromatography-mass spectrometry (GC-MS) was developed to determine arbutin and hydroquinone content in strawberry tree (Arbutus unedo L., Ericaceae) leaves. The method showed good linearity (R2>0.9987) in the tested concentration range (0.5-200 ?g mL(-1)), as well as good precision (RSD<5%), analytical recovery (96.2-98.0%), and sensitivity (limit of detection=0.009 and 0.004 ?g mL(-1) for arbutin and hydroquinone, respectively). The results obtained by the validated GC-MS method corresponded well to those obtained by high performance liquid chromatography (HPLC) method. The proposed method was then applied for determining arbutin and hydroquinone content in methanolic leaf extracts. The amount of arbutin in the leaves collected on the island of Kolo?ep (6.82 mg g(-1) dry weight) was found to be higher (tpaired=43.57, tc=2.92) in comparison to the amount of arbutin in the leaves collected on the island of Mali Loinj (2.75 mg g(-1) dry weight). Hydroquinone was not detected in any of the samples. The analytical features of the proposed GC-MS method demonstrated that arbutin and hydroquinone could be determined alternatively by gas chromatography. Due to its wide concentration range, the method could also be suitable for arbutin and hydroquinone analysis in leaves of other plant families (Rosaceae, Lamiaceae, etc.). PMID:26444340

  10. Structural elucidation of chemical constituents from Benincasa hispida seeds and Carissa congesta roots by gas chromatography: Mass spectroscopy

    PubMed Central

    Doshi, Gaurav M.; Nalawade, Vivek V.; Mukadam, Aaditi S.; Chaskar, Pratip K.; Zine, Sandeep P.; Somani, Rakesh R.; Une, Hemant D.

    2015-01-01

    Background: Benincasa hispida (BH) and Carissa congesta (CC) are regarded as ethnopharmacological imperative plants in Asian countries. Objective: Phytochemical screening of the extracts has shown the presence of steroids, flavonoids, saponins, glycosides, tannins, phenolic compounds, fixed oils, and fats in the BH and CC extracts. The presence of lupeol has been reported previously by us using high-performance thin-layer chromatography and high-performance liquid chromatography. Materials and Methods: Present research studies encompasses identification of chemical constituents in BH seeds and CC roots petroleum ether extracts by hyphenated technique such as gas chromatography-mass spectroscopy (MS) which when coupled gives a clear insight of constituents. Results: The components were identified by matching mass spectra with MS libraries. There were 13 and 10 different compounds analyzed from CC and BH, respectively. The components present were Pentanoic acid, 5-hydroxy, 2,4-butylphenyl; n-Hexadecanoic acid (Palmitic acid); Sulfurous acid, 2-ethylhexylhepatdecyl ester; n-Tridecane; 6-methyltridecane; (9E, 12E)-9,12-Octadecadienyl chloride, Hexadecanoic acid, 3-(trimethylsilyl)-oxy] propyl ester; 9,12-Octadecadenoic acid, 2 hydroxy-1-(hyroxymethylethyl) ester; 9,12-Octadecadienoic acid, 2,3 dihydroxypropyl ester; n-Propyl-9,12-Octadecadienoate, Lupeol; Taraxasterol; 6a, 14a-Methanopicene, perhydro-12,4a, 61a, 9,9,12a-hepatmethyl-10-hydoxy and 9-Octadecene; 2-Isoprpenyl-5-methyl-6-hepten-1-ol; n-Hexadecanoic acid, 2-hyroxy-1-(hydroxymethyl) ethyl ether; Butyl-9,12-Octadecadieonate; Friedoolean-8-en-3-one; friedours-7-en-3-one; 13,27-Cyclosuran-3-one; Stigmaste-7,25-dien-3-ol (3β, 5α); Stigmasta-7,16-dien-3-ol; chrondrillasterol in BH seeds and CC roots extracts respectively. Conclusion: Eluted components from the extracts could provide further researchers to work with various pharmacological activities related models and studies. PMID:26130941

  11. Urinary metabolites of cannabidiol in dog, rat and man and their identification by gas chromatography-mass spectrometry.

    PubMed

    Harvey, D J; Samara, E; Mechoulam, R

    1991-01-01

    Urinary metabolites of cannabidiol (CBD), a non-psychoactive cannabinoid of potential therapeutic interest, were extracted from dog, rat and human urine, concentrated by chromatography on Sephadex LH-20 and examined by gas chromatography-mass spectrometry as trimethylsilyl (TMS), [2H9]TMS, methyl ester-TMS and methyloxime-TMS derivatives. Fragmentation of the metabolites under electron-impact gave structurally informative fragment ions; computer-generated single-ion plots of these diagnostic ions were used extensively to aid metabolite identification. Over fifty metabolites were identified with considerable species variation. CBD was excreted in substantial concentration in human urine, both in the free state and as its glucuronide. In dog, unusual glucoside conjugates of three metabolites (4"- and 5"-hydroxy- and 6-oxo-CBD), not excreted in the unconjugated state, were found as the major metabolites at early times after drug administration. Other metabolites in all three species were mainly acids. Side-chain hydroxylated derivatives of CBD-7-oic acid were particularly abundant in human urine but much less so in dog. In the latter species the major oxidized metabolites were the products of beta-oxidation with further hydroxylation at C-6. A related, but undefined pathway resulted in loss of three carbon atoms from the side-chain of CBD in man with production of 2"-hydroxy-tris,nor-CBD-7-oic acid. Metabolism by the epoxide-diol pathway, resulting in dihydro-diol formation from the delta-8 double bond, gave metabolites in both dog and human urine. It was concluded that CBD could be used as a probe of the mechanism of several types of biotransformation; particularly those related to carboxylic acid metabolism as intermediates of the type not usually seen with endogenous compounds were excreted in substantial concentration. PMID:2026700

  12. Development of a thermal desorption-gas chromatography-mass spectrometry method for determining personal care products in air.

    PubMed

    Ramrez, Noelia; Marc, Rosa Maria; Borrull, Francesc

    2010-06-25

    This study describes the development of a new analytical method for determining 14 personal care products (PCPs) - nine synthetic musks, four parabens and one insect repellent - in air samples. The method is based on active sampling on sorbent tubes and thermal desorption-gas chromatography-mass spectrometry analysis, and is rapid, sensitive and drastically reduces the risk of sample contamination. Three kinds of tubes and traps were tested, those filled with Tenax TA being the most suitable for this study. Method validation showed good repeatability and reproducibility, low detection limits (between 0.03 ng m(-3) for DPMI and 12.5 ng m(-3) for propyl paraben) and good linearity for all compounds. Stability during storage indicated that samples must be kept refrigerated at 4 degrees C and analysed within 1 week of collection. The applicability of the technique to real samples was tested in different indoor and outdoor atmospheres. The total PCP values for indoor air ranged from 135 ng m(-3) in a pharmacy to 2838 ng m(-3) in a hairdresser's, whereas the values for outdoor air ranged from 14 ng m(-3) for a suburban environment to 26 ng m(-3) for an urban environment. In general, the most abundant synthetic musks were galaxolide (5.9-1256 ng m(-3)), musk xylene (1.6-766 ng m(-3)) and tonalide (1.1-138 ng m(-3)). Methyl and ethyl paraben (2.4-313 ng m(-3) and 1.8-117 ng m(-3), respectively) were the most abundant parabens. Although thermal desorption methods have been widely used for determining volatile organic compounds, they are rarely used with semi-volatile compounds. This study thus demonstrates that the thermal desorption method performs well with semi-volatile compounds and, for the first time, that it can be used for determining PCPs. PMID:20483421

  13. Estimation of D-Arabinose by Gas Chromatography/Mass Spectrometry as Surrogate for Mycobacterial Lipoarabinomannan in Human Urine

    PubMed Central

    De, Prithwiraj; Amin, Anita G.; Valli, Eloise; Perkins, Mark D.; McNeil, Michael; Chatterjee, Delphi

    2015-01-01

    Globally, tuberculosis is slowly declining each year and it is estimated that 37 million lives were saved between 2000 and 2013 through effective diagnosis and treatment. Currently, diagnosis relies on demonstration of the bacteria, Mycobacterium tuberculosis (Mtb), in clinical specimens by serial sputum microscopy, culture and molecular testing. Commercial immunoassay lateral flow kits developed to detect Mtb lipoglycan lipoarabinomannan (LAM) in urine as a marker of active TB exhibit poor sensitivity, especially in immunocompetent individuals, perhaps due to low abundance of the analyte. Our present study was designed to develop methods to validate the presence of LAM in a quantitative fashion in human urine samples obtained from culture-confirmed TB patients. Herein we describe, a consolidated approach for isolating LAM from the urine and quantifying D-arabinose as a proxy for LAM, using Gas Chromatography/Mass Spectrometry. 298 urine samples obtained from a repository were rigorously analyzed and shown to contain varying amounts of LAM-equivalent ranging between ~10–40 ng/mL. To further substantiate that D-arabinose detected in the samples originated from LAM, tuberculostearic acid, the unique 10-methyloctadecanoic acid present at the phosphatidylinositol end of LAM was also analyzed in a set of samples and found to be present confirming that the D-arabinose was indeed derived from LAM. Among the 144 samples from culture-negative TB suspects, 30 showed presence of D-arabinose suggesting another source of the analyte, such as disseminated TB or from non-tuberculosis mycobacterium. Our work validates that LAM is present in the urine samples of culture-positive patients in small but readily detectable amounts. The study further substantiates LAM in urine as a powerful biomarker for active tuberculosis. PMID:26633829

  14. Cerumen of Australian stingless bees ( Tetragonula carbonaria): gas chromatography-mass spectrometry fingerprints and potential anti-inflammatory properties

    NASA Astrophysics Data System (ADS)

    Massaro, Flavia Carmelina; Brooks, Peter Richard; Wallace, Helen Margaret; Russell, Fraser Donald

    2011-04-01

    Cerumen, or propolis, is a mixture of plant resins enriched with bee secretions. In Australia, stingless bees are important pollinators that use cerumen for nest construction and possibly for colony's health. While extensive research attests to the therapeutic properties of honeybee ( Apis mellifera) propolis, the biological and medicinal properties of Australian stingless bee cerumen are largely unknown. In this study, the chemical and biological properties of polar extracts of cerumen from Tetragonula carbonaria in South East Queensland, Australia were investigated using gas chromatography-mass spectrometry (GC-MS) analyses and in vitro 5-lipoxygenase (5-LOX) cell-free assays. Extracts were tested against comparative (commercial tincture of A. mellifera propolis) and positive controls (Trolox and gallic acid). Distinct GC-MS fingerprints of a mixed diterpenic profile typical of native bee cerumen were obtained with pimaric acid (6.31 ± 0.97%, w/w), isopimaric acid (12.23 ± 3.03%, w/w), and gallic acid (5.79 ± 0.81%, w/w) tentatively identified as useful chemical markers. Characteristic flavonoids and prenylated phenolics found in honeybee propolis were absent. Cerumen extracts from T. carbonaria inhibited activity of 5-LOX, an enzyme known to catalyse production of proinflammatory mediators (IC50 19.97 ± 2.67 μg/ml, mean ± SEM, n = 4). Extracts had similar potency to Trolox (IC50 12.78 ± 1.82 μg/ml), but were less potent than honeybee propolis (IC50 5.90 ± 0.62 μg/ml) or gallic acid (IC50 5.62 ± 0.35 μg/ml, P < 0.001). These findings warrant further investigation of the ecological and medicinal properties of this stingless bee cerumen, which may herald a commercial potential for the Australian beekeeping industry.

  15. Estimation of D-Arabinose by Gas Chromatography/Mass Spectrometry as Surrogate for Mycobacterial Lipoarabinomannan in Human Urine.

    PubMed

    De, Prithwiraj; Amin, Anita G; Valli, Eloise; Perkins, Mark D; McNeil, Michael; Chatterjee, Delphi

    2015-01-01

    Globally, tuberculosis is slowly declining each year and it is estimated that 37 million lives were saved between 2000 and 2013 through effective diagnosis and treatment. Currently, diagnosis relies on demonstration of the bacteria, Mycobacterium tuberculosis (Mtb), in clinical specimens by serial sputum microscopy, culture and molecular testing. Commercial immunoassay lateral flow kits developed to detect Mtb lipoglycan lipoarabinomannan (LAM) in urine as a marker of active TB exhibit poor sensitivity, especially in immunocompetent individuals, perhaps due to low abundance of the analyte. Our present study was designed to develop methods to validate the presence of LAM in a quantitative fashion in human urine samples obtained from culture-confirmed TB patients. Herein we describe, a consolidated approach for isolating LAM from the urine and quantifying D-arabinose as a proxy for LAM, using Gas Chromatography/Mass Spectrometry. 298 urine samples obtained from a repository were rigorously analyzed and shown to contain varying amounts of LAM-equivalent ranging between ~10-40 ng/mL. To further substantiate that D-arabinose detected in the samples originated from LAM, tuberculostearic acid, the unique 10-methyloctadecanoic acid present at the phosphatidylinositol end of LAM was also analyzed in a set of samples and found to be present confirming that the D-arabinose was indeed derived from LAM. Among the 144 samples from culture-negative TB suspects, 30 showed presence of D-arabinose suggesting another source of the analyte, such as disseminated TB or from non-tuberculosis mycobacterium. Our work validates that LAM is present in the urine samples of culture-positive patients in small but readily detectable amounts. The study further substantiates LAM in urine as a powerful biomarker for active tuberculosis. PMID:26633829

  16. Screening for petrochemical contamination in seafood by headspace solid-phase microextraction gas chromatography-mass spectrometry.

    PubMed

    Bencsath, F Aladar; Benner, Ronald A; Abraham, Ann; Wang, Yuesong; El Said, Kathleen R; Jester, Edward L E; Plakas, Steven M

    2015-05-01

    A headspace solid-phase microextraction gas chromatography-mass spectrometry (SPME GC-MS) method is described, to screen seafood for volatile organic compounds (VOCs) associated with petrochemical taint. VOCs are extracted from the headspace of heated sample homogenates by adsorption onto a SPME fiber and desorbed for analysis by GC-MS. Targeted compounds are determined semi-quantitatively using representative calibration standards for the various classes (alkanes, alkylbenzenes, indanes/tetralins, and naphthalenes) of VOCs analyzed. Sample preparation is minimal, and the analyses are rapid and automated with a capacity of 50 samples per day. The method was optimized in terms of headspace temperature, sample heating time, extraction time, and desorption time using oyster samples fortified with target compounds. Calibrations for hydrocarbon components were linear in the range of 8.3-167 ng/g; the limit of detection ranged between 0.05 and 0.21 ng/g, and the limit of quantitation between 0.16 and 0.69 ng/g. Good precision (RSD < 10 % at 16.7 ng/g for individual VOCs) and accuracy (recovery range 89-118 % at 25 ng/g) were obtained in oyster, crab, shrimp, and finfish matrices. The trueness of the method was demonstrated by quantifying VOCs at 1-2-ppb levels in oyster fortified with certified reference material NIST SRM 1491a. Following single laboratory validation, the method was employed for the determination of VOCs in seafood exposed to oil contaminated seawater and for the determination of background VOC levels in seafood species from the Gulf of Mexico and local food stores. The method as described can be used to supplement human sensory testing for petrochemical taint in seafood. PMID:25796529

  17. Accurate analysis of trace earthy-musty odorants in water by headspace solid phase microextraction gas chromatography-mass spectrometry.

    PubMed

    Ma, Kang; Zhang, Jin Na; Zhao, Min; He, Ya Juan

    2012-06-01

    A simple and sensitive method was developed for the simultaneous separation and determination of trace earthy-musty compounds including geosmin, 2-methylisoborneol, 2-isobutyl-3-methoxypyrazine, 2-isopropyl-3-methoxypyrazine, 2,3,4-trichloroanisole, 2,4,6-trichloroanisole, and 2,3,6-trichloroanisole in water samples. This method combined headspace solid-phase microextraction (HS-SPME) with gas chromatography-mass spectrometry and used naphthalene-d(8) as internal standard. A divinylbenzene/carboxen/polydimethylsiloxane fiber exposing at 90C for 30 min provided effective sample enrichment in HS-SPME. These compounds were separated by a DB-1701MS capillary column and detected in selected ion monitoring mode within 12 min. The method showed a good linearity from 1 to 100 ng L(-1) and detection limits within (0.25-0.61 ng L(-1)) for all compounds. Using naphthalene-d(8) as the internal standard, the intra-day relative standard deviation (RSD) was within (2.6-3.4%), while the inter-day RSD was (3.5-4.9%). Good recoveries were obtained for tap water (80.5-90.6%), river water (81.5-92.4%), and lake water (83.5-95.2%) spiked at 10 ng L(-1). Compared with other methods using HS-SPME for determination of odor compounds in water samples, this present method had more analytes, better precision, and recovery. This method was successfully applied for analysis of earthy-musty odors in water samples from different sources. PMID:22740259

  18. Serum level of 19-hydroxyandrostenedione during pregnancy and at delivery determined by gas chromatography/mass spectrometry

    SciTech Connect

    Osawa, Y.; Ohnishi, S.; Yarborough, C.; Ohigashi, S.; Kosaki, T.; Hashino, M.; Yanaihara, T.; Nakayama, T. )

    1990-04-01

    19-Hydroxyandrostenedione (19-OHA) is secreted from the adrenal glands in men and women and also from the placenta during pregnancy. It has been found to cause hypertension in animal models. We have synthesized (7,7-2H2)-19-OHA with high deuterium content and, together with (7,7-2H2)A and (9,11-2H2)estrone (E1), have developed a quantitative assay of serum level 19-OHA, A, and E1 using the gas chromatography/mass spectrometry-mass fragmentography method to monitor individual subjects throughout pregnancy. The labeled 19-OHA, used as internal standard, showed only 6.73% of unlabeled compound. Recovery of standard 19-OHA, A, and E1 (5,000 pg each) added to male plasma was 97.4 +/- 2.3%, 96.3 +/- 2.1%, and 100.1 +/- 4.1% (mean +/- SD), respectively; the intraassay coefficient of variation was 2.1%, 3.5%, and 3.8%, respectively. Ten pregnant subjects without complications and 10 pregnant subjects near term with hypertension were selected (with informed consent). The 19-OHA and E1 serum concentrations of maternal venous blood from uncomplicated pregnancies increased significantly as gestation progressed (19-OHA: first trimester, 225 +/- 72; second trimester, 656 +/- 325; third trimester, 1,518 +/- 544 pg/ml), reaching the highest level at delivery (19-OHA: 1,735 +/- 684 pg/ml). Whereas a positive correlation was found between the level of 19-OHA and E1, no apparent change of the A level was observed during pregnancy. Levels of the three steroid hormones in pregnancy complicated by hypertension in the second and third trimester were not found to be significantly different from those of normal pregnancy (19-OHA of hypertensive subjects: second trimester, 762 +/- 349; third trimester, 1,473 +/- 491 pg/ml).

  19. Comparison of four extraction methods for the determination of fungicide residues in grapes through gas chromatography-mass spectrometry.

    PubMed

    Lagunas-Allué, L; Sanz-Asensio, J; Martínez-Soria, M T

    2012-12-28

    Four different methods for simultaneous extraction of vinclozolin, dichlofluanid, penconazole, captan, quinoxyfen, fluquinconazol, boscalid and pyraclostrobin from grapes were optimized and further tested. Microwave assisted extraction (MAE), matrix solid-phase dispersion (MSPD), solid-liquid extraction (SLE) and QuEChERS were compared in terms of their limits of detection and quantification and recoveries. For MAE, MSPD and ethyl acetate extraction, the optimal conditions were optimized by using experimental designs. The analysis was performed using gas chromatography-mass spectrometry in the selected ion monitoring mode (GC-MS, SIM). The proposed methods showed good sensitivity, limits of quantification were lower than MRLs and precision (expressed as relative standard deviation) ranged from 2.9 to 11.1%. The recoveries obtained from MAE, MSPD, SLE and QuEChERS were in the range 78-100%, 66-102%, 58-88% and 68-96%, respectively. In addition, the four methods were compared in two ways: by means of calibration curves obtained with 10 fortified samples in the studied range of concentrations and by the application of statistical tests such as Levene's test (to study variance homogeneity), ANOVA and Tukey's test (in case of Levene's test was satisfactory) for the assessment of the information obtained in the analysis of real samples. Both ways of comparison led to the same results: no differences between the four methods for the extraction of vinclozolin, dichofluanid, quinoxyfen, fluquinconazol and pyraclostrobin were found. However, there were differences for the analysis of captan, boscalid and penconazole. PMID:23182285

  20. Hyphenated and comprehensive liquid chromatography×gas chromatography-mass spectrometry for the identification of Mycobacterium tuberculosis.

    PubMed

    Mourão, Marta P B; Denekamp, Ilse; Kuijper, Sjoukje; Kolk, Arend H J; Janssen, Hans-Gerd

    2016-03-25

    Tuberculosis is one of the world's most emerging public health problems, particularly in developing countries. Chromatography based methods have been used to tackle this epidemic by focusing on biomarker detection. Unfortunately, interferences from lipids in the sputum matrix, particularly cholesterol, adversely affect the identification and detection of the marker compounds. The present contribution describes the serial combination of normal phase liquid chromatography (NPLC) with thermally assisted hydrolysis and methylation followed by gas chromatography-mass spectrometry (THM-GC-MS) to overcome the difficulties of biomarker evaluation. The in-series combination consists of an LC analysis where fractions are collected and then transferred to the THM-GC-MS system. This was either done with comprehensive coupling, transferring all the fractions, or with hyphenated interfacing, i.e. off-line multi heart-cutting, transferring only selected fractions. Owing to the high sensitivity and selectivity of LC as a sample pre-treatment method, and to the high specificity of the MS as a detector, this analytical approach, NPLC×THM-GC-MS, is extremely sensitive. The results obtained indicate that this analytical set-up is able to detect down to 1×10(3) mycobacteria/mL of Mycobacterium tuberculosis strain 124, spiked in blank sputum samples. It is a powerful analytical tool and also has great potential for full automation. If further studies demonstrate its usefulness when applied blind in real sputum specimens, this technique could compete with the current smear microscopy in the early diagnosis of tuberculosis. PMID:26585206

  1. Determination of alkylamines in atmospheric aerosol particles: a comparison of gas chromatography-mass spectrometry and ion chromatography approaches

    NASA Astrophysics Data System (ADS)

    Huang, R.-J.; Li, W.-B.; Wang, Y.-R.; Wang, Q. Y.; Jia, W. T.; Ho, K.-F.; Cao, J. J.; Wang, G. H.; Chen, X.; Haddad, I. EI; Zhuang, Z. X.; Wang, X. R.; Prévôt, A. S. H.; O'Dowd, C. D.; Hoffmann, T.

    2014-07-01

    In recent years low molecular weight alkylamines have been recognized to play an important role in particle formation and growth in the lower atmosphere. However, major uncertainties are associated with their atmospheric processes, sources and sinks, mostly due to the lack of ambient measurements and the difficulties in accurate quantification of alkylamines at trace level. In this study, we present the evaluation and optimization of two analytical approaches, i.e., gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC), for the determination of alkylamines in aerosol particles. Alkylamines were converted to carbamates through derivatization with isobutyl chloroformate for GC-MS determination. A set of parameters affecting the analytical performances of the GC-MS approach, including reagent amount, reaction time and pH value, was evaluated and optimized. The accuracy is 84.3-99.1%, and the limits of detection obtained are 1.8-3.9 pg (or 0.02-0.04 ng m-3). For the IC approach, a solid-phase extraction (SPE) column was used to separate alkylamines from interfering cations before IC analysis. 1-2% (v/v) of acetone (or 2-4% (v/v) of acetonitrile) was added to the eluent to improve the separation of alkylamines on the IC column. The limits of detection obtained are 2.1-15.9 ng (or 0.9-6.4 ng m-3), and the accuracy is 55.1-103.4%. The lower accuracy can be attributed to evaporation losses of amines during the sample concentration procedure. Measurements of ambient aerosol particle samples collected in Hong Kong show that the GC-MS approach is superior to the IC approach for the quantification of primary and secondary alkylamines due to its lower detection limits and higher accuracy.

  2. Determination of alkyl amines in atmospheric aerosol particles: a comparison of gas chromatography-mass spectrometry and ion chromatography approaches

    NASA Astrophysics Data System (ADS)

    Huang, R.-J.; Li, W.-B.; Wang, Y.-R.; Wang, Q. Y.; Ho, K.-F.; Cao, J. J.; Wang, G. H.; Chen, X.; Haddad, I. EI; Zhuang, Z. X.; Wang, X. R.; Prévôt, A. S. H.; O'Dowd, C. D.; Hoffmann, T.

    2014-03-01

    In recent years low molecular weight alkyl amines have been recognized to play an important role in particle formation and growth in the lower atmosphere. However, major uncertainties are associated with their atmospheric processes, sources and sinks, mostly due to the lack of ambient measurements and the difficulties in accurate quantification of alkyl amines at trace level. In this study, we present the evaluation and optimization of two analytical approaches, i.e., gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC), for the determination of alkyl amines in aerosol particles. Alkyl amines were converted to carbamates through derivatization with isobutyl chloroformate for GC-MS determination. A set of parameters affecting the analytical performances of the GC-MS approach, including reagent amount, reaction time and pH value, was evaluated and optimized. The accuracy is 84.3-99.1%, and the limits of detection obtained are 1.8-3.9 pg. For the IC approach, a solid phase extraction (SPE) column was used to separate alkyl amines from interfering cations before IC analysis. 1-2% (v/v) of acetone (or 2-4% (v/v) of acetonitrile) was added to the eluent to improve the separation of alkyl amines on the IC column. The limits of detection obtained are 2.1-15.9 ng and the accuracy is 55.1-103.4%. The lower accuracy can be attributed to evaporation losses of amines during the sample concentration procedure. Measurements of ambient aerosol particle samples collected in Hong Kong show that the GC-MS approach is superior to the IC approach for the quantification of primary and secondary alkyl amines due to its lower detection limits and higher accuracy.

  3. Cerumen of Australian stingless bees (Tetragonula carbonaria): gas chromatography-mass spectrometry fingerprints and potential anti-inflammatory properties.

    PubMed

    Massaro, Flavia Carmelina; Brooks, Peter Richard; Wallace, Helen Margaret; Russell, Fraser Donald

    2011-04-01

    Cerumen, or propolis, is a mixture of plant resins enriched with bee secretions. In Australia, stingless bees are important pollinators that use cerumen for nest construction and possibly for colony's health. While extensive research attests to the therapeutic properties of honeybee (Apis mellifera) propolis, the biological and medicinal properties of Australian stingless bee cerumen are largely unknown. In this study, the chemical and biological properties of polar extracts of cerumen from Tetragonula carbonaria in South East Queensland, Australia were investigated using gas chromatography-mass spectrometry (GC-MS) analyses and in vitro 5-lipoxygenase (5-LOX) cell-free assays. Extracts were tested against comparative (commercial tincture of A. mellifera propolis) and positive controls (Trolox and gallic acid). Distinct GC-MS fingerprints of a mixed diterpenic profile typical of native bee cerumen were obtained with pimaric acid (6.31 0.97%, w/w), isopimaric acid (12.23 3.03%, w/w), and gallic acid (5.79 0.81%, w/w) tentatively identified as useful chemical markers. Characteristic flavonoids and prenylated phenolics found in honeybee propolis were absent. Cerumen extracts from T. carbonaria inhibited activity of 5-LOX, an enzyme known to catalyse production of proinflammatory mediators (IC?? 19.97 2.67 ?g/ml, mean SEM, n?=?4). Extracts had similar potency to Trolox (IC?? 12.78 1.82 ?g/ml), but were less potent than honeybee propolis (IC?? 5.90 0.62 g/ml) or gallic acid (IC?? 5.62 0.35 ?g/ml, P < 0.001). These findings warrant further investigation of the ecological and medicinal properties of this stingless bee cerumen, which may herald a commercial potential for the Australian beekeeping industry. PMID:21347735

  4. Determination of amphetamine and methamphetamine in serum via headspace derivatization solid-phase microextraction-gas chromatography-mass spectrometry.

    PubMed

    Lee, M R; Song, Y S; Hwang, B H; Chou, C C

    2000-10-27

    This study evaluates solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) to determine trace levels of amphetamine and methamphetamine in serum. Headspace post-derivatization in a laboratory-made design with heptafluorobutyric anhydride vapor following SPME was compared with that without derivatization SPME. The SPME experimental procedures to extract amphetamine and methamphetamine in serum were optimized with a relatively non-polar poly(dimethylsiloxane) coated fiber at pH 9.5, extraction time for 40 min and desorption at 260 degrees C for 2 min. Experimental results indicate that the concentration of the serum matrix diluted to a quarter of original (1:3) ratio by using one volume of buffer solution of boric acid mixed with sodium hydroxide and two volumes of water improves the extraction efficiency. Headspace derivatization following SPME was performed by using 6 microl 20% (v/v) heptafluorobutyric anhydride ethyl acetate solution at an oil bath temperature of 270 degrees C for 10 s. The precision was below 7% for analysis for without derivatization and below 17% for headspace derivatization. Detection limits were obtained at the ng/l level, one order better obtained in headspace derivatization than those achieved without derivatization. The feasibility of applying the methods to determine amphetamine and methamphetamine in real samples was examined by analyzing serum samples from methamphetamine abused suspects. Concentrations of the amphetamine and methamphetamine ranged from 6.0 microg/l (amphetamine) to 77 microg/l (methamphetamine) in serum. PMID:11093661

  5. Selective pressurized liquid extraction of estrogenic compounds in soil and analysis by gas chromatography-mass spectrometry.

    PubMed

    Zhang, Zulin; Rhind, Stewart M; Kerr, Christine; Osprey, Mark; Kyle, Carol E

    2011-01-24

    A selective pressurized liquid extraction (SPLE) method, followed by gas chromatography-mass spectrometry (GC-MS), for the simultaneous extraction and clean-up of estrone (E1), 17?-estradiol (E2), 17?-ethynylestradiol (EE2), estriol (E3) and bisphenol A (BPA) from soil samples is described. The on-line clean-up of soil by SPLE was achieved using different organic matter retainers, including silica, alumina and Florisil, the most effective being silica. Thus, different amounts of silica, in conjunction with different extraction solvents (acetone, ethyl acetate, isohexane and dichloromethane), either alone or in combination, were used to extract the target chemicals from spiked soil samples. It was shown that 3g silica resulted in satisfactory rates of recovery of target compounds and acetone:dichloromethane (1:3, v/v) was efficient in extracting and eluting estrogenic compounds for SPLE. Variables affecting the SPLE efficiency, including temperature and pressure were studied; the optimum parameters were 60C and 1500 psi, respectively. The limits of detection (LODs) of the proposed method were 0.02-0.37 ng g(-1) for the different estrogenic chemicals studied. The outputs using the proposed method were linear over the range from 0.1 to 120 ng g(-1) for E1, E2, EE2, 0.2-120 ng g(-1) for E3, and 0.5-120 ng g(-1) for BPA. The optimized method was further verified by performing spiking experiments in natural soil matrices; good rates of recovery and reproducibility were achieved for all selected compounds and the method was successfully applied to soil samples from Northeast Scotland, for the determination of the target compounds. PMID:21168548

  6. Determination of organochlorine pesticides in water samples by dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Cortada, Carol; Vidal, Lorena; Pastor, Raul; Santiago, Noemi; Canals, Antonio

    2009-09-01

    A rapid and simple dispersive liquid-liquid microextraction (DLLME) has been developed to preconcentrate eighteen organochlorine pesticides (OCPs) from water samples prior to analysis by gas chromatography-mass spectrometry (GC-MS). The studied variables were extraction solvent type and volume, disperser solvent type and volume, aqueous sample volume and temperature. The optimum experimental conditions of the proposed DLLME method were: a mixture of 10 microL tetrachloroethylene (extraction solvent) and 1 mL acetone (disperser solvent) exposed for 30 s to 10 mL of the aqueous sample at room temperature (20 degrees C). Centrifugation of cloudy solution was carried out at 2300 rpm for 3 min to allow phases separation. Finally, 2 microL of extractant was recovered and injected into the GC-MS instrument. Under the optimum conditions, the enrichment factors ranged between 46 and 316. The calculated calibration curves gave a high-level linearity for all target analytes with correlation coefficients ranging between 0.9967 and 0.9999. The repeatability of the proposed method, expressed as relative standard deviation, varied between 5% and 15% (n=8), and the detection limits were in the range of 1-25 ng L(-1). The LOD values obtained are able to detect these OCPs in aqueous matrices as required by EPA methods 525.2 and 625. Analysis of spiked real water samples revealed that the matrix had no effect on extraction for river, surface and tap waters; however, urban wastewater sample shown a little effect for five out of eighteen analytes. PMID:19699397

  7. Identification of microorganisms based on headspace analysis of volatile organic compounds by gas chromatography-mass spectrometry.

    PubMed

    Boots, A W; Smolinska, A; van Berkel, J J B N; Fijten, R R R; Stobberingh, E E; Boumans, M L L; Moonen, E J; Wouters, E F M; Dallinga, J W; Van Schooten, F J

    2014-06-01

    The identification of specific volatile organic compounds (VOCs) produced by microorganisms may assist in developing a fast and accurate methodology for the determination of pulmonary bacterial infections in exhaled air. As a first step, pulmonary bacteria were cultured and their headspace analyzed for the total amount of excreted VOCs to select those compounds which are exclusively associated with specific microorganisms. Development of a rapid, noninvasive methodology for identification of bacterial species may improve diagnostics and antibiotic therapy, ultimately leading to controlling the antibiotic resistance problem. Two hundred bacterial headspace samples from four different microorganisms (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Klebsiella pneumoniae) were analyzed by gas chromatography-mass spectrometry to detect a wide array of VOCs. Statistical analysis of these volatiles enabled the characterization of specific VOC profiles indicative for each microorganism. Differences in VOC abundance between the bacterial types were determined using ANalysis of VAriance-principal component analysis (ANOVA-PCA). These differences were visualized with PCA. Cross validation was applied to validate the results. We identified a large number of different compounds in the various headspaces, thus demonstrating a highly significant difference in VOC occurrence of bacterial cultures compared to the medium and between the cultures themselves. Additionally, a separation between a methicillin-resistant and a methicillin-sensitive isolate of S. aureus could be made due to significant differences between compounds. ANOVA-PCA analysis showed that 25 VOCs were differently profiled across the various microorganisms, whereas a PCA score plot enabled the visualization of these clear differences between the bacterial types. We demonstrated that identification of the studied microorganisms, including an antibiotic susceptible and resistant S. aureus substrain, is possible based on a selected number of compounds measured in the headspace of these cultures. These in vitro results may translate into a breath analysis approach that has the potential to be used as a diagnostic tool in medical microbiology. PMID:24737039

  8. Optimization of pressurized liquid extraction and purification conditions for gas chromatography-mass spectrometry determination of UV filters in sludge.

    PubMed

    Negreira, N; Rodríguez, I; Rubí, E; Cela, R

    2011-01-14

    This work presents an effective sample preparation method for the determination of eight UV filter compounds, belonging to different chemical classes, in freeze-dried sludge samples. Pressurized liquid extraction (PLE) and gas chromatography-mass spectrometry (GC-MS) were selected as extraction and determination techniques, respectively. Normal-phase, reversed-phase and anionic exchange materials were tested as clean-up sorbents to reduce the complexity of raw PLE extracts. Under final working conditions, graphitized carbon (0.5 g) was used as in-cell purification sorbent for the retention of co-extracted pigments. Thereafter, a solid-phase extraction cartridge, containing 0.5 g of primary secondary amine (PSA) bonded silica, was employed for off-line removal of other interferences, mainly fatty acids, overlapping the chromatographic peaks of some UV filters. Extractions were performed with a n-hexane:dichloromethane (80:20, v:v) solution at 75°C, using a single extraction cycle of 5 min at 1500 psi. Flush volume and purge time were set at 100% and 2 min, respectively. Considering 0.5 g of sample and 1 mL as the final volume of the purified extract, the developed method provided recoveries between 73% and 112%, with limits of quantification (LOQs) from 17 to 61 ng g(-1) and a linear response range up to 10 μg g(-1). Total solvent consumption remained around 30 mL per sample. The analysis of non-spiked samples confirmed the sorption of significant amounts of several UV filters in sludge with average concentrations above 0.6 μg g(-1) for 3-(4-methylbenzylidene) camphor (4-MBC), 2-ethylhexyl-p-methoxycinnamate (EHMC) and octocrylene (OC). PMID:21144528

  9. Response to weaning and dietary L-glutamine supplementation: metabolomic analysis in piglets by gas chromatography/mass spectrometry.

    PubMed

    Xiao, Ying-ping; Wu, Tian-xing; Hong, Qi-hua; Sun, Jiang-ming; Chen, An-guo; Yang, Cai-mei; Li, Xiao-yan

    2012-07-01

    A novel metabolomic method based on gas chromatography/mass spectrometry (GC-MS) was applied to determine the metabolites in the serum of piglets in response to weaning and dietary L-glutamine (Gln) supplementation. Thirty-six 21-d-old piglets were randomly assigned into three groups. One group continued to suckle from the sows (suckling group), whereas the other two groups were weaned and their diets were supplemented with 1% (w/w) Gln or isonitrogenous L-alanine, respectively, representing Gln group or control group. Serum samples were collected to characterize metabolites after a 7-d treatment. Results showed that twenty metabolites were down-regulated significantly (P<0.05) in control piglets compared with suckling ones. These data demonstrated that early weaning causes a wide range of metabolic changes across arginine and proline metabolism, aminosugar and nucleotide metabolism, galactose metabolism, glycerophospholipid metabolism, biosynthesis of unsaturated fatty acid, and fatty acid metabolism. Dietary Gln supplementation increased the levels of creatinine, D-xylose, 2-hydroxybutyric acid, palmitelaidic acid, and ?-L-galactofuranose (P<0.05) in early weaned piglets, and were involved in the arginine and proline metabolism, carbohydrate metabolism, and fatty acid metabolism. A leave-one-out cross-validation of random forest analysis indicated that creatinine was the most important metabolite among the three groups. Notably, the concentration of creatinine in control piglets was decreased (P=0.00001) compared to the suckling piglets, and increased (P=0.0003) in Gln-supplemented piglets. A correlation network for weaned and suckling piglets revealed that early weaning changed the metabolic pathways, leading to the abnormality of carbohydrate metabolism, amino acid metabolism, and lipid metabolism, which could be partially improved by dietary Gln supplementation. These findings provide fresh insight into the complex metabolic changes in response to early weaning and dietary Gln supplementation in piglets. PMID:22761248

  10. Chemometric Analysis of Gas Chromatography Mass Spectrometry Data using Fast Retention Time Alignment via a Total Ion Current Shift Function

    SciTech Connect

    Nadeau, Jeremy S.; Wright, Bob W.; Synovec, Robert E.

    2010-04-15

    A critical comparison of methods for correcting severely retention time shifted gas chromatography-mass spectrometry (GC-MS) data is presented. The method reported herein is an adaptation to the Piecewise Alignment Algorithm to quickly align severely shifted one-dimensional (1D) total ion current (TIC) data, then applying these shifts to broadly align all mass channels throughout the separation, referred to as a TIC shift function (SF). The maximum shift varied from (-) 5 s in the beginning of the chromatographic separation to (+) 20 s toward the end of the separation, equivalent to a maximum shift of over 5 peak widths. Implementing the TIC shift function (TIC SF) prior to Fisher Ratio (F-Ratio) feature selection and then principal component analysis (PCA) was found to be a viable approach to classify complex chromatograms, that in this study were obtained from GC-MS separations of three gasoline samples serving as complex test mixtures, referred to as types C, M and S. The reported alignment algorithm via the TIC SF approach corrects for large dynamic shifting in the data as well as subtle peak-to-peak shifts. The benefits of the overall TIC SF alignment and feature selection approach were quantified using the degree-of-class separation (DCS) metric of the PCA scores plots using the type C and M samples, since they were the most similar, and thus the most challenging samples to properly classify. The DCS values showed an increase from an initial value of essentially zero for the unaligned GC-TIC data to a value of 7.9 following alignment; however, the DCS was unchanged by feature selection using F-Ratios for the GC-TIC data. The full mass spectral data provided an increase to a final DCS of 13.7 after alignment and two-dimensional (2D) F-Ratio feature selection.

  11. Response to weaning and dietary L-glutamine supplementation: metabolomic analysis in piglets by gas chromatography/mass spectrometry*

    PubMed Central

    Xiao, Ying-ping; Wu, Tian-xing; Hong, Qi-hua; Sun, Jiang-ming; Chen, An-guo; Yang, Cai-mei; Li, Xiao-yan

    2012-01-01

    A novel metabolomic method based on gas chromatography/mass spectrometry (GC-MS) was applied to determine the metabolites in the serum of piglets in response to weaning and dietary L-glutamine (Gln) supplementation. Thirty-six 21-d-old piglets were randomly assigned into three groups. One group continued to suckle from the sows (suckling group), whereas the other two groups were weaned and their diets were supplemented with 1% (w/w) Gln or isonitrogenous L-alanine, respectively, representing Gln group or control group. Serum samples were collected to characterize metabolites after a 7-d treatment. Results showed that twenty metabolites were down-regulated significantly (P<0.05) in control piglets compared with suckling ones. These data demonstrated that early weaning causes a wide range of metabolic changes across arginine and proline metabolism, aminosugar and nucleotide metabolism, galactose metabolism, glycerophospholipid metabolism, biosynthesis of unsaturated fatty acid, and fatty acid metabolism. Dietary Gln supplementation increased the levels of creatinine,D-xylose, 2-hydroxybutyric acid, palmitelaidic acid, and ?-L-galactofuranose (P<0.05) in early weaned piglets, and were involved in the arginine and proline metabolism, carbohydrate metabolism, and fatty acid metabolism. A leave-one-out cross-validation of random forest analysis indicated that creatinine was the most important metabolite among the three groups. Notably, the concentration of creatinine in control piglets was decreased (P=0.00001) compared to the suckling piglets, and increased (P=0.0003) in Gln-supplemented piglets. A correlation network for weaned and suckling piglets revealed that early weaning changed the metabolic pathways, leading to the abnormality of carbohydrate metabolism, amino acid metabolism, and lipid metabolism, which could be partially improved by dietary Gln supplementation. These findings provide fresh insight into the complex metabolic changes in response to early weaning and dietary Gln supplementation in piglets. PMID:22761248

  12. Chlorinated hydrocarbons in the atmosphere - Analysis at the parts-per-trillion level by GC-MS. [Gas Chromatography-Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Tyson, B. J.

    1975-01-01

    The propellant gases (Freons) used in aerosol spray cans can diffuse into the earth's upper atmosphere where they can react with the unfiltered ultraviolet radiation from the sun to reduce the earth's protective ozone layer. These Freons have been identified commonly by gas chromatography. Mass spectrometer data confirm other reports on the widespread concentrations of the Freons in the troposphere and demonstrate the presence of Freon 113 which has not been previously identified.

  13. Determination of parts-per-billion concentrations of dioxane in water and soil by purge and trap gas chromatography/mass spectrometry or charcoal tube enrichment gas chromatography

    SciTech Connect

    Epstein, P.S.; Mauer, T.; Wagner, M.; Chase, S.; Giles, B.

    1987-08-01

    Two methods for the determination of 1,4-dioxane in water have been studied. The first method is a heated purge and trap gas chromatography/mass spectrometry system following salting out with sodium sulfate. The second method is an adsorption on coconut-shell charcoal and solvent desorption with carbon disulfide/methanol followed by analysis of the desorbate by gas chromatography with flame ionization detection. The first method is also successful for the determination of 1,4-dioxane in solids and sediments. The second method is shown to be successful for 2-butanone, 4-methyl-2-pentanone, and butoxyethanol in water. The two methods are compared by analyzing 15 samples by both methods and achieving similar results.

  14. Characterization of odor-active compounds of various Chrysanthemum essential oils by gas chromatography-olfactometry, gas chromatography-mass spectrometry and their correlation with sensory attributes.

    PubMed

    Xiao, Zuobing; Fan, Binbin; Niu, Yunwei; Wu, Minling; Liu, Junhua; Ma, Shengtao

    2016-01-15

    Volatiles of five kinds of Chrysanthemum essential oils with different manufactures were characterized by descriptive sensory analysis, gas chromatography-olfactometry (GC-O), gas chromatography-mass spectrometry (GC-MS) and statistics analysis. Six sensory attributes (floral, woody, grassy, fruity, sour and minty) were selected to assess Chrysanthemum essential oils. A total of 38 volatile compounds were detected and quantified using standard substances by GC-O and GC-MS. Terpenes constituted the largest chemical group among the volatiles of the essential oils. Then partial least squares regression (PLSR) was used to elucidate the relationship between sensory attributes and aroma compounds. The result showed that α-pinene, β-thujene, α-terpinolen, β-cubebene, caryophyllene, (Z)β-farnesene, (-)-spathulenol, linalool, camphor, camphene, 4-terpineol, Z-citral and 4-isopropyltoluene were typical aroma compounds covaried with characteristic aroma of Chrysanthemum essential oils. PMID:26735711

  15. Monitoring the ripening process of Cheddar cheese based on hydrophilic component profiling using gas chromatography-mass spectrometry.

    PubMed

    Ochi, H; Sakai, Y; Koishihara, H; Abe, F; Bamba, T; Fukusaki, E

    2013-01-01

    We proposed an application methodology that combines metabolic profiling with multiple appropriate multivariate analyses and verified it on the industrial scale of the ripening process of Cheddar cheese to make practical use of hydrophilic low-molecular-weight compound profiling using gas chromatography-mass spectrometry to design optimal conditions and quality monitoring of the cheese ripening process. Principal components analysis provided an overview of the effect of sodium chloride content and kind of lactic acid bacteria starter on the metabolic profile in the ripening process of Cheddar cheese and orthogonal partial least squares-discriminant analysis unveiled the difference in characteristic metabolites. When the sodium chloride contents were different (1.6 and 0.2%) but the same lactic acid bacteria starter was used, the 2 cheeses were classified by orthogonal partial least squares-discriminant analysis from their metabolic profiles, but were not given perfect discrimination. Not much difference existed in the metabolic profile between the 2 cheeses. Compounds including lactose, galactose, lactic acid, 4-aminobutyric acid, and phosphate were identified as contents that differed between the 2 cheeses. On the other hand, in the case of the same salt content of 1.6%, but different kinds of lactic acid bacteria starter, an excellent distinctive discrimination model was obtained, which showed that the difference of lactic acid bacteria starter caused an obvious difference in metabolic profiles. Compounds including lactic acid, lactose, urea, 4-aminobutyric acid, galactose, phosphate, proline, isoleucine, glycine, alanine, lysine, leucine, valine, and pyroglutamic acid were identified as contents that differed between the 2 cheeses. Then, a good sensory prediction model for "rich flavor," which was defined as "thick and rich, including umami taste and soy sauce-like flavor," was constructed based on the metabolic profile during ripening using partial least squares regression analysis. The amino acids proline, leucine, valine, isoleucine, pyroglutamic acid, alanine, glutamic acid, glycine, lysine, tyrosine, serine, phenylalanine, methionine, aspartic acid, and ornithine were extracted as ripening process markers. The present study is not limited to Cheddar cheese and can be applied to various maturation-type natural cheeses. This study provides the technical platform for designing optimal conditions and quality monitoring of the cheese ripening process. PMID:24140316

  16. Trimethylsilyl speciations of cathine, cathinone and norephedrine followed by gas chromatography mass spectrometry: Direct sample preparation and analysis of khatamines.

    PubMed

    Molnár, Borbála; Fodor, Blanka; Boldizsár, Imre; Molnár-Perl, Ibolya

    2016-04-01

    A literature criticism is given on methods using currently gas chromatography mass spectrometry (GC/MS) to determine cathine (CAT), cathinone (CTN) and norephedrine (NE), jointly khatamines. In this study, khatamines' oximation, trimethylsilylation and mass fragmentation properties-applying N-Methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA), its trimethyliodosilane (TMIS) catalyst containing version (MSTFA(TMIS)), N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and hexamethyldisilazane (HMDS)-was highlighted, at first. Derivatization, mass fragmentation and quantitation related, optimized model investigations have been carried out as a function of the reaction times and conditions. Special emphasis was put (i) on the stability of the primarily formed (CAT-2TMS, NE-2TMS, CTN-TMS(TMS-oximes)1,2), then transformed, fully derived (CAT-3TMS, NE-3MTS, CTN-2TMS(TMS-oximes)1,2) species, and, (ii) on the proportionally formed stable products, suitable to selective quantitation of all three natural amines, simultaneously. Results, as novelty to the field confirmed that (i) TMIS catalyzed trimethylsilyation triggers to form fully derivatized species unfortunately, in part only; while, (ii) khatamines' simultaneous quantitation needs to be carried out in a two steps derivatization process consisting of oximation (1st step, hydroxylamine in pyridine) and trimethylsilylation (2nd step, MSTFA), to the CAT-2TMS, NE-2TMS, CTN-TMS(TMS-oximes)1,2. These species were characterized with their retention, mass fragmentation and analytical performance properties, in model solutions and in the presence of plant tissues, as well: R(2), limit of quantitation (LOQ) data, expressed in pg/1μL injection basis, proved to be 62.5pg (CAT), 20pg (NE) and 62.5pg (CTN), respectively. The practical utility of proposal was enormously enhanced by the novel, direct sample preparation method. In this process, the freshly harvested, freeze-dried, then pulverized leaves of Catha edulis FORKS were directly derivatized, in the presence of the matrix. Reproducibility (in average 2.07 RSD% varying between 0.15 and 5.5 RSD%), linearity (0.9990-0.9994) and recovery (95.7-99.1%) values of the new sample preparation protocol was confirmed by the standard addition method for CAT, NE and CTN equally. From plant leaf, 0.061w/w% CAT and 0.014w/w% NE contents were obtained. In this tissue CTN was not found. Very likely attributable to the unfavorable climate for the plant: grown in Hungary of temperate zone and naturalized in the tropical Africa. PMID:26928873

  17. Simultaneous determination of amphetamine-type stimulants and cannabinoids in fingernails by gas chromatography-mass spectrometry.

    PubMed

    Kim, Jin Young; Cheong, Jae Chul; Kim, Min Kyoung; Lee, Jae Il; In, Moon Kyo

    2008-06-01

    A gas chromatography-mass spectrometric (GC-MS) method was developed and validated for the simultaneous detection and quantification of four amphetamine-type stimulants (amphetamine (AP), methamphetamine (MA), 3,4-methylenedioxyamphetamine (MDA) and 3,4-methylenedioxymethamphetamine (MDMA)) and two cannabinoids (Delta9-tetrahydrocannabinol (Delta9-THC) and 11-nor-Delta9-tetrahydrocannabinol-9-carboxylic acid (THCCOOH)) in fingernails. Fingernail clippings (30 mg) were washed with distilled water and methanol, and then incubated in 1.0 M sodium hydroxide at 95 degrees C for 30 min. The compounds of interest were isolated by liquid-liquid extraction followed by derivatization with N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA) at 70 degrees C for 15 min. The derivatized compounds were analyzed by GC-MS in the selective ion monitoring (SIM) mode. The linear ranges were 0.1-15.0 ng/mg for AP, 0.2-15.0 ng/mg for MDA, Delta9-THC and THCCOOH, and 0.2-30.0 ng/mg for MA and MDMA, with good correlation coefficients (r2 > 0.9991). The intra-day, inter-day, and inter-person precisions were within 10.6%, 6.3%, and 5.3%, respectively. The intra-day, inter-day and inter-person accuracies were between -6.1 and 5.0%, -6.2 and 5.7%, and -6.4 and 5.6%, respectively. The limits of detection (LODs) and quantification (LOQs) for each compound were lower than 0.056 and 0.2 ng/mg, respectively. The recoveries were in the range of 74.0-94.8%. Positive GC-MS results were obtained from specimens of nine suspected MA or cannabis abusers. The concentration ranges of MA, AP, and THCCOOH were 0.10-1.41, 0.12-2.64, and 0.20 ng/mg, respectively. Based on these results, the method proved to be effective for the simultaneous qualification and quantification of amphetamine-type stimulants and cannabinoids in fingernails. PMID:18563365

  18. A new reliable sample preparation for high throughput focused steroid profiling by gas chromatography-mass spectrometry.

    PubMed

    Anizan, Sébastien; Bichon, Emmanuelle; Monteau, Fabrice; Cesbron, Nora; Antignac, Jean-Philippe; Le Bizec, Bruno

    2010-10-22

    The use of steroid hormones as growth promoters in cattle has been banned within the European Union since 1988 but can still be fraudulently employed in animal breeding farms for anabolic purposes. If an efficient monitoring of synthetic compounds (screening and confirmation) is ensured today by many laboratories, pointing out suspicious samples from a natural steroids abuse remains a tricky challenge due to the difficulty to set relevant threshold levels for these endogenous compounds. The development of focused profiling or untargeted metabolomic approaches is then emerging in this context, with the objective to reveal potential biomarkers signing an exogenous administration of such natural steroids. This study aimed to assess sample preparation procedures based on microextraction and adapt them to high throughput urinary profiling or metabolomic analyses based on gas chromatography-mass spectrometry measurement. Two techniques have been tested and optimised, namely solid phase microextraction (SPME) and microextraction by packed sorbent (MEPS), using five model steroid metabolites (16α-hydroxyandrosterone, 2α-hydroxytestosterone, 11-keto,5β-androstanedione, 6α-hydroxyestradiol and 7β-hydroxypregnenolone). The considered performance criteria included not only the absolute response of the targeted compounds but also the robustness of the materials, and the global aspect of the diagnostic ion chromatograms obtained. After only five successive urinary extractions, a clear degradation of the SPME fiber was observed which led to discard this method as a relevant technique for profiling, whereas no degradation was observed on MEPS sorbent. Repeatability and recovery yields were calculated from urine samples fortified at 500 μg L⁻¹ and extracted by MEPS. They were found respectively below 11% and above 60% for all model compounds. Detection limits were in the 5-15 μg L⁻¹ range depending on the compounds, and a good linearity was observed on the 10-75 μg L⁻¹ range (R² > 0.99). This methodology was applied on urine samples collected from control versus androstenedione-treated bovines, revealing a significant concentration increase for several well-known metabolites such as etiocholanolone, 5α-androstane-3β,17α-diol, 5β-androstane-3α,17α-diol and 5-androstene-3β,17α-diol. Finally, these results allowed to confirm the suitability of the developed strategy and give to this new MEPS application a promising interest in the field of GC-MS based steroid profiling and metabolomic. PMID:20537338

  19. Pressurized liquid extraction-gas chromatography-mass spectrometry analysis of fragrance allergens, musks, phthalates and preservatives in baby wipes.

    PubMed

    Celeiro, Maria; Lamas, J Pablo; Garcia-Jares, Carmen; Llompart, Maria

    2015-03-01

    Baby wipes and wet toilet paper are specific hygiene care daily products used on newborn and children skin. These products may contain complexes mixtures of harmful chemicals. A method based on pressurized liquid extraction (PLE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed for the simultaneous determination of sixty-five chemical compounds (fragrance allergens, preservatives, musks, and phthalates) in wipes and wet toilet paper for children. These compounds are legislated in Europe according Regulation EC No 1223/2009, being twelve of them banned for their use in cosmetics, and one of them, 3-iodo-2-propynyl butylcarbamate (IPBC), is banned in products intended for children under 3 years. Also, propyl-, and butylparaben will be prohibited in leave-on cosmetic products designed for application on the nappy area of children under 3 years from April 2015. PLE is a fast, simple, easily automated technique, which permits to integrate a clean-up step during the extraction process reducing analysis time and stages. The proposed PLE-based procedure was optimized on real non-spiked baby wipe samples by means of experimental design to study the influence on extraction of parameters such as extraction solvent, temperature, extraction time, and sorbent type. Under the selected conditions, the method was validated showing satisfactory linearity, and intra-day, and inter-day precision. Recoveries were between 80-115% for most of the compounds with relative standard deviations (RSD) lower than 15%. Finally, twenty real samples were analyzed. Thirty-six of the target analytes were detected, highlighting the presence of phenoxyethanol in all analyzed samples at high concentration levels (up to 0.8%, 800μgg(-1)). Methyl paraben (MeP), and ethyl paraben (EtP) were found in 40-50% of the samples, and the recently banned isobutyl paraben (iBuP) and isopropyl paraben (iPrP), were detected in one and seven samples, respectively, at concentrations between 0.093 and 247μgg(-1). In the case of phthalates, the forbidden phthalates dibutyl phtalate (DBP) and di(2-ethylhexyl)phthalate (DEHP) were also found in thirteen samples at low levels. All the samples contained fragrance allergens in many cases at high levels (up to 2400μgg(-1)) and three musks were detected in the samples. Excluding the banned compounds, all samples complied with the concentration limits established by the European Regulation although 25% of them did not fulfill the labeling requirements for fragrance allergens. PMID:25662066

  20. Validation of a gas chromatography/mass spectrometry method for the quantification of aerosolized Jet Propellant 8.

    PubMed

    Dietzel, Katherine D; Campbell, Jerry L; Bartlett, Michael G; Witten, Mark L; Fisher, Jeffrey W

    2005-11-01

    Jet Propellant 8 (JP-8) jet fuel is a kerosene-based fuel containing hundreds of hydrocarbons used by the military in NATO countries. Previous rodent inhalation studies carried out with aerosolized JP-8 never evaluated the exposure chamber atmosphere. For this reason, our laboratory developed an analytical method, with an accuracy of better than 80% and precision of better than 20%, for JP-8 aerosol and vapor samples using gas chromatography/mass spectrometry (GC/MS). A method was developed for quantification of selected individual components of JP-8 and for the total amount of JP-8 in aerosolized fuel. A 34 component surrogate hydrocarbon mixture (SHM) was developed and used for simultaneous analysis of the individual components. Three separate runs containing a standard curve and five replicates each at the selected concentrations were analyzed for both the SHM and neat JP-8. The resulting interday accuracy (100-percent relative error) and precision (relative standard deviation) values for the SHM were 86.5% or better and 8.0% or better, respectively. The intraday accuracy and precision values ranged from 99.29% to 84.50% and 0.97% to 12.4%, respectively. For the total amount of JP-8 in aerosol and vapor, the interday accuracy was 83.7% or better and interday precision was 7.0% or better. The intraday accuracy and precision values ranged from 94.8% to 80.4% and 2.4% to 10.5%, respectively. We then used this method to analyze samples collected from an inhalation chamber. From the data obtained, we are able to account for approximately 40-44% of the mass of the aerosol portion and 68-70% of the mass of the vapor portion. The aerosol represented 6-10% of the total mass of the aerosolized JP-8 fuel with the remaining portion being the vapor. From these experiments individual components were identified for further in vivo and in vitro toxicological testing. PMID:16233866

  1. [Feasibility investigation of hydrogen instead of helium as carrier gas in the determination of five organophosphorus pesticides by gas chromatography-mass spectrometry].

    PubMed

    Liu, Zhenxue; Zhou, Shixue

    2015-01-01

    Helium is almost the only choosable carrier gas used in gas chromatography-mass spectrometry (GC-MS). A mixed standard solution of five organophosphorus pesticides was analyzed by using GC-MS, and hydrogen or helium as carrier gas, so as to study the feasibility of hydrogen instead of helium as carrier gas for the determination of organophosphorus pesticides. Combining a mass spectrum database built by ourselves, the results were deconvolved and identified by Automated Mass Spectral Deconvolution & Identification System (AMDIS32), a software belonging to the workstation of the instrument. Then, the statistical software, IBM SPSS Statistics 19.0 was used for the clustering analysis of the data. The results indicated that when hydrogen was used as carrier gas, the peaks of the pesticides detected were slightly earlier than those when helium used as carrier gas, but the resolutions of the chromatographic peaks were lower, and the fraction good indices (Frac. Good) were lower, too. When hydrogen was used as carrier gas, the signals of the pesticides were unstable, the measuring accuracies of the pesticides were reduced too, and even more, some compounds were undetectable. Therefore, considering the measuring accuracy, the signal stability, and the safety, etc., hydrogen should be cautiously used as carrier gas in the determination of organophosphorus pesticides by GC-MS. PMID:25958668

  2. Determination of alkyl anilines and alkyl pyridines in solvent refined coal distillates and aqueous extracts by gas chromatography/mass spectrometry

    SciTech Connect

    Felice, L.T.

    1982-05-01

    Derivatization with acetic anhydride in aqueous media coupled with capillary gas chromatography/mass spectrometry was used to distinguish alkyl anilines from alkyl pyridines. By use of this approach aniline, C-1 anilines, and C-2 anilines, as well as lesser quantities of C-2 pyridines and C-3 pyridines, were positively identified in a solvent refined coal (SRC-II) blended distillate and in an aqueous extract of the distillate. The extraction procedure and acetylation conditions employed were examined in detail and found suitable for quantitative analysis when combined with capillary gas chromatography.

  3. Analysis of pharmaceutical and other organic wastewater compounds in filtered and unfiltered water samples by gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Zaugg, Steven D.; Phillips, Patrick; Smith, Steven G.

    2014-01-01

    Research on the effects of exposure of stream biota to complex mixtures of pharmaceuticals and other organic compounds associated with wastewater requires the development of additional analytical capabilities for these compounds in water samples. Two gas chromatography/mass spectrometry (GC/MS) analytical methods used at the U.S. Geological Survey National Water Quality Laboratory (NWQL) to analyze organic compounds associated with wastewater were adapted to include additional pharmaceutical and other organic compounds beginning in 2009. This report includes a description of method performance for 42 additional compounds for the filtered-water method (hereafter referred to as the filtered method) and 46 additional compounds for the unfiltered-water method (hereafter referred to as the unfiltered method). The method performance for the filtered method described in this report has been published for seven of these compounds; however, the addition of several other compounds to the filtered method and the addition of the compounds to the unfiltered method resulted in the need to document method performance for both of the modified methods. Most of these added compounds are pharmaceuticals or pharmaceutical degradates, although two nonpharmaceutical compounds are included in each method. The main pharmaceutical compound classes added to the two modified methods include muscle relaxants, opiates, analgesics, and sedatives. These types of compounds were added to the original filtered and unfiltered methods largely in response to the tentative identification of a wide range of pharmaceutical and other organic compounds in samples collected from wastewater-treatment plants. Filtered water samples are extracted by vacuum through disposable solid-phase cartridges that contain modified polystyrene-divinylbenzene resin. Unfiltered samples are extracted by using continuous liquid-liquid extraction with dichloromethane. The compounds of interest for filtered and unfiltered sample types were determined by use of the capillary-column gas chromatography/mass spectrometry. The performance of each method was assessed by using data on recoveries of compounds in fortified surface-water, wastewater, and reagent-water samples. These experiments (referred to as spike experiments) consist of fortifying (or spiking) samples with known amounts of target analytes. Surface-water-spike experiments were performed by using samples obtained from a stream in Colorado (unfiltered method) and a stream in New York (filtered method). Wastewater spike experiments for both the filtered and unfiltered methods were performed by using a treated wastewater obtained from a single wastewater treatment plant in New York. Surface water and wastewater spike experiments were fortified at both low and high concentrations and termed low- and high-level spikes, respectively. Reagent water spikes were assessed in three ways: (1) set spikes, (2) a low-concentration fortification experiment, and (3) a high-concentration fortification experiment. Set spike samples have been determined since 2009, and consist of analysis of fortified reagent water for target compounds included for each group of 10 to18 environmental samples analyzed at the NWQL. The low-concentration and high-concentration reagent spike experiments, by contrast, represent a one-time assessment of method performance. For each spike experiment, mean recoveries ranging from 60 to 130 percent indicate low bias, and relative standard deviations (RSDs) less than ( Of the compounds included in the filtered method, 21 had mean recoveries ranging from 63 to 129 percent for the low-level and high-level surface-water spikes, and had low ()132 percent]. For wastewater spikes, 24 of the compounds included in the filtered method had recoveries ranging from 61 to 130 percent for the low-level and high-level spikes. RSDs were 130 percent) or variable recoveries (RSDs >30 percent) for low-level wastewater spikes, or low recoveries ( Of the compounds included in the unfiltered method, 17 had mean spike recoveries ranging from 74 to 129 percent and RSDs ranging from 5 to 25 percent for low-level and high-level surface water spikes. The remaining compounds had poor mean recoveries (130 percent), or high RSDs (>29 percent) for these spikes. For wastewater, 14 of the compounds included in the unfiltered method had mean recoveries ranging from 62 to 127 percent and RSDs 130 percent), or low mean recoveries (33 percent) for the low-level wastewater spikes. Of the compounds found in wastewater, 24 had mean set spike recoveries ranging from 64 to 104 percent and RSDs Separate method detection limits (MDLs) were computed for surface water and wastewater for both the filtered and unfiltered methods. Filtered method MDLs ranged from 0.007 to 0.14 microgram per liter (μg/L) for the surface water matrix and from 0.004 to 0.62 μg/L for the wastewater matrix. Unfiltered method MDLs ranged from 0.014 to 0.33 μg/L for the surface water matrix and from 0.008 to 0.36 μg/L for the wastewater matrix.

  4. Titan's Organic Aerosols : Molecular Composition And Structure Inferred From Systematic Pyrolysis Gas Chromatography Mass Spectrometry Analysis of Analogues

    NASA Astrophysics Data System (ADS)

    Morisson, Marietta; Szopa, Cyril; Buch, Arnaud; Carrasco, Nathalie; Gautier, Thomas

    2015-04-01

    In spite of numerous studies carried out to characterize the chemical composition of laboratory analogues of Titan aerosols (tholins), their molecular composition as well as their structuration are still little known. If Pyrolysis gas chromatography mass spectrometry (Pyr-GCMS) has been used for years to give clues about this composition, the highly disparate results obtained show that they can be attributed to the analytical conditions used, to differences in the nature of the analogues studied, or both. In order to have a better description of Titan's tholins molecular composition, we led a systematic analysis of these materials by pyr-GCMS, exploring the analytical parameters to estimate the biases this technique can induce. With this aim, we used the PAMPRE experiment, a capacitively coupled RF cold plasma reactor (Szopa et al. 2006), to synthetize tholins with 2%, 5% and 10% of CH4 in N2. The three samples were systematically pyrolyzed in the temperature range 200-600°C with a 100°C step. The evolved gases were then injected into a GC-MS device for molecular identification. This systematic pyr-GC-MS analysis had two major objectives: (i) optimizing all the analytical parameters for the detection of a wide range of compounds and thus a characterization of the tholins composition as comprehensive as possible, and (ii) highlighting the role of the CH4 ratio on the tholins molecular structure. About a hundred of molecules have been identified in the pyrolysis products. Although an identical major pattern of nitriles and ethylene appears clearly for the three samples, some discriminant signatures were highlighted. The samples mainly differ by the number of released compounds. The results show especially an increase in the hydrocarbonaceous chains when the CH4 ratio increases. At the opposite, the formation of poly-nitrogenous compounds seems to be easier for lower CH4 ratios. We also performed a semi-quantitative study on the best represented chemical family in our chromatograms - namely nitriles: the existence of a relation between the quantity of a released compound and its molecular mass is consistent with the quantification of nitriles in the PAMPRE gas phase done by Gautier et al., 2011. Moreover, numerous species are present both in tholins and in the gas phase. That allowed us to make out potential precursors of the solid organic particles. From all these results, we conclude that the optimal pyrolysis temperature for a GC-MS analysis of our tholins is 600°C. This temperature choice results from the best compromise between the number of released compounds, the quality of the signal and the appearance of pyrolysis artefacts. Lastly, thanks to a review of pyr-GCMS studies carried out on Titan tholins since the first work of Khare et al. (1981), we compared all the previous analyses between them and with our own results in order to better understand the differences. References B. N. Khare et al., Icarus, vol. 48, no. 2, pp. 290-297, Nov. 1981. C. Szopa et al., Planet. Space Sci., vol. 54, no. 4, pp. 394-404, Apr. 2006. T. Gautier et al., Icarus, vol. 213, no. 2, pp. 625-635, Jun. 2011.

  5. Chapter 3. Determination of semivolatile organic compounds and polycyclic aromatic hydrocarbons in solids by gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Zaugg, Steven D.; Burkhardt, Mark R.; Burbank, Teresa L.; Olson, Mary C.; Iverson, Jana L.; Schroeder, Michael P.

    2006-01-01

    A method for the determination of 38 polycyclic aromatic hydrocarbons (PAHs) and semivolatile organic compounds in solid samples is described. Samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from the solid sample twice at 13,800 kilopascals; first at 120 degrees Celsius using a water/isopropyl alcohol mixture (50:50, volume-to-volume ratio), and then the sample is extracted at 200 degrees Celsius using a water/isopropyl alcohol mixture (80:20, volume-to-volume ratio). The compounds are isolated using disposable solid-phase extraction (SPE) cartridges containing divinylbenzene-vinylpyrrolidone copolymer resin. The cartridges are dried with nitrogen gas, and then sorbed compounds are eluted from the SPE material using a dichloromethane/diethyl ether mixture (80:20, volume-to-volume ratio) and passed through a sodium sulfate/Florisil SPE cartridge to remove residual water and to further clean up the extract. The concentrated extract is solvent exchanged into ethyl acetate and the solvent volume reduced to 0.5 milliliter. Internal standard compounds are added prior to analysis by capillary-column gas chromatography/mass spectrometry. Comparisons of PAH data for 28 sediment samples extracted by Soxhlet and the accelerated solvent extraction (ASE) method described in this report produced similar results. Extraction of PAH compounds from standard reference material using this method also compared favorably with Soxhlet extraction. The recoveries of PAHs less than molecular weight 202 (pyrene or fluoranthene) are higher by up to 20 percent using this ASE method, whereas the recoveries of PAHs greater than or equal to molecular weight 202 are equivalent. This ASE method of sample extraction of solids has advantages over conventional Soxhlet extraction by increasing automation of the extraction process, reducing extraction time, and using less solvent. Extract cleanup also is greatly simplified because SPE replaces commonly used gel permeation chromatography. The performance of the method (as expressed by mean recoveries and mean precision) was determined using Ottawa sand, a commercially available topsoil, and an environmental stream sediment, fortified at 1.5 and 15 micrograms per compound. Recoveries of PAH and semivolatile compounds in Ottawa sand samples fortified at 1.5 micrograms averaged 88 percent ? 9.4 percent relative standard deviation, and calculated initial method detection limits per compound averaged 14 micrograms per kilogram, assuming a 25-gram sample size. The recovery for 1,2,4-trichlorobenzene is less than 60 percent; thus, the concentration of this compound will always be reported as estimated with the E remark code. The analysis of 25 alkylated PAH homolog groups also can be determined with this method with extra data analysis and review, but because of the lack of authentic reference standard compounds, these results are considered to be semiquantitative. The PAH homolog groups are quantitated using the response factor of a parent PAH method compound, if available. Precision data for the alkylated PAH homologs detected in a marine sediment standard reference material (SRM 1944) also are presented to document and demonstrate method capability.

  6. Determination of the chemical composition of titan4s aerosols analogues using pyrolysis gas chromatography mass spectrometry

    NASA Astrophysics Data System (ADS)

    He, J.; Buch, A.; Szopa, C.; Carrasco, N.

    2013-12-01

    The in situ chemical characterization of Titan's aerosols with the ACP-GCMS (Aerosol Collector and Pyrolyze-Gas Chromatograph and Mass Spectrometer) experiments onboard the Cassini-Huygens mission showed that the aerosols heated at 600°C were releasing two main gaseous compounds: NH3 and HCN. To better understand the process of production of these species at high temperature, and their relationship to the solid aerosol composition, it is possible to mimic in laboratory the Titan's atmosphere chemistry to produce analogues of Titan's aerosols (tholins), chemical and physical properties of which can be studied with laboratory instrumentation. In the present work, we studied the thermal decomposition of tholins produced with the PAMPRE cold plasma experiment[1]. For this study, pyrolysis at various temperatures, coupled to gas chromatography mass spectrometry (Pyr-GCMS), has been used in order to understand the origin and formation mechanism of the NH3 and HCN compounds. With this aim, two samples were produced using different initial CH4/N2 gaseous mixtures with different concentration ratios: (5:95) and (10:90). Pyr-GCMS was applied to characterize their chemical composition and molecule structure. In order to study the evolution of chemical compounds released as a function of temperature, the final pyrolysis temperature has been set from 100°C to 900°C with a 100°C step increment. The results show that the major compounds released are similar for the two different studied samples. They include hydrocarbon compounds, nitriles, ammonia, hydrogen cyanide, and some pyrrole isomers. Moreover, whatever the final temperature is, acetonitrile is the most abundant compound released by the samples. At 100°C only water contribution can be detected. Then the number of compounds released increases with the temperature up to 600°C. With the temperature increase the nature of the gaseous species detected does not change significantly. Pyrrole was not detected until the temperature exceeds 600°C for (5:95) sample and 400°C for (10:90) sample. Benzene has also been detected at 800°C for the (5:95) sample and 700°C for (10:90) sample. In the same way, toluene has been detected for the (10:90) sample at 700°C but it has not been detected for the (5:95) sample. This could indicate that carbon percentage is directly related to the benzene and toluene production. HCN and NH3 as the major compounds detected in the ACP instrument were also found in our results. It confirms that the aerosol analogues produced in PAMPRE set-up are among the most similar to Titan's aerosols, as found in [2]. [1] C. Szopa, G. Cernogora, L. Boufendi, et al. : PAMPRE: A dusty plasma experiment for Titan's tholins production and study, Planetary and Space Science, vol. 54, no. 4, pp. 394-404, 2006. [2] P. Coll, R. Navarro-González, C. Szopa, et al. : Can laboratory tholins mimic the chemistry producing Titan's aerosols? A review in light of ACP experimental results, Planetary and Space Science, vol. 77, pp. 91-103, 2013.

  7. Plant- versus microbial signature in densimetric fractions of mediterranean forest soils: a study by thermochemolysis gas chromatography mass spectrometry

    NASA Astrophysics Data System (ADS)

    Rovira, Pere; Grasset, Laurent

    2015-04-01

    Plant- versus microbial signature in densimetric fractions of mediterranean forest soils: a study by thermochemolysis gas chromatography mass spectrometry The ageing of a given organic substrate decomposing in soil is strongly dependant of its microbial utilization and transformation (reworking) by the soil microflora. How far a given substrate or soil fraction has gone in this evolution is usually measured by means of molecular signatures, ratios between organic compounds which enlighten us about the origin and/or the degree of microbial reworking of a specific group of compounds: lipids, proteins, lignin, carbohydrates, etc. Owing to the biochemical heterogeneity of decomposing substrates it is unlikely that the degree of microbial reworking can be approached with a single signature. Applying a couple of them is much better, but obtaining a wide collection of molecular signatures can be time consuming. Here, instead of applying specific methods to obtain a collection of specific signatures, we apply TMAH-thermochemolysis to obtain a panoramic view of the biochemical composition of a series of densimetric fractions of soils. From the compounds identified after TMAH-thermochemolysis, a collection of indicators was obtained: (a) ratio between short and long-chained linear alkanoic acids; (b) ratio between branched and long-chained linear alkanoic acids; (c) ratio between C16 and total alpha-omega-alkanedioic acids; (d) ratio microbial to plant-derived 1-methoxyalkanes; (e) ratio syringyl to total lignin-derived phenolic compounds; (f) vanillic acid to vanillin ratio; (g) fucose/glucose ratio; and (h) xylose/glucose ratio. From these indicators a single numerical value is distilled, allowing to order a couple of densimetric fractions of soil organic matter according to its degree of microbial reworking. This approach was applied to the comparison of a couple of densimetric fractions of soil organic matter of three organic H horizons from mediterranean forest soils. Fractions were obtained by a sequential extraction with sodium polytungstate (NaPT) at density 1.6, 1.8 and 2.0, after ultrasonic disintegration of the sample. Before ultrasonic treatment, a previous extraction was done with NaPT d = 1.6, to isolate the free light fraction. Results were overall consistent in the sense that occluded fractions of density <1.8, and particularly those of density < 1.6, appear as the most microbially evolved. The free light fraction was overall the most fresh-, least evolved fraction. The dense fraction (d > 2.0), made of organomineral complexes with fine silt plus clay, was overall fresh and poorly microbially reworked. Our future work will be the application of this approach to the study of complete soil profiles and soil fractions, thus allowing to obtain a panoramic view of the stabilization of soil organic matter at different depths.

  8. Identification of volatile organic compounds emitted by a naturally aged book using solid-phase microextraction/gas chromatography/mass spectrometry.

    PubMed

    Lattuati-Derieux, Agns; Bonnassies-Termes, Sylvette; Lavdrine, Bertrand

    2004-02-13

    Solid-phase microextraction (SPME) coupled to gas chromatography/mass spectrometry (GC/MS) has been applied to the analysis of volatile organic compounds emitted from a naturally aged groundwood pulp paper originating from an old book in order to access the products produced through the decomposition reactions occurring in paper upon ageing. Two different extraction methods were developed and compared: headspace SPME and contact SPME. The influence of few extraction parameters were tested in order to define the best extraction conditions. An optimised non-destructive contact SPME method was elaborated and allowed the characterisation of more than 50 individual constituents. PMID:14870711

  9. Identification of organic compounds in a mutagenic extract of a surface drinking water by a computerized gas chromatography/mass spectrometry system (gc/ms/com)

    SciTech Connect

    Coleman, W.E.; Melton, R.G.; Kopfler, F.C.; Barone, K.A.; Aurand, T.A.; Jellison, M.G.

    1980-05-01

    Research report: The organics in a Cincinnati drinking water sample were concentrated by a reverse osmosis process. The mutagenic diethyl ether soluble extract of the reverse osmosis concentrate was partitioned into acid and base/neutral fractions. These fractions were analyzed for the presence of organics using a computerized gas chromatography/mass spectrometry system equipped with glass capillary columns. About 460 compounds were identified in the drinking water extract, including 41 polynuclear aromatics, 15 PCB's, and numerous amines, amides, and other halogenated species. (1 diagrams, 4 graphs, 34 references, 1 tables)

  10. Innovative method for carbon dioxide determination in human postmortem cardiac gas samples using headspace-gas chromatography-mass spectrometry and stable labeled isotope as internal standard.

    PubMed

    Varlet, V; Smith, F; de Froidmont, S; Dominguez, A; Rinaldi, A; Augsburger, M; Mangin, P; Grabherr, S

    2013-06-19

    A novel approach to measure carbon dioxide (CO2) in gaseous samples, based on a precise and accurate quantification by (13)CO2 internal standard generated in situ is presented. The main goal of this study was to provide an innovative headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable in the routine determination of CO2. The main drawback of the GC methods discussed in the literature for CO2 measurement is the lack of a specific internal standard necessary to perform quantification. CO2 measurement is still quantified by external calibration without taking into account analytical problems which can often occur considering gaseous samples. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in situ an internal labeled standard gas ((13)CO2) on the basis of the stoichiometric formation of CO2 by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH(13)CO3). This method allows a precise measurement of CO2 concentration and was validated on various human postmortem gas samples in order to study its efficiency. PMID:23746406

  11. Analysis of vinylidene chloride and 1-chlorobutane in foods packaged with polyvinylidene chloride casing films by headspace gas chromatography/mass spectrometry (GC/MS).

    PubMed

    Ohno, H; Kawamura, Y

    2006-08-01

    A headspace gas chromatography/mass spectrometry method was developed for the simultaneous determination of vinylidene chloride and 1-chlorobutane in foods packaged with polyvinylidene chloride casing films. The solid foodstuff was homogenized with an equal mass of distilled water. The homogenate was incubated for 1 h at 90 degrees C in a sealed headspace vial, and the headspace gas was then analysed by gas chromatography/mass spectrometry in selected ion-monitoring mode using a bonded porous polymer-coated capillary column. The recovery rates of vinylidene chloride and 1-chlorobutane in foodstuffs were 94.5-103.9 and 85.8-120.3%, respectively. Among 13 samples tested, vinylidene chloride was detected at 0.001-0.020 microg g(-1) in 11 foodstuffs, and 1-chlorobutane was detected at 0.004-0.040 microg g(-1) in all 13 foodstuffs. Furthermore, vinylidene chloride was detected at 0.04 microg g(-1) in one casing film, and 1-chlorobutane was detected in all casing films. The results indicate that these compounds migrated from the casing films into the foodstuffs. PMID:16807210

  12. Use of greatly-reduced gas flows in flow-modulated comprehensive two-dimensional gas chromatography-mass spectrometry.

    PubMed

    Tranchida, Peter Q; Franchina, Flavio A; Dugo, Paola; Mondello, Luigi

    2014-09-12

    The present research is specifically based on the use of greatly-reduced gas flows, in flow-modulator (FM) comprehensive two-dimensional gas chromatography systems. In particular, focus of the present research is directed to FM devices characterized by an accumulation stage, and a much briefer re-injection step. It has been widely accepted that the operation of such FM systems requires high gas flows (?20mL/min), to re-inject the gas-phase contents of sample (or accumulation) loops, onto the second column. On the contrary, it will be herein demonstrated that much lower gas flows (? 6-8mL/min) can efficiently perform the modulation step of re-injection. The possibility of using such improved operational conditions is given simply by a fine optimization of the processes of accumulation and re-injection. The application of lower gas flows not only means that second-dimension separations are carried out under better analytical conditions, but, even more importantly, greatly reduces problems which arise when using mass spectrometry (i.e., sensitivity and instrumental pumping capacity). PMID:25108766

  13. Determination of breath gas composition of lung cancer patients using gas chromatography/mass spectrometry with monolithic material sorptive extraction.

    PubMed

    Ma, Wen; Gao, Peng; Fan, Jun; Hashi, Yuki; Chen, Zilin

    2015-06-01

    A gas chromatographic-mass spectrometric method with monolithic material sorptive extraction (MMSE) pretreatment was developed to determine the breath gas composition in lung cancer patients. MonoTrap silica monolithic and hybrid adsorbent was selected as the extraction medium during MMSE, given its strong capacity to extract volatile organic compounds (VOC) from exhaled gas. Under the appropriate conditions, high extraction efficiency was achieved. Using the selected ion-monitoring mode, the limit of detection (signal-to-noise ratio 3) for the benzene series was 0.012-2.172?ng?L(-1) . The limit of quantitation (signal-to-noise ratio, 10) was 0.042-7.24?ng?L(-1) . The linearity range of the method was 4-400?ng?L(-1) . Average recovery of the benzene series at lower concentrations was 65-74% (20?ng?L(-1) ). The relative standard deviation of benzene series contents determined within the linear range of detection was <10% of the mean level determined. Our proposed method is simple, rapid and sensitive, and can be competently applied to determine the breath gas composition of lung cancer patients. PMID:25421853

  14. Molecularly imprinted solid-phase extraction for the selective determination of methamphetamine, amphetamine, and methylenedioxyphenylalkylamine designer drugs in human whole blood by gas chromatography-mass spectrometry.

    PubMed

    Kumazawa, Takeshi; Hasegawa, Chika; Hara, Kenji; Uchigasaki, Seisaku; Lee, Xiao-Pen; Seno, Hiroshi; Suzuki, Osamu; Sato, Keizo

    2012-03-01

    A novel method is described for the extraction of methamphetamine, amphetamine, and methylenedioxyphenylalkylamine designer drugs, such as 3,4-methylenedioxy-methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxyethylamphetamine, N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine, and 3,4-(methylenedioxyphenyl)-2-butanamine, from human whole blood using molecularly imprinted solid-phase extraction as highly selective sample clean-up technique. Whole blood samples were diluted with 10 mmol/L ammonium acetate (pH 8.6) and applied to a SupelMIP-Amphetamine molecularly imprinted solid-phase extraction cartridge. The cartridge was then washed to eliminate interferences, and the amphetamines of interest were eluted with formic acid/methanol (1:100, v/v). After derivatization with trifluoroacetic anhydride, the analytes were quantified using gas chromatography-mass spectrometry. Recoveries of the seven amphetamines spiked into whole blood were 89.1-102%. The limits of quantification for each compound in 200 μL of whole blood were between 0.25 and 1.0 ng. The maximum intra- and inter-day coefficients of variation were 9.96 and 13.8%, respectively. The results show that methamphetamine, amphetamine, and methylenedioxyphenylalkyl-amine designer drugs can be efficiently extracted from crude biological samples such as whole blood by molecularly imprinted solid-phase extraction with good reproducibility. This extraction method will be useful for the pretreatment of human samples before gas chromatography-mass spectrometry. PMID:22271670

  15. Characterization of odor-active compounds of various cherry wines by gas chromatography-mass spectrometry, gas chromatography-olfactometry and their correlation with sensory attributes.

    PubMed

    Niu, Yunwei; Zhang, Xiaoming; Xiao, Zuobing; Song, Shiqing; Eric, Karangwa; Jia, Chengsheng; Yu, Haiyan; Zhu, Jiancai

    2011-08-01

    To characterize the aroma of cherry wine, five samples were analyzed by quantitative descriptive sensory analysis, gas chromatography-mass spectrometry (GC-MS) and gas chromatography-olfactometry (GC-O). The aroma of cherry wines was described by 6 sensory terms as fruity, sour, woody, fermentation, cameral and floral. Fifty-one odor-active (OA) compounds were detected by GC-O and quantified by GC-MS, and 45 of them were identified. Twenty-nine OA compounds having more than 50% detection frequency were selected as specific compounds correlated to sensory attributes by partial least squares regression (PLSR). The correlation result showed ethyl 2-methyl propionate, 2,3-butanedione, ethyl butyrate, ethyl pentanoate, 3-methyl-1-butanol, ethyl hexanoate, 3-hydroxy-2-butanone, ethyl lactate, 1-hexanol, (Z)-3-hexen-1-ol, ethyl hydroxyacetate, acetic acid, furfural, 2-ethyl-1-hexanol, benzaldehyde, propanoic acid, butanoic acid, guaiacol, beta-citronellol, hexanoic acid, 2-methoxy-4-methylphenol, 2-ethyl-3-hydroxy-4H-pyran-4-one, ethyl cinnamate, 2-methoxy-4-vinylphenol were typical OA compounds, which covaried with characteristic aroma of cherry wines. PMID:21727038

  16. Evaluation of the matrix effect on gas chromatography - mass spectrometry with carrier gas containing ethylene glycol as an analyte protectant.

    PubMed

    Fujiyoshi, Tomoharu; Ikami, Takahito; Sato, Takashi; Kikukawa, Koji; Kobayashi, Masato; Ito, Hiroshi; Yamamoto, Atsushi

    2016-02-19

    The consequences of matrix effects in GC are a major issue of concern in pesticide residue analysis. The aim of this study was to evaluate the applicability of an analyte protectant generator in pesticide residue analysis using a GC-MS system. The technique is based on continuous introduction of ethylene glycol into the carrier gas. Ethylene glycol as an analyte protectant effectively compensated the matrix effects in agricultural product extracts. All peak intensities were increased by this technique without affecting the GC-MS performance. Calibration curves for ethylene glycol in the GC-MS system with various degrees of pollution were compared and similar response enhancements were observed. This result suggests a convenient multi-residue GC-MS method using an analyte protectant generator instead of the conventional compensation method for matrix-induced response enhancement adding the mixture of analyte protectants into both neat and sample solutions. PMID:26810804

  17. Characterisation of the aroma profiles of different honeys and corresponding flowers using solid-phase microextraction and gas chromatography-mass spectrometry/olfactometry.

    PubMed

    Seisonen, Sirli; Kivima, Evelin; Vene, Kristel

    2015-02-15

    The aroma profiles of thirteen different honey samples from four botanical origins: heather (Calluna vulgaris), raspberry (Rubus idaeus), rape (Brassica napus), alder buckthorn (Frangula alnus) and the blossoms of the four corresponding flowers were investigated to find odour-active compounds exclusively representing specific honeys based on odour-active compounds from the blossoms. Gas-chromatography-mass spectrometry (GC-MS) and gas-chromatography-olfactometry were used to determine and identify the odour-active compounds. Data was analysed using agglomerative hierarchical clustering and correspondence analysis. Honeys from the same botanical origin clustered together; however, none of the identified compounds were exclusive to a particular honey/blossom combination. Heather honey had the flavour profile most different to the others. Isophorone and 2-methylbutyric acid were found only in heather honeys. Heather honey was characterised by having more "sweet" and "candy-like" notes, raspberry honeys had more "green" notes, while alder buckthorn had more "honey" and "floral" notes. PMID:25236195

  18. Determination of alkyl anilines and alkyl pyridines in solvent refined coal distillates and aqueous extracts by gas chromatography/mass spectrometry

    SciTech Connect

    Felice, L.J.

    1982-05-01

    Derivatization with acetic anhydride in aqueous media coupled with capillary gas chromatography/mass spectrometry was used to distinguish alkyl anilines from alkyl pyridines. By use of this approach aniline, C-1 anilines, and C-2 anilines, as well as lesser quantities of C-2 pyridines and C-3 pyridines, were positively identified in a solvent refined coal (SRC)-II blended distallate and in an aqueous extract of the distallate. The extraction procedure and acetylation conditions employed were examined in detail and found suitable for quantitative analysis when combined with capiliary gas chromatography. The SRC-II blended distillate contained 8200-9025 ..mu..g/mL anilines and 1335 ..mu..g/mL pyridines. Distilled water equilibrated with the distillate (1:100, SRC-II:H/sub 2/O) contained 65.9-78.9 ..mu..g/mL anilines and 5.6 ..mu..g/mL pyridines.

  19. Determination of alkyl anilines and alkyl pyridines in solvent refined coal distillates and aqueous extracts by gas chromatography/mass spectrometry

    SciTech Connect

    Felice, L.J.

    1983-05-01

    Derivation with acetic anhydride in aqueous media coupled with capillary gas chromatography mass spectrometry was used to distinguish alkyl anilines from alkyl pyridines. By use of this approach aniline, C-1 anilines, and C-2 anilines, as well as lesser quantities of C-2 pyridines and C-3 pyridines, were positively identified in a solvent refined coal (SRC)-II blended distillate and in an aqueous extract of the distillate. The extraction procedure and acetylation conditions employed were examined in detail and found suitable for quantitative analysis when combined with capillary gas chromatography. The SRC-II blended distillate contained 8200-9025 ..mu..g/mL anilines and 1335 /sup +/g/mL pyridines. Distilled water equilibrated with the distillate (1:100, SRC-II:H/sub 2/O) contained 65.9-78.9 /sup +/g/mL anilines and 5.6 /sup +/g/mL pyridines. 3 figures, 1 table.

  20. Identification of the position and the stereochemistry of the double bond in monounsaturated fatty acid methyl esters by gas chromatography/mass spectrometry of dimethyl disulfide derivatives

    SciTech Connect

    Scribe, P.; Guezennec, J.; Dagaut, J.; Pepe, C.; Saliot, A.

    1988-05-01

    A single-step derivatization procedure using dimethyl disulfide (DMDS) is described for monounsaturated fatty acid esters (MUFAME). The analysis of DMDS adducts by gas chromatography/mass spectrometry is detailed: The mass spectra (electron impact 70 eV) show molecular ions (M/sup +/) and give key fragments that permit determination of the position of the original double bond. Alkylthiolation of Z- and E-MUFAME as a specific antiaddition leads, respectively, to the threo and erythro adducts. The two isomers are well-separated by gas chromatography, permitting precise stereochemistry of the initial double bond. Nevertheless, for a complex environmental mixture of MUFAME, the stereochemical identification is restricted to the linear series. This procedure is suitable for the analysis of trace compounds at the nanogram level such as encountered in the natural environment. An application is presented for the analysis of planktonic and bacterially derived fatty acids in recent marine sediments.

  1. A salting out-acetonitrile homogeneous extraction coupled with gas chromatography-mass spectrometry method for the simultaneous determination of thirteen N-nitrosamines in skin care cosmetics.

    PubMed

    Dong, Hao; Guo, Xindong; Xian, Yanping; Luo, Haiying; Wang, Bin; Wu, Yuluan

    2015-11-27

    A sensitive gas chromatography-mass spectrometry method was established for the simultaneous determination of thirteen N-nitrosamines (NAs) in skin care cosmetics. The cosmetics samples were firstly dispersed by water and subsequently extracted and purified using salting out-acetonitrile homogeneous extraction method. Finally, the extracting solution was concentrated by slow nitrogen gas blowing. All of the samples were separated by INNOWAX capillary chromatographic column, and detected by selected ion monitoring (SIM) mode of gas chromatography-mass spectrometry (GC-MS) and quantified by isotope internal standard method. The method was validated for linearity and range, accuracy, precision and sensitivity. Under the optimized condition, the calibration curves were linear over the selected concentration ranges of 2-500?g/L for all the thirteen analytes, with calculated coefficients of determination (R(2)) of greater than 0.996. The limits of detection (LODs) and the limits of quantitation (LOQs) of the method were 3-15?g/kg and 10-50?g/kg, respectively. Recoveries were calculated at three levels of concentration spiked in two kinds of cosmetics (skin care cream and water). The values were found between 93.8% and 121.0% with relative standard deviation (RSD) values of 2.5-7.2% for intra-day precision (n=6) and 3.3-6.7% for inter-day precision (n=5). The method was successfully applied to analyze twenty-two cosmetics samples and N-nitrosodimethylamine (NDMA) was detected in one sample with the concentration of 207?g/kg. PMID:26518490

  2. The characterization of eight maceral concentrates by means of Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Nip, Margriet; De Leeuw, J. W.; Schenck, P. A.

    1988-03-01

    In order to study the relationships between the chemical structures of coals, coal macerals and their precursors (plant tissues), eight coal macerals originating from the Yorkshire coal basin (U.K.) were studied by Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry. The samples were selected on the basis of a previous study of a large set of macerals. The macerals were studied in order to relate structural moieties of the macerals, as reflected by their pyrolysis products, to structural elements of their likely precursors, plant tissues. The maceral pyrolysates mainly consist of alkylbenzenes, alkylnaphthalenes, alkylphenols and series of straight-chain alk-l-enes and alkanes over a wide molecular weight range. The relative contribution of the (hydroxy)aromatic pyrolysis products and of the straight-chain alk-l-enes and alkanes to each maceral pyrolysate was calculated, although the internal distribution patterns of the alkyl derivatives of these pyrolysis products exhibited to a certain extent dissimilarities. Differences between the relative contributions of these pyrolysis products to the pyrolysates of different macerals with the same coal rank and to those of similar macerals with different coal rank depend on differences in precursor material and the chemical modification of these precursors upon increasing coalification. Multivariate data treatment by means of factor analysis was chosen to compare the pyrolysis data - represented by these histograms - with the petrographic data and the proximate and ultimate analysis values of the macerals. In addition, similar analyses was performed on the macerals using such a low Curie temperature (358°C), that from some of the macerals "thermal extracts" were obtained, containing a series of n-alkanes and some isoprenoids such as pristane and phytane. Although these thermal extracts represent only a low percentage by weight of the maceral samples, their existence probably will affect both the chemical and physical properties of the macerals, although they are in fact no pan of the coal structure itself.

  3. Gas chromatography-mass spectrometry and high-performance liquid chromotagraphy analysis of the drug absorption characteristics in the buccal mucosa via a circulating device

    PubMed Central

    WU, XIN; LI, YUBO; XU, DAOQING; ZHOU, HONG; WANG, JINLEI; GUO, XUEJUN; ZHANG, YANJUN

    2015-01-01

    The aim of the present study was to investigate the characteristics of Su Xiao Jiu Xin dripping pill absorption in the buccal mucosa of healthy volunteers. This pill is a traditional Chinese medicine that is widely used as an emergency treatment for cardiovascular and cerebrovascular diseases. It is sublingually administered and can be absorbed in the buccal mucosa. In the present study, a method was developed to investigate the absorption characteristics in the buccal mucosa of healthy volunteers via a circulating device by gas chromatography-mass spectrometry and high-performance liquid chromatography. The five main efficacy components associated with cardiovascular and cerebrovascular diseases, which are borneol, isoborneol, ligustilide, n-butylphthalide and ferulic acid, were detected and rapidly absorbed. Among these components, four exhibited good absorption, thus confirming that the method developed is efficient for analysis of the absoption characteristics. PMID:25469246

  4. Preparation of durable graphene-bonded titanium fibers for efficient microextraction of phthalates from aqueous matrices and analysis with gas chromatography-mass spectrometry.

    PubMed

    Zhang, Bo-Tao; Li, Hai-Fang; Zheng, Xiaoxia; Teng, Yanguo; Liu, Yan; Lin, Jin-Ming

    2014-11-28

    A solid-phase microextraction fiber (SPME) was synthesized for pre-concentration of 15 phthalates from aqueous samples. Graphene oxide was immobilized on Ti wire with titanol groups using a cross-linking agent and subsequently reduced to yield a folded and wrinkled graphene coating. This graphene-Ti fiber demonstrated durable mechanical robustness and enhanced stability for more than 200 extraction cycles due to the Ti substrate and chemical bond. The extraction efficiencies reached highest when the graphene layers were four and their performances were superior to commercial SPME fibers. The prepared fiber was used for pre-concentration of phthalates from aqueous samples by direct immersion extraction and thermal desorption for gas chromatography-mass spectrometry analysis. The method was utilized for the simultaneous analysis of 15 phthalates with satisfactory recoveries in the range of 82.8-97.8% for bottled water and 73.3-102.0% for intravenous drips in plastic packaging. PMID:25454125

  5. Direct chemical-analysis of uv laser-ablation products of organic polymers by using selective ion monitoring mode in gas-chromatography mass-spectrometry

    USGS Publications Warehouse

    Cho, Yirang; Lee, H.W.; Fountain, S.T.; Lubman, D.M.

    1994-01-01

    Trace quantities of laser ablated organic polymers were analyzed by using commercial capillary column gas chromatography/mass spectrometry; the instrument was modified so that the laser ablation products could be introduced into the capillary column directly and the constituents of each peak in the chromatogram were identified by using a mass spectrometer. The present study takes advantage of the selective ion monitoring mode for significantly improving the sensitivity of the mass spectrometer as a detector, which is critical in analyzing the trace quantities and confirming the presence or absence of the species of interest in laser ablated polymers. The initial composition of the laser ablated polymers was obtained by using an electron impact reflectron time-of-flight mass spectrometer and the possible structure of the fragments observed in the spectra was proposed based on the structure of the polymers.

  6. A quasi non-destructive approach for amber geological provenance assessment based on head space solid-phase microextraction gas chromatography-mass spectrometry.

    PubMed

    van der Werf, I D; Aresta, A; Truic?, G I; Radu, G L; Palmisano, F; Sabbatini, L

    2014-02-01

    Head space (HS) solid-phase micro-extraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) was used to analyze the volatile fraction of ambers of different geological origin. In particular, Romanian (romanite) and Baltic (succinite) amber samples were studied. Both types of amber have nearly similar bulk chemical compositions and could probably reflect only some differences of paleobiological and/or diagenetic origin. The present study shows that amber head space fingerprint, obtained by SPME/GC-MS, can provide a simple and quasi non-destructive method capable of romanite/succinite differentiation. Among the numerous compounds present in the head space, a number of few informative variables could be selected that were able to differentiate the ambers as demonstrated by Principal Component and Cluster Analysis. PMID:24401437

  7. Determination of musty-odor compounds in water by gas chromatography-mass spectrometry with a needle-type sample-preparation device.

    PubMed

    Ueta, Ikuo; Mitsumori, Tomoki; Kawakubo, Susumu; Saito, Yoshihiro

    2014-01-01

    The musty-odor compounds (MOCs) 2-methylisoborneol (2-MIB) and geosmin in water samples were determined by a purge-and-trap method using a needle-type extraction device followed by gas chromatography-mass spectrometry. For the extraction of these compounds, a triple-layer-type extraction needle containing divinylbenzene and activated carbon particles as the particulate extraction media was introduced. Several experimental parameters, including the sample temperature during extraction, the addition of sodium chloride, and desorption conditions, were thoroughly optimized in this study. The detection limits for 2-MIB and geosmin were 1.0 and 0.5 ng L(-1), respectively. The method was successfully applied to the simultaneous determination of MOCs and other volatile organic compounds in tap-water samples. PMID:25312628

  8. Identification of polar organic compounds in coal-gasification condensate water by gas chromatography-mass spectrometry analysis of high-performance liquid chromatography fractions

    SciTech Connect

    Mohr, D.H.; King, C.J.

    1985-10-01

    A novel combination of analytical techniques was employed to identify polar organic compounds, including the first report of hydantoins, in condensate waters from a slagging fixed-bed coal-gasification process. The analytical technique consists of high-performance liquid chromatography (HPLC) separation and gas chromatography-mass spectrometry (GC-MS) analysis of HPLC fractions. Entrainer distillation was used to concentrate the HPLC fractions and remove water before GC-MS analysis. Analyses of four samples accounted for 69-84% of the measured chemical oxygen demand (COD), including 1-6% of the COD as dimethylhydantoin. This compound is highly polar and difficult to remove by solvent extraction. Other identified compounds included phenols, di-hydroxybenzenes, methanol, acetone, and acetonitrile. Many of the unidentified compounds (16-31% of the COD) were difficult to extract, had low volatility relative to water, and contained organic nitrogen. Some chemical changes were observed during storage of condensate water samples.

  9. Metabolomic profiling of human follicular fluid from patients with repeated failure of in vitro fertilization using gas chromatography/mass spectrometry

    PubMed Central

    Xia, Lan; Zhao, Xiaoming; Sun, Yun; Hong, Yan; Gao, Yuping; Hu, Shuanggang

    2014-01-01

    Objective: To establish a gas chromatography/mass spectrometry (GC/MS)-based metabolomics method to compare the metabolites in the follicular fluid (FF) from patients with in vitro fertilization (IVF) and repeated IVF failure (RIF). Methods: A prospective study was employed in Center for Reprodutive Medcine, Renji Hospital, Shanghai, China, between January and October 2010. FF samples were collected from 13 patients with RIF and 15 patients who achieved pregnancy after the first IVF cycle. Results: Partial least squares (PLS) discriminant analysis of the PCA data revealed that the samples were scattered into two different regions. FF from the two groups differed with respect to 20 metabolites. FF from RIF group showed elevated levels of several amino acids (valine, threonine, isoleucine, cysteine, serine, proline, alanine, phenylalanine, lysine, methionine and ornithine), and reduced levels of dicarboxylic acids, cholesterol and some organic acids. Conclusions: The studies corroborated successful determination of the levels of metabolite in the FF. PMID:25400819

  10. Biosynthesis of Gold Nanoparticles and Identification of Capping Agent Using Gas Chromatography-Mass Spectrometry and Matrix Assisted Laser Desorption Ionization-Mass Spectrometry.

    PubMed

    Karthick, V; Kumar, V Ganesh; Dhas, T Stalin; Govindaraju, K; Sinha, Sweta; Singaravelu, G

    2015-06-01

    In the present study, gold nanoparticles (AuNPs) were synthesized using leaf extract of Syzygium jambolanum and capping agent has been explored. The synthesized AuNPs have been characterized using UV-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR), high resolution transmission electron microscopy (HRTEM) and atomic force microscopic (AFM) analysis. The AuNPs show intense surface plasmon resonance (SPR) band at 528 nm and were found to be spherical and hexagonal in shape with particle size ranging from 20-30 nm. Transmission electron microscopy and atomic force microscopy were used to analyze the surface morphology of synthesized AuNPs. The capping ligand has been evaluated using matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) and gas chromatography-mass spectrometry (GC-MS) analysis. PMID:26369012

  11. Determination of volatile organic contaminants in bulk oils (edible, injectable, and other internal medicinal) by purge-and-trap gas chromatography/mass spectrometry

    SciTech Connect

    Thompson, D.W.

    1994-05-01

    Purge-and-trap gas chromatography/mass spectrometry is evaluated for the quantitation of part-per-billion levels of volatile organic contaminants in bulk vegetable oils. Results using 2 purge techniques (direct purging of the heated oil and purging after dispersing the oil on an aluminum oxide powder) and 2 quantitative methods (standard curve and deuterium-labeled internal standard addition) are reported. Twenty volatile compounds and 8 vegetable oils were investigated. Recovery data and estimated detection limits for each compound are reported for each purge technique. Generally acceptable recoveries (70-130% for more than 90% of the analyte spikes) and acceptable detection levels (approximately 4-10 ppb) were obtained for all compounds using either the external standard curve of the deuterium-isotope-labeled internal standard. The use of a dispersant (such as alumina) for sample purging resulted in poor recoveries of the highly volatile contaminants. 16 refs., 3 figs., 4 tabs.

  12. Gas chromatography-mass spectrometric analysis of products from on-line pyrolysis/silylation of plant gums used as binding media

    NASA Astrophysics Data System (ADS)

    Chiantore, Oscar; Riedo, Chiara; Scalarone, Dominique

    2009-07-01

    Plant gums are complex polysaccharides used in the field of cultural heritage especially as binding media. Classification of polysaccharides may be achieved on the basis of monosaccharides composition after cleavage of glycosidic bond. Characterization of plant gums in works of art is complicated by the necessity of to use a method minimally invasive and requiring a small mount of sample. Pyrolisys is an useful method to obtain polysaccharides decomposition and generally pyrolysis products can be identified by the use of gas chromatography-mass spectrometry. This paper describes a method where two plant gums, arabic and tragacanth, were pyrolized in presence of silylating agents (HMDS e BSTFA alone and with TMCS as catalyst) using an on-line Py-GC/MS apparatus. Some characteristic trimethylsilyl derivatives of monosaccharides were identified on the basis of mass spectra. The presence of characteristic pyrolysis products of sugars allows to distinguish the two gums.

  13. Determination of stable isotopic enrichment and concentration of glycerol in plasma via gas chromatography-mass spectrometry for the estimation of lipolysis in vivo.

    PubMed

    Flakoll, P J; Zheng, M; Vaughan, S; Borel, M J

    2000-07-01

    Measuring glycerol's rate of appearance into the plasma compartment provides an excellent estimation of whole-body lipolysis. The glycerol rate of appearance can be calculated by estimating the plasma dilution of continuously infused stable or radioactive isotopes of glycerol. Previously, determination of glycerol stable isotopic enrichment has required either chemical ionization gas chromatography-mass spectrometry (GC-MS) or electron impact ionization GC-MS in which a fragment containing only a portion of the glycerol molecule was measured. The present method uses tert.-butyldimethylsilyl (tBDMS) derivatization and electron impact ionization to measure a fragment including the entire glycerol molecule. The method determines concentration and enrichment of plasma glycerol in a simple, precise, and cost-efficient manner, providing a basis from which lipid homeostasis can be assessed. PMID:10985565

  14. Microwave distillation followed by headspace single drop microextraction coupled to gas chromatography-mass spectrometry (GC-MS) for fast analysis of volatile components of Echinophora platyloba DC.

    PubMed

    Gholivand, Mohammad Bagher; Abolghasemi, Mir Mahdi; Piryaei, Marzieh; Maassoumi, Sayed Mohammad; Papzan, Abdolhamid

    2013-05-01

    To avoid the traditional and time consuming hydrodistillation, the analyses of volatile components in aerial parts of Echinophora platyloba DC was carried out by a simple microwave distillation followed by headspace single drop microextraction (MD-HS-SDME) coupled to gas chromatography-mass spectrometry (GC-MS). The headspace volatile compounds were collected after irradiation using a single drop of n-heptadecan. The extraction conditions were optimised using the relative peak areas as index. The chemical composition of the MD-HS-SDME extracts was confirmed according to their retention indexes and mass spectra. Fifty-three components were extracted and identified by using the MD-HS-SDME method. E-?-ocimene (53.81%), R-D-decalactone (12.75%), ?-pinene (6.43%), n-heptanol (6.27%), ?-phellanderne (2.70%) and linalool (1.89%) were the major constituents. PMID:23265484

  15. Determination of testosterone in plasma from men by gas chromatography/mass spectrometry, with high-resolution selected-ion monitoring and metastable peak monitoring

    SciTech Connect

    Finlay, E.M.; Gaskell, S.J.

    1981-07-01

    Highly specific methods are described for determining testosterone in plasma or serum from men. Extract fractions obtained by selective isolation procedures are converted to tert-butyldimethylsilyl (TBDMS) oximes/TBDMS ethers or methyl oximes/TBDMS ethers and analyzed by gas chromatography/mass spectrometry in the high-resolution selected-ion monitoring or metastable peak-monitoring modes. (2H3)Testosterone and unlabeled 17-epitestosterone are used as the respective internal standards. When we applied the two procedures to analysis of samples of pooled plasma and serum used for external quality assessment of routine assays, the results agreed well. Interlaboratory values for mean concentrations obtained by routine immunoassays (y) consistently exceeded values obtained by our technique (x), although the values closely correlated (r . 0.997; y . 1.008x + 0.564 nmol/L).

  16. SIMPLE AND RAPID ASSAY METHOD FOR SIMULTANEOUS QUANTIFICATION OF URINARY NICOTINE AND COTININE USING MICRO-EXTRACTION BY PACKED SORBENT AND GAS CHROMATOGRAPHY-MASS SPECTROMETRY

    PubMed Central

    IWAI, MASAE; OGAWA, TADASHI; HATTORI, HIDEKI; ZAITSU, KEI; ISHII, AKIRA; SUZUKI, OSAMU; SENO, HIROSHI

    2013-01-01

    ABSTRACT A simple and rapid method for determination of nicotine and cotinine levels in urine was developed using samples prepared by micro-extraction by packed sorbent (MEPS) and subjected to gas chromatography-mass spectrometry (GC-MS) analysis. This method provided good reproducibility, as well as good linearity of calibration curves in the range of 1100 and 501000 ng/mL for quality control samples spiked with nicotine and cotinine, respectively. The detection limit of nicotine and cotinine was as low as 0.25 and 20 ng/mL, respectively. An evaporation procedure is not suitable for nicotine determination, thus an advantage of the present MEPS assay method is direct testing with GC-MS without the need for evaporation to a dry solvent. Our findings show that it may be useful for determining nicotine levels in various types of research studies. PMID:24640182

  17. Simultaneous determination of anabolic steroids and synthetic hormones in meat by freezing-lipid filtration, solid-phase extraction and gas chromatography-mass spectrometry.

    PubMed

    Seo, Jungju; Kim, Hye-Young; Chung, Bong Chul; Hong, Jongki

    2005-03-01

    Estradiol, testosterone, progesterone, zeranol and diethylstilbestrol including estradiol metabolites were determined simultaneously in meat. Extraction of growth hormones was carried out by ultasonication using a methanol-water mixture. The growth hormones in the meat extract can be effectively separated from lipids by freezing-lipid filtration, followed by C8-solid phase extraction (SPE). During freezing-lipid filtration, about 90% of lipids are removed without any significant loss of growth hormones. For further clean-up, silica- and aminopropyl-SPE were used. To enhance detection sensitivity, the growth hormones are derivatized with trimethylsilyl reagents. Quantitation using isotope-labelled internal standards was performed by gas chromatography-mass spectrometry in the selected ion monitoring mode. The method detection limits were 0.1-0.4 microg/kg for all growth hormones. Overall recoveries of synthetic and natural growth hormones were 68-106% with coefficients of variation of 5-16% for the complete procedure. PMID:15844536

  18. Coordinating fingerprint determination of solid-phase microextraction/gas chromatography-mass spectrometry and chemometric methods for quality control of oxidized tallow.

    PubMed

    Song, Shiqing; Zhang, Xiaoming; Hayat, Khizar; Xiao, Zuobing; Niu, Yunwei; Eric, Karangwa

    2013-02-22

    Based on optimized solid-phase microextraction/gas chromatography-mass spectrometry (SPME/GC-MS) and chemometric methods, simple, reliable and reproducible methods were described for the first time for developing a chromatographic fingerprint of oxidized tallow. Eight optimal oxidized tallow samples were used to establish the chromatographic fingerprint. Spectral correlative chromatogram was adopted to identify 33 "common components". The validation of fingerprint analysis was performed based on the relative retention time, the relative peak area of common peaks, sample stability and similarity analysis. The correlation coefficient of similarity of eight optimal oxidized tallow samples was more than 0.962, which showed that samples from different batches were consistent to some extent in spite of slightly different chemical indexes. Through principal component analysis (PCA), 14 constituents were further screened out to be the main chemical markers, which could be applied to more accurate quantitative discrimination and quality control of oxidized tallow. PMID:23332870

  19. Study of the precision in the purge-and-trap-gas chromatography-mass spectrometry analysis of volatile compounds in honey.

    PubMed

    Soria, Ana Cristina; Martínez-Castro, Isabel; Sanz, Jesús

    2009-04-10

    Data precision in the analysis by purge-and-trap coupled on-line to gas chromatography-mass spectrometry (P&T-GC-MS) of honey volatiles has been studied by statistical analysis. The contribution of non-random factors to dispersion of quantitative results was proven by comparing several statistical parameters (correlation coefficients, principal component analysis (PCA) eigenvalues and loadings) from both experimental and simulated data. PCA was also useful for grouping volatiles with similar dispersion behaviour; these groups being generally related to compounds with common properties or structural features. The use of area ratios improves data precision for compounds within the same group. Results from this study could be used for a better selection of internal standards in quantitative analysis of volatiles by P&T-GC-MS. PMID:19203763

  20. Monitoring pesticide residues in greenhouse tomato by combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by gas-chromatography-mass spectrometry.

    PubMed

    Melo, Armindo; Cunha, Sara C; Mansilha, Catarina; Aguiar, Ana; Pinho, Olvia; Ferreira, Isabel M P L V O

    2012-12-01

    A multiclass and multiresidue method for pesticide analysis in tomato was validated. Extraction and pre-concentration of the pesticide residues from acetonitrile extracts was performed by using dispersive liquid-liquid microextraction (DLLME) technique, followed by gas chromatography-mass detection. DLLME was performed using carbon tetrachloride as extractive solvent and acetonitrile extract as dispersive solvent, in order to increase enrichment factor of the extraction procedure. Validation parameters indicated the suitability of the method for routine analyses of thirty pesticides in a large number of samples. In general, pesticide recoveries ranged between 70% and 110% and repeatability ranged between 1% and 20%. The proposed method was applied to the monitoring of pesticides in tomatoes grown during winter in greenhouses. Among the compounds considered in this work, cyprodinil was found in tomato at concentrations of 0.33mg/kg, other pesticides like azoxystrobin, fenhexanid, tolyfluanid, ?-cyhalothrin and trifloxystrobin were also detected, but, not quantified. PMID:22953826

  1. Triclosan and methyl-triclosan monitoring study in the northeast of Spain using a magnetic particle enzyme immunoassay and confirmatory analysis by gas chromatography mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kantiani, Lina; Farr, Marinella; Asperger, Danijela; Rubio, Fernando; Gonzlez, Susana; Lpez de Alda, Maria J.; Petrovi?, Mira; Shelver, Weilin L.; Barcel, Dami

    2008-10-01

    SummaryFor the first time, the occurrence of triclosan and its metabolite methyl-triclosan was investigated in a typical Mediterranean area using a two-step methodology based on screening using a magnetic particle immunoassay (IA) and confirmatory analysis by solid phase extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS). In this study, 95 environmental samples were analyzed. A commercial immunoassay was assessed for use in the different types of water selected for this study. A large monitoring study was performed on the influent and the effluent of eight wastewater treatment plants (WWTPs), water samples from Ebro and Llobregat rivers, and drinking water. All wastewater samples tested in this study (influents and effluents) showed the presence of triclosan, with concentrations for raw influents being high (10 ?g/L as average value). The percentages of triclosan removal for the WWTPs were evaluated (30-70%) along the different treatment processes showing that the best removal rates were obtained by the processes equipped with membrane bioreactors (MBRs). However, important concentrations of triclosan were detected even after treatment by MBRs. The presence of this biocide was confirmed in 50% of the river samples analyzed. Twenty two drinking water samples from the Barcelona city area were investigated, and in this case no triclosan was detected. Due to its properties and the widespread usage of triclosan, there is a need for monitoring and controlling the amounts present in wastewater effluents, river water, drinking water catchments areas, and drinking water. To this end, we present a feasible methodology using a magnetic particle-based immunoassay as a screening, followed by confirmatory analysis using solid phase extraction-gas chromatography-mass spectrometry (SPE-GC-MS).

  2. Molecularly imprinted solid phase extraction for simultaneous determination of ?9-tetrahydrocannabinol and its main metabolites by gas chromatography-mass spectrometry in urine samples.

    PubMed

    Nesti?, Marina; Babi?, Sandra; Pavlovi?, Dragana Mutavdi?; Sutlovi?, Davorka

    2013-09-10

    In presented paper analytical method based on solid-phase extraction using molecularly imprinted polymer and gas chromatography-mass spectrometry has been developed and validated for the confirmation of THC, THC-OH and THC-COOH in urine samples. Non-covalent molecularly imprinted polymers of THC-OH were prepared using different functional monomers (methacrylic acid, 4-vinylpyridine, and 2-hydroxyethyl methacrylate), ethylene glycol dimethacrylate as a cross-linker and 2,2'-azobis-isobutyronitrile as an initiator of radical polymerization. Analytes were extracted from urine samples using prepared polymer sorbent with highest binding selectivity and capability. Before extraction, urine samples were hydrolyzed with alkaline. Elution was performed with chloroform:ethyl acetate (60:40, v/v). Dry extracts were silylated with BSTFA+1% TMCS. Detection and quantification were performed using gas chromatography-mass spectrometry in single ion recording mode. The developed method was linear over the range from LOQ to 150 ng mL(-1) for all three analytes. For THC, THC-OH and THC-COOH LOD was 2.5, 1 and 1 ng mL(-1), and LOQ was 3, 2 and 2 ng mL(-1), respectively. The precision, accuracy, recovery and matrix effect were investigated at 5, 25 and 50 ng mL(-1). In the investigated concentration range recoveries were 71.9% for THC, 78.6% for THC-OH and 75.2% for THC-COOH. Matrix effect was not significant (<10%) for all analytes in the concentration range from 5 ng mL(-1) to 50 ng mL(-1). Extraction recovery on non-imprinted polymer was relatively high indicating high non-specific binding. Optimized and validated method was applied to 15 post-mortem urine samples. PMID:23890655

  3. Pyrolysis-gas chromatography/mass spectrometry of a coal extract and its fractions separated by planar chromatography: correlation of structural features with molecular mass

    PubMed

    Islas; Suelves; Carter; Herod; Kandiyoti

    2000-01-01

    The structural characterisation of a coal liquefaction extract and its three fractions separated by planar chromatography has been described. Size exclusion chromatography showed the molecular mass distributions to become progressively larger with decreasing mobility on the plate. UV-fluorescence spectroscopy of the fractions indicated parallel increases in the sizes of polynuclear aromatic ring systems. Analysis by probe-mass spectrometry of the 'whole' coal extract showed the expected array of small polynuclear aromatic groups extending to m/z 450. The probe mass spectra of the lightest fraction ('mobile in pyridine and acetonitrile') showed similar features, except for effects due to vacuum drying to remove solvent. In sharp contrast, the two heaviest fractions ('mobile in pyridine and immobile in acetonitrile' and 'immobile in pyridine') showed no significant ions other than those from residual NMP solvent (m/z 98 and 99). Pyrolysis-gas chromatography/mass spectrometry of these two heaviest fractions showed only traces of aromatic compounds or fragments. The aromatic pyrolysis products of these fractions were too large and involatile to pass through the GC column. The major components observed in the pyrolysis-gas chromatography/mass spectrometry of the two heavy fractions were alkanes and alkenes, ranging between C10-C25. Since none of the samples contained free alkanes, alkenes or cycloalkanes before pyrolysis, they were generated during the pyrolysis step. The shifts of UV-fluorescence spectral intensity to shorter wavelengths with decreasing size indicated by size exclusion chromatography (SEC) provide direct evidence of differences in structure with changing molecular mass. This evidence strongly suggests that species identified as being of large molecular mass in this extract sample are not composed of molecular aggregates. It remains difficult to establish whether and when it would be legitimate to invoke molecular aggregates to explain the large molecular masses (MMs) identified here and in other work. Copyright 2000 John Wiley & Sons, Ltd. PMID:11006584

  4. Fast determination of octinoxate and oxybenzone uv filters in swimming pool waters by gas chromatography/mass spectrometry after solid-phase microextraction.

    PubMed

    Y?lmazcan, ; Kanakaki, C; Izgi, B; Rosenberg, E

    2015-07-01

    A fast gas chromatography/mass spectrometry method was developed and validated for the analysis of the potential endocrine disrupters octinoxate and oxybenzone in swimming pool water samples based on the solvent-free solid-phase microextraction technique. The low-pressure gas chromatography/mass spectrometry method used for the fast identification of UV filter substances was compared to a conventional method in terms of sensitivity and speed. The fast method proposed resulted in 2 min runs, leading to an eightfold decrease in the total analysis time and a sevenfold improvement in detection limits. The main parameters affecting the solid-phase microextraction process were also studied in detail and the optimized conditions were as follows: fiber coating, polyacrylate; extraction mode, direct immersion; extraction temperature, 25C; sample volume, 5 mL; extraction time 45 min; pH 6.5. Under the optimized conditions, a linear response was obtained in the concentration range of 0.5-25 ?g/L with correlation coefficients in the range 0.990-0.999. The limits of detection were 0.17-0.29 ?g/L, and the recoveries were 80-83%. Combined method uncertainty was assessed and found to be less than 7% for both analytes for concentrations equal to or higher than 5 ?g/L. Pool water samples were analyzed to demonstrate the applicability of the proposed method. Neither octinoxate nor oxybenzone were detected in the swimming pool water samples at concentrations above the respective limits of detection. PMID:25931007

  5. Polycyclic aromatic hydrocarbon emissions in diesel exhaust using gas chromatography-mass spectrometry with programmed temperature vaporization and large volume injection

    NASA Astrophysics Data System (ADS)

    Vieira de Souza, Carolina; Corrêa, Sergio Machado

    2015-02-01

    Diesel engines are significant sources of Polycyclic Aromatic Compounds (PAHs) in urban atmospheres. These compounds are widely known for their carcinogenic potential and mutagenic properties. In this study, a method was developed for the analysis of 16 priorities PAHs using gas chromatography-mass spectrometry (GC-MS) with programmable temperature vaporizer large volume injection (PTV-LVI), which allowed to be obtained detection limits below 2.0 ng mL-1. This method was evaluated in samples from stratified particulate matter and gas phase from the emissions of diesel vehicle employing diesel commercial S10 (sulfur 10 mg L-1) and B5 (biodiesel 5% v/v). A sampling system that does not employ exhaust products dilution was used to evaluate the PAHs gas-particle partition. Six PAHs were identified in extracts and gas-phase PAHs took percentage of 80% in the total PAHs emissions. The sampling system without dilution not caused a strong nucleation/condensation of the most volatile PAHs. PAHs size-particle distribution was found in higher levels in the accumulation mode.

  6. ON SITE SOLID-PHASE EXTRACTION AND LABORATORY ANALYSIS OF ULTRA-TRACE SYNTHETIC MUSKS IN MUNICIPAL SEWAGE EFFLUENT USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY. FULL-SCAN MODE

    EPA Science Inventory

    Fragrance materials such as synthetic musks in aqueous samples, are normally determined by gas chromatography/mass spectrometry in the selected ion monitoring (SIM) mode to provide maximum sensitivity after liquid-liquid extraction of I -L samples. Full-scan mass spectra are requ...

  7. ON-SITE SOLID-PHASE EXTRACTION AND LABORATORY ANALYSIS OF ULTRA-TRACE SYNTHETIC MUSKS IN MUNICIPAL SEWAGE EFFLUENT USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY IN THE FULL-SCAN MODE

    EPA Science Inventory

    Fragrance materials such as synthetic musks in aqueous samples, are normally determined by gas chromatography/mass spectrometry in the selected ion monitoring (SIM) mode to provide maximum sensitivity after liquid-liquid extraction of I -L samples. Full-scan mass spectra are requ...

  8. A METHOD FOR AUTOMATED ANALYSIS OF 10 ML WATER SAMPLES CONTAINING ACIDIC, BASIC, AND NEUTRAL SEMIVOLATILE COMPOUNDS LISTED IN USEPA METHOD 8270 BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GAS CHROMATOGRAPHY/MASS SPECTROMETRY

    EPA Science Inventory

    Data is presented showing the progress made towards the development of a new automated system combining solid phase extraction (SPE) with gas chromatography/mass spectrometry for the single run analysis of water samples containing a broad range of acid, base and neutral compounds...

  9. Identification of Bound Nitro Musk-Protein Adduct in Fish Liver By Gas Chromatography-Mass Sectrometry: Biotransformation, Dose-Response and Toxicokinetics of Nitro Musk Metabolites Protein Adducts in Trout Liver as Biomarker of Exposure

    EPA Science Inventory

    Ubiquitous occurrences of synthetic nitro musks are evident in the literature. The In vivo analysis of musk xylene (MX) and musk ketone (MK) - protein adducts in trout liver have been performed by gas chromatography-mass spectrometry using selected ion monitoring (GC-SIM-MS). Bio...

  10. NHEXAS PHASE I REGION 5 STUDY--STANDARD OPERATING PROCEDURE--ANALYSIS OF VOLATILE ORGANIC COMPOUNDS FROM CHARCOAL BADGES BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (RTI/ACS-AP-209-112)

    EPA Science Inventory

    This protocol provides guidelines for determining volatile organic hydrocarbons (VOCs) in air samples by gas chromatography/mass spectrometry (GC/MS). This method is for the analysis of VOCs in air by GC/MS in the selected ion monitoring mode (SIM). Charcoal badge samplers are ex...

  11. Identification of odorants in frankincense (Boswellia sacra Flueck.) by aroma extract dilution analysis and two-dimensional gas chromatography-mass spectrometry/olfactometry.

    PubMed

    Niebler, Johannes; Buettner, Andrea

    2015-01-01

    Frankincense has been known, traded and used throughout the ages for its exceptional aroma properties, and is still commonly used in both secular and religious settings to convey a pleasant odor. Surprisingly, the odoriferous principle(s) underlying its unique odor profile have never been published. In this study, resin samples of Boswellia sacra Flueck. from both Somalia and Oman were investigated by aroma extract dilution analysis. In a comprehensive, odor-activity guided approach both chemo-analytical and human-sensory parameters were used to identify odor active constituents of the volatile fraction of B. sacra. Among the key odorants found were ?-pinene, ?-myrcene, linalool, p-cresol and two unidentified sesquiterpenoids. Overall, a total of 23 odorants were detected and analyzed by gas chromatography-olfactometry and heart-cut two-dimensional gas chromatography-mass spectrometry/olfactometry. The majority of the identified odorant compounds were oxygenated monoterpenes, along with some relevant mono- and sesquiterpenes and only one diterpenoid substance. Several of these compounds were reported here for the first time as odorous constituents in B. sacra. Identifying bioactive compounds might support a better understanding with regard to the potential benefits of frankincense, for example in aromatherapy or ecclesial settings. PMID:25468535

  12. Resolution of volatile fuel compound profiles from Ascocoryne sarcoides: a comparison by proton transfer reaction-mass spectrometry and solid phase microextraction gas chromatography-mass spectrometry

    PubMed Central

    2012-01-01

    Volatile hydrocarbon production by Ascocoryne sacroides was studied over its growth cycle. Gas-phase compounds were measured continuously with a proton transfer reaction-mass spectrometry (PTR-MS) and at distinct time points with gas chromatography-mass spectrometry (GC-MS) using head space solid phase microextraction (SPME). The PTR-MS ion signal permitted temporal resolution of the volatile production while the SPME results revealed distinct compound identities. The quantitative PTR-MS results showed the volatile production was dominated by ethanol and acetaldehyde, while the concentration of the remainder of volatiles consistently reached 2,000 ppbv. The measurement of alcohols from the fungal culture by the two techniques correlated well. Notable compounds of fuel interest included nonanal, 1-octen-3-ol, 1-butanol, 3-methyl- and benzaldehyde. Abiotic comparison of the two techniques demonstrated SPME fiber bias toward higher molecular weight compounds, making quantitative efforts with SPME impractical. Together, PTR-MS and SPME GC-MS were shown as valuable tools for characterizing volatile fuel compound production from microbiological sources. PMID:22480438

  13. Evaluation of headspace-gas chromatography/mass spectrometry for the analysis of benzene in vitamin C drinks; pitfalls of headspace in benzene detection.

    PubMed

    Ju, Hyun Kyoung; Park, Jeong Hill; Kwon, Sung Won

    2008-08-01

    Recently, there have been reports regarding the presence of benzene in vitamin C drinks. This is caused by sodium benzoate and ascorbic acid (vitamin C), which can react together to induce benzene formation. While the headspace gas chromatography method is well known for the detection of benzene, there could be pitfalls in the process of benzene extraction. This study was performed to check if benzene could be generated under high-temperature incubation conditions. As a result, the amount of benzene detected by headspace-gas chromatography/mass spectrometry (HSGC/MS) was affected by temperature changes. As the temperature of the sample vial was increased, newly generated benzene from the headspace also increased, causing false-positive determination of benzene. Although 80 degrees C is generally accepted for the temperature of headspace sample vials, lower temperatures, such as 40 degrees C, minimize the false-positive identification of benzene. Considering that this minimization allows benzene to be quantified at around 5 ppb, this lower temperature should definitely be considered since benzene, which is formed in sodium benzoate, can appear in vitamin C drinks under certain circumstances. The proposed analysis method of benzene in vitamin C drinks by HSGC/MS at 40 degrees C is an accurate and universal method for the monitoring of benzene without false-positive identification. PMID:18506678

  14. Determination of off-flavor compounds, 2-methylisoborneol and geosmin, in salmon fillets using stir bar sorptive extraction-thermal desorption coupled with gas chromatography-mass spectrometry.

    PubMed

    Ruan, E D; Aalhus, J L; Summerfelt, S T; Davidson, J; Swift, B; Jurez, M

    2013-12-20

    A sensitive and solvent-less method for the determination of musty and earthy off-flavor compounds, 2-methylisoborneol (MIB) and geosmin (GSM), in salmon tissue was developed using stir bar sorptive extraction-thermal desorption coupled with gas chromatography-mass spectrometry (SBSE-TD-GCMS). MIB and GSM were solid phase extracted using polydimethylsiloxane (PDMS) coated stir bars, analyzed by gas chromatography, and detected in full scan mode of mass selective detector (MSD). Using this method, the calibration curves of MIB and GSM were linear in the range of 0.3-100ng/L, with a correlation coefficient above 0.999 and RSDs less than 4% (n=4). The limit of detection (LOD, S/N=3, n=6) and limit of quantification (LOQ, S/N=10, n=6) of MIB and GSM were both ?0.3 and 1ng/L, respectively. The recoveries of MIB and GSM were 22% and 29% by spike in 30ng/L standard compounds, 23% and 30% by spike-in 100ng/L standard compounds in salmon tissue samples with good precision (<8% of RSDs, n=6), respectively. The recoveries of MIB and GSM were better than reported methodologies using SPME fibres (<10%) in fish tissue samples. This method was successfully applied to monitor and characterize depurated salmon fillet samples (0, 3, 6 and 10 days). PMID:24252650

  15. Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.

    PubMed

    Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

    2014-08-01

    For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. PMID:24929909

  16. The quantitative analysis of inhalational anaesthetics in forensic samples by gas chromatography/mass spectrometry/selected ion monitoring.

    PubMed

    Maruyama, K; Takatsu, A; Obata, T

    1995-01-01

    The quantitative analysis of volatile anaesthetics for biomedical applications by means of gas chromatograph/mass spectrometry/selected ion monitoring (GC/MS/SIM) was studied. Xenon gas was selected as an internal standard for the assay by adding to a closed system, because of its stability and inactivity. In the assay of inhalational anaesthetics, isoflurane and nitrous oxide (laughing gas), in forensic samples (serum and cerebrospinal fluid), the calibration of the anaesthetic was linear from 0.12 to 12 nmol/mL in isoflurane and from 30 to 300 nmol/mL in nitrous oxide. Our results suggest that this new method is suitable for the quantitative analysis of inhalational anaesthetics in the biomedical field. PMID:8520207

  17. Separation and determination of ephedrine alkaloids and tetramethylpyrazine in Ephedra sinica Stapf by gas chromatography-mass spectrometry.

    PubMed

    Li, H X; Ding, M Y; Lv, K; Yu, J Y

    2001-09-01

    A simple, sensitive, and reliable method using gas chromatography (GC)-mass spectrometry (MS) is developed for the simultaneous determination of ephedrine alkaloids and 2,3,5,6-tetramethylpyrazine (TMP) in Ephedra sinica Stapf. The sample is extracted with ethyl ether and submitted to GC-MS for identification and quantitation without derivatization. The column used for GC is an HP-5 (30.0 m x 250 microm x 0.25 microm, 5% phenyl methyl siloxane), and the carrier gas is helium. The detection limits for ephedrine, pseudoephedrine, and TMP are 0.4 ng 0.7 ng, and 0.02 ng (signal-to-noise ratio of 3), respectively. The reproducibility of the total procedure is proved to be acceptable (RSD < 2%), and the recoveries are above 93%. PMID:11565946

  18. Precolumn sample-enrichment device for analysis of ambient volatile organics by gas chromatography-mass spectrometry

    SciTech Connect

    Arnts, R.R.

    1985-01-01

    Gas chromatographic-mass spectrometric (GC/MS) identification of air pollutants generally requires a preconcentration step to provide sufficient sample for analysis. Cryogenic trapping is often used to enrich the sample since nitrogen and oxygen are not condensed. It does, however, concentrate enormous quantities of water and carbon dioxide - enough to plug high-resolution narrow-bore capillary columns needed for separation of complex environmental samples. Whole-air samples were collected in stainless steel containers or Tedlar bags for analysis by gas chromatography with flame ionization detection (GC/FID). In order to provide identification of unknown peaks and confirmation of tentatively named peaks, the system described herein was designed and built to enrich samples for GC/MS analysis of volatile organics. The preconcentration system consists of a solid sorbent trap and a cryogenic trap used in sequence to collect organic vapors and focus them for analysis by GC/MS.

  19. GC-MS in the analysis of organic compounds in meteorites. [Gas Chromatography-Mass Spectroscopy approaches

    NASA Technical Reports Server (NTRS)

    Lawless, J. G.; Romiez, M. P.

    1974-01-01

    The application of an analytical approach combining gas chromatography with mass spectrometry (GC-MS) has shown that the amino acid composition of meteorite extracts is quite complex. A computer was used in the evaluation of the data obtained in the investigations. The computer programs developed have been concerned solely with the mass spectra of amino acids. Specialized programs have been written to determine the number of carbon atoms in an amino acid which is a member of any of three subclasses.

  20. Determination of boiling point of petrochemicals by gas chromatography-mass spectrometry and multivariate regression analysis of structural activity relationship.

    PubMed

    Fakayode, Sayo O; Mitchell, Breanna S; Pollard, David A

    2014-08-01

    Accurate understanding of analyte boiling points (BP) is of critical importance in gas chromatographic (GC) separation and crude oil refinery operation in petrochemical industries. This study reported the first combined use of GC separation and partial-least-square (PLS1) multivariate regression analysis of petrochemical structural activity relationship (SAR) for accurate BP determination of two commercially available (D3710 and MA VHP) calibration gas mix samples. The results of the BP determination using PLS1 multivariate regression were further compared with the results of traditional simulated distillation method of BP determination. The developed PLS1 regression was able to correctly predict analytes BP in D3710 and MA VHP calibration gas mix samples, with a root-mean-square-%-relative-error (RMS%RE) of 6.4%, and 10.8% respectively. In contrast, the overall RMS%RE of 32.9% and 40.4%, respectively obtained for BP determination in D3710 and MA VHP using a traditional simulated distillation method were approximately four times larger than the corresponding RMS%RE of BP prediction using MRA, demonstrating the better predictive ability of MRA. The reported method is rapid, robust, and promising, and can be potentially used routinely for fast analysis, pattern recognition, and analyte BP determination in petrochemical industries. PMID:24881546

  1. High-temperature gas chromatography-mass spectrometry with glass capillary columns for the screening of natural products.

    PubMed

    dos, SantosPereirAlberto; Carbonell, Silvia Albero; de, AquinoNetoFranciscoRadler; do, AmaralAnaClaudiaFernandes; Barnes, Roderick A

    2002-02-22

    High-temperature high resolution gas chromatography (HT-HRGC) and HT-HRGC coupled to mass spectrometry (HT-HRGC-MS) are powerful but relatively unexplored tools for the analysis of crude extracts and fractions of natural products. To illustrate the scope of the technique the direct characterization of several compounds, present in crude extracts of leaves and stems of Croton hemiargyreus Muell. Arg. var. hemiargyreus was undertaken, without derivatization or clean-up procedures. Both practical aspects and limitations of HT-HRGC and HT-HRGC-MS were evaluated resulting in a simple, straightforward and extremely powerful technique for the analysis of complex mixtures. PMID:11883659

  2. Screening of steroids in horse urine and plasma by using electron impact and chemical ionization gas chromatography-mass spectrometry.

    PubMed

    Singh, A K; Gordon, B; Hewetson, D; Granley, K; Ashraf, M; Mishra, U; Dombrovskis, D

    1989-10-01

    Gas chromatography with chemical ionization mass spectrometry and selected-ion monitoring provided a sensitive method for the screening and confirmation of steroids in horse urine and plasma. Chemical ionization mass spectrometry was more sensitive than the electron impact ionization mass spectrometry for most of the steroids except for testosterone, prednisone-metabolite-2 and prednisolone-metabolite-2. The chromatographic conditions used in this study provided clean separation of different natural and synthetic steroids. Approximately 75-85% of the steroids added to plasma and approximately 65-70% of the steroids added to urine were recovered by the extraction procedure used in this study. PMID:2808600

  3. Ancient wood of the Acqualadrone rostrum: materials history through gas chromatography/mass spectrometry and sulfur X-ray absorption spectroscopy.

    PubMed

    Frank, Patrick; Caruso, Francesco; Caponetti, Eugenio

    2012-05-15

    In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge X-ray absorption spectroscopy (XAS) and gas chromatography/mass spectrometry (GC/MS). GC/MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was about 2% and 7% in black and brown wood, respectively, while pyritic sulfur was about 12% and 6%. About 2% of the sulfur in both wood types was modeled as trimethylsulfonium, possibly reflecting biogenic (dimethylsulfonio)propionate. High-valent sulfur was exclusively represented by sulfate esters, consistent with bacterial sulfotransferase activity. Traces of chloride were detected, but no free sulfate ion. In summary, the rostrum was manufactured of pine wood and subsequently waterproofed with pine pitch. The subsequent 2300 years included battle, foundering, and marine burial followed by anoxia, bacterial colonization, sulfate reduction, and mobilization of transition metals, which produced pyrite and copious appended sulfur functionality. PMID:22545724

  4. Detection of Stimulants and Narcotics by Liquid Chromatography-Tandem Mass Spectrometry and Gas Chromatography-Mass Spectrometry for Sports Doping Control.

    PubMed

    Ahrens, Brian D; Kucherova, Yulia; Butch, Anthony W

    2016-01-01

    Sports drug testing laboratories are required to detect several classes of compounds that are prohibited at all times, which include anabolic agents, peptide hormones, growth factors, beta-2 agonists, hormones and metabolic modulators, and diuretics/masking agents. Other classes of compounds such as stimulants, narcotics, cannabinoids, and glucocorticoids are also prohibited, but only when an athlete is in competition. A single class of compounds can contain a large number of prohibited substances and all of the compounds should be detected by the testing procedure. Since there are almost 70 stimulants on the prohibited list it can be a challenge to develop a single screening method that will optimally detect all the compounds. We describe a combined liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) testing method for detection of all the stimulants and narcotics on the World Anti-Doping Agency prohibited list. Urine for LC-MS/MS testing does not require sample pretreatment and is a direct dilute and shoot method. Urine samples for the GC-MS method require a liquid-liquid extraction followed by derivatization with trifluoroacetic anhydride. PMID:26660193

  5. Optimization of a Solid-Phase Microextraction method for the Gas Chromatography-Mass Spectrometry analysis of blackberry (Rubus ulmifolius Schott) fruit volatiles.

    PubMed

    D'Agostino, M F; Sanz, J; Sanz, M L; Giuffr, A M; Sicari, V; Soria, A C

    2015-07-01

    A Solid-Phase Microextraction method for the Gas Chromatography-Mass Spectrometry analysis of blackberry (Rubus sp.) volatiles has been fully optimized by means of a Box-Behnken experimental design. The optimized operating conditions (Carboxen/Polydimethylsiloxane fiber coating, 66C, 20 min equilibrium time and 16 min extraction time) have been applied to the characterization for the first time of the volatile composition of Rubus ulmifolius Schott blackberries collected in Italy and Spain. A total of 74 volatiles of different functionality were identified; esters and aliphatic alcohols were the predominant classes in both sample types. Methylbutanal (2.02-25.70%), ethanol (9.84-68.21%), 2,3-butanedione (2.31-14.71%), trans-2-hexenal (0.49-17.49%), 3-hydroxy-2-butanone (0.08-7.39%), 1-hexanol (0.56-16.39%), 1-octanol (0.49-10.86%) and methylbutanoic acid (0.53-21.48%) were the major compounds in most blackberries analyzed. Stepwise multiple regression analysis of semiquantitative data showed that only two variables (ethyl decanoate and ethyl acetate) were necessary for a successful differentiation of blackberries according to their harvest location. PMID:25704677

  6. Studies on the human metabolism and the toxicologic detection of the cough suppressant dropropizine in urine using gas chromatography-mass spectrometry.

    PubMed

    Staack, Roland F; Theobald, Denis S; Maurer, Hans H

    2004-08-01

    Studies are described on the metabolism and the toxicologic analysis of the nonopioid cough suppressant dropropizine [R,S-3-(4-phenyl-1-piperazinyl)1,2-propandiol, DRO] in human urine using gas chromatography-mass spectrometry (GC-MS). The metabolism studies showed that DRO was metabolized in humans mainly by hydroxylation of the aromatic ring, by N-dealkylation of the parent drug and of the hydroxyl-metabolite to the corresponding N-phenylpiperazines, and by degradation of the piperazine moiety. The authors' systematic toxicologic analysis (STA) procedure using full-scan GC-MS after acid hydrolysis, liquid-liquid extraction, and microwave-assisted acetylation allowed the unambiguous detection of DRO and its above-mentioned metabolites in human urine up to about 32 hours after intake of a single common therapeutic dose. The target analytes were found to be the parent compound DRO (earlier phase of excretion) and the hydroxylated metabolite para-hydroxy-DRO (later phase of excretion). Both allowed unambiguous detection of an intake of DRO and also differentiation from other phenylpiperazine derivatives. PMID:15257075

  7. Contribution of oxidized tallow to aroma characteristics of beeflike process flavour assessed by gas chromatography-mass spectrometry and partial least squares regression.

    PubMed

    Song, Shiqing; Zhang, Xiaoming; Xiao, Zuobing; Niu, Yunwei; Hayat, Khizar; Eric, Karangwa

    2012-09-01

    Flavour profiles of seven beeflike process flavours (BFs) including non-oxidized or oxidized tallow were comparatively analysed by electronic nose, gas chromatography-mass spectrometry (GC-MS) and descriptive sensory analysis to characterize the headspace of BFs. Analysis of volatiles by GC-MS indicated that the effect of oxidized tallow with moderate oxidization level on Maillard reaction was more prominent than that of others, which potentially could result in an optimal meat flavour with strong, harmony and species-specific characteristics detected by sensory analysis. In addition, electronic nose data confirmed the accuracy of the GC-MS and sensory analysis results. Correlation analysis of the electronic nose measurements, sensory evaluation and characteristic compounds through Partial Least Squares Regression (PLSR) further explained that moderate oxidized tallow with peroxide value (PV) of 87.67-160 mequiv./kg, the p-anisidine value (p-AV) of 30.57-50, and the acid value (AV) of 1.8-2.2 mg KOH/g tallow was a desirable precursor for imparting aroma characteristics of beef flavour. PMID:22858364

  8. Determination of sex-based differences in serum ?-linoleic acid and dihomo-?-linoleic acid using gas chromatography-mass spectrometry.

    PubMed

    Onozato, Mayu; Nishikiori, Minami; Iizuka, Hideaki; Ichiba, Hideaki; Sadamoto, Kiyomi; Fukushima, Takeshi

    2015-08-01

    Because serum unsaturated fatty acids can provide useful information on disease diagnosis, the simultaneous determination of several fatty acids in small volumes of human serum would be beneficial for clinical applications. In the present study, serum fatty acids were extracted with n-heptane/chloroform from 10?L of serum collected from 26 healthy Japanese subjects (11 men, ages 23-37 years; 15 women, ages 18-37 years) after deproteinization with perchloric acid, derivatization to their methyl ester using p-toluenesulfonic acid as an acid catalyst, and subsequent separation and measurement by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring mode. Nine types of fatty acids (palmitoleic acid [PLA], oleic acid [OA], lenoleic acid [LA], ?-linolenic acid [GLA], ?-linolenic acid [ALA], dihomo-GLA [DGLA], arachidonic acid [AA], eicosapentaenoic acid [EPA], and docosahexaenoic acid [DHA]) were analyzed in the serum within 35 min by GC-MS. The concentrations of these fatty acids in serum ranged from 3.640.38?M (GLA) to 41326.3 ?M (LA). Among these nine fatty acids, GLA and DGLA levels were significantly lower in women than in men (p=0.0034 and 0.0012, respectively), suggesting that there may be sex-based differences in the biosynthetic production or metabolic processes of GLA and DGLA in humans. PMID:26113452

  9. Fully automated determination of macrocyclic musk fragrances in wastewater by microextraction by packed sorbents and large volume injection gas chromatography-mass spectrometry.

    PubMed

    Vallecillos, Laura; Pocurull, Eva; Borrull, Francesc

    2012-11-16

    A fully automated method has been developed for the determination of eight macrocyclic musk fragrances in urban wastewater. The procedure includes the enrichment of the analytes by microextraction by packed sorbent (MEPS) followed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). The main factors in the MEPS technique were optimized. For all of the analytes, the highest enrichment factors were achieved when 4 mL samples were extracted by using C18 MEPS-sorbent and 50 ?L of ethyl acetate were used for desorption. The eluate was directly analysed by GC-MS. Detection limits were found to be between 5 ng L(-1) and 10 ng L(-1), depending on the target analytes. In addition, under optimized conditions, the method gave good levels of intra-day and inter-day repeatability in wastewater samples with relative standard deviation (RSD) (n=3, 1,000 ng L(-1)) less than 5% and 9%, respectively. The applicability of the method was tested with wastewater samples from two influent and effluent urban wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the macrocylic musks at concentrations higher than the method quantification limits (MQLs), being the most abundant analyte ambrettolide at 9.29 ?g L(-1). In addition, the analyses of effluent urban wastewater showed a decrease in the concentrations with macrocyclic musk concentrations of between not detected (n.d.) and 2.26 ?g L(-1) being detected. PMID:23062975

  10. Fast determination of synthetic polycyclic musks in sewage sludge and sediments by microwave-assisted headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    PubMed

    Wu, Shin-Fang; Ding, Wang-Hsien

    2010-04-23

    One-step in situ microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS) analysis is presented as a fast and solvent-free technique to determine synthetic polycyclic musks in sewage sludge and sediment samples. Six synthetic polycyclic musks (galaxolide (HHCB), tonalide (AHTN), celestolide (ADBI), traseolide (ATII), cashmeran (DPMI) and phantolide (AHMI)) were selected in the method development and validation. The effects of extraction parameters for the quantitative extraction of these analytes by one-step MA-HS-SPME were systematically investigated. The dewatered solid sample mixed with 20-mL deionized water (containing 3 g of NaCl in a 40-mL sample-vial) was efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the extraction slurry was microwave irradiated at 80 W for 5 min. The limits of detection (LODs) ranged from 0.04 to 0.1 ng/g, and the limits of quantification (LOQs) ranged from 0.1 to 0.3 ng/g (fresh weight). A preliminary analysis of sludge and sediment samples revealed that HHCB and AHTN were the two most commonly detected synthetic polycyclic musks; using a standard addition method, their total concentrations were determined to range from 0.3 to 10.9 ng/g (fresh weight) with relative standard deviation (RSD) ranging from 4% to 10%. PMID:20303495

  11. Determination of synthetic polycyclic musks in aqueous samples by ultrasound-assisted dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry.

    PubMed

    Yang, Ching-Ya; Ding, Wang-Hsien

    2012-02-01

    A simple and solvent-minimized procedure for the determination of six commonly found synthetic polycyclic musks in aqueous samples using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) is described. The parameters affecting the extraction efficiency of analytes from water samples were systematically investigated. The best extraction conditions involved the rapid injection of a mixture of 1.0 mL of isopropyl alcohol (as a dispersant) and 10 ?L of carbon tetrachloride (as an extractant) into 10 mL of water containing 0.5 g of sodium chloride in a conical-bottom glass tube. After ultrasonication for 1.0 min and centrifugation at 5,000 rpm (10 min), the sedimented phase 1.0 ?L was directly injected into the GC-MS system. The limits of quantitation (LOQs) were less than 0.6 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), was less than 11% for both intra- and interday analysis. Accuracy, expressed as the mean extraction recovery, was between 71 and 104%. Their total concentrations were determined in the range from 8.3 to 63.9 ng/L in various environmental samples by using a standard addition method. PMID:22139524

  12. Determination of synthetic polycyclic musks in water by microwave-assisted headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    PubMed

    Wang, Yu-Chen; Ding, Wang-Hsien

    2009-10-01

    This paper describes a rapid and solvent-free method, microwave-assisted headspace solid-phase microextraction (MA-HS-SPME), for the extraction of six commonly used synthetic polycyclic musks: galaxolide (HHCB), tonalide (AHTN), celestolide (ADBI), traseolide (ATII), cashmeran (DPMI) and phantolide (AHMI) from water samples prior to their determination using gas chromatography-mass spectrometry (GC-MS). The effects of various extraction parameters for the quantitative extraction of these analytes by MA-HS-SPME were systematically investigated and optimized. The analytes in a 20-mL water sample (in a 40-mL sample-vial containing 4 g of NaCl) were efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the system was microwave irradiated at 180 W for less than 4 min. The limits of detection (LODs) ranged from 0.05 to 0.1 ng/L, and the limits of quantification (LOQs) were less than 0.2 ng/L. A preliminary analysis of wastewater samples revealed that HHCB and AHTN were the two most commonly detected synthetic polycyclic musks; using a standard addition method, their concentration were determined to range from 1.2 to 37.3 ng/L with relative standard deviation (RSD) ranging from 2 to 6%. The results obtained using this approach are better than those from the conventional oil-bath HS-SPME. PMID:19720378

  13. At-line microextraction by packed sorbent-gas chromatography-mass spectrometry for the determination of UV filter and polycyclic musk compounds in water samples.

    PubMed

    Moeder, Monika; Schrader, Steffi; Winkler, Ursula; Rodil, Rosario

    2010-04-23

    An at-line analysis protocol is presented that allows the determination of four UV filters, two polycyclic musk compounds and caffeine in water at concentration level of ng L(-1). The fully automated method includes analytes enrichment by Microextraction by packed sorbent (MEPS) coupled directly to large volume injection-gas chromatography-mass spectrometry. Two common SPE phases, C8 and C18, were examined for their suitability to extract the target substances by MEPS. The analytes were extracted from small sample volumes of 800 microL with recoveries ranging from 46 to 114% for the C8-sorbent and 65-109% for the C18-sorbent. Limits of detection between 34 and 96 ng L(-1) enable the determination of the analytes at common environmental concentration levels. Both sorbents showed linear calibration curves for most of the analytes up to a concentration level of 20 ng mL(-1). Carryover was minimized by washing the sorbents 10 times with 100 microL methanol. After this thorough cleaning, the MEPS are re-used and up to 70 analyses can be performed with the same sorbent. The fully automated microextraction GC-MS protocol was evaluated for the influence of matrix substances typical for wastewater. Dilution of samples prior to MEPS is recommended when the polar caffeine is present at high concentration. Real water samples were analyzed by the MEPS-GC-MS method and compared to standard SPE. PMID:20334867

  14. Simultaneous determination of parabens and synthetic musks in water by stir-bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry.

    PubMed

    Ramrez, Noelia; Borrull, Francesc; Marc, Rosa Maria

    2012-02-01

    This study focuses on a method for simultaneously determining personal care products in a wide range of polarities in different water matrices. The method is based on stir-bar sorptive extraction followed by thermal desorption-gas chromatography-mass spectrometry. Prior to extraction, the parabens were acetylated to improve their affinity for the polydimethylsiloxane phase of the stir bar. The method showed good linearity, repeatability and reproducibility between days for all compounds and limits of detection at low ng/L levels (between 0.02 and 0.3?ng/L). The proposed method is also environmentally friendly, because it does not use organic solvents, and reduces the risk of external pollution, due to the minimal manipulation of the sample required. The method developed was successfully applied for the analysis of personal care products in different kinds of water matrices: influents and effluents of urban and industrial wastewater treatment plants, effluents of a reverse osmosis treatment plant and river waters. The influents of urban treatment plants generally showed the highest values for synthetic musks, with concentrations of up to 2219?ng/L of galaxolide, whereas the highest concentrations of parabens were detected in the industrial treatment plants influents. PMID:22282419

  15. One-step microwave-assisted headspace solid-phase microextraction for the rapid determination of synthetic polycyclic musks in oyster by gas chromatography-mass spectrometry.

    PubMed

    Wu, Shin-Fang; Liu, Li-Lian; Ding, Wang-Hsien

    2012-07-15

    A rapid, simple and solvent-free procedure was developed for the determination of synthetic polycyclic musks in oyster samples by using one-step microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) and gas chromatography-mass spectrometry (GC-MS). Two commonly used synthetic polycyclic musks, galaxolide (HHCB) and tonalide (AHTN), were selected in the method development and validation. The parameters (microwave irradiation power, extraction time, amount of water added, pH value and addition of NaCl) affecting the extraction efficiency of analytes from oyster slurry were systematically investigated and optimised. The best extraction conditions were achieved when the oyster tissue mixed with 10-mL deionised water (containing 3g of NaCl in a 40-mL sample-vial) was microwave irradiated at 80 W for 5 min. The limit of quantification (LOQ) was 0.1 ng/g in 5-g of wet tissue. The good precision and accuracy of one-step MA-HS-SPME coupled with GC-MS for the determination of trace level of AHTN in oyster samples was also demonstrated. PMID:25683427

  16. Multiresidue method for the determination of pharmacologically active substances in egg and honey using a continuous solid-phase extraction system and gas chromatography-mass spectrometry.

    PubMed

    Azzouz, Abdelmonaim; Ballesteros, Evaristo

    2015-07-01

    A sensitive, selective, efficient gas chromatography-mass spectrometry method for the simultaneous determination of 22 pharmacologically active substances (antibacterials, nonsteroidal antiinflammatories, antiseptics, antiepileptics, lipid regulators, ?-blockers and hormones) in eggs and honey was developed. The sample pretreatment includes precipitation of proteins and lipids with acetonitrile:water (3:2, v/v), centrifugation and continuous solid-phase extraction for cleanup and preconcentration. The proposed method was validated with quite good analytical results including limits of detection of 0.4-3.3 ng/kg for 2g of sample and good linearity (r(2)>0.995) throughout the studied concentration ranges. The recoveries of analytes from real honey and egg samples spiked at concentrations of 15-2,000 ng/kg fell in the range 87-102%, with relative standard deviations from 2.6% to 7.0%. The method was successfully used to determine the target compounds in various types of eggs (hen, quail and duck) and honey samples (flower, forest, acacia, sunflower, clover and pine tree). Two samples of hen eggs bought at supermarkets and one of quail eggs were found to contain florfenicol, pyrimethamine, estrone and 17?-estradiol at levels from 0.095 to 2.7 ?g/kg. PMID:25704684

  17. Gas chromatography-mass spectrometry determination of earthy-musty odorous compounds in waters by two phase hollow-fiber liquid-phase microextraction using polyvinylidene fluoride fibers.

    PubMed

    Yu, Shengbing; Xiao, Qin; Zhu, Binghui; Zhong, Xiuhua; Xu, Yinghua; Su, Guangning; Chen, Min

    2014-02-14

    A rapid and sensitive method for the determination of earthy-musty odorous compounds, 2-methylisoborneol, 2-isopropyl-3-methoxy pyrazine, 2,4,6-trichloroanisole, 2,3,6-trichloroanisole, and geosmin, in water samples has been developed. The method was based on coupling a new polyvinylidene fluoride (PVDF) hollow-fiber liquid-phase microextraction system with gas chromatography-mass spectrometry (GC-MS). The PVDF hollow fibers have high porosity and an enhanced solvent compatibility for extraction of the target analytes. Experimental conditions were optimized by investigating the type of extraction solvent, sample pH, sodium chloride concentration, stirring speed, extraction time, and GC-MS conditions. Under optimized conditions, the earthy-musty odorous compounds exhibited good linearity (R>0.995) in the concentration range of 6.2-250ng/L. The repeatability and reproducibility of the method were lower than 6.8% and 9.8%, respectively. The limit of detection and limit of quantification values were lower than 2.0 and 6.2ng/L, respectively. The analysis of different water samples such as tap, pond, rive and waste water indicated minimal matrix effects. Analyte recoveries for real samples spiked at different concentrations were between 84.4% and 117.5%. PMID:24456707

  18. Determination of hydroxy metabolites of polycyclic aromatic hydrocarbons by fully automated solid-phase microextraction derivatization and gas chromatography-mass spectrometry.

    PubMed

    Luan, Tiangang; Fang, Shenghong; Zhong, Yin; Lin, Li; Chan, Sidney M N; Lan, Chongyu; Tam, Nora F Y

    2007-11-30

    A fully automated sample pretreatment method was developed for the detection of mono and dihydroxy metabolites of polycyclic aromatic hydrocarbons (PAHs) by gas chromatography-mass spectrometry in the selected ion monitoring mode. Direct immersion solid-phase microextraction for the extraction of target compounds and the headspace on-fiber silylation with N,O-bis(trimethylsilyl)trifluoroacetamide were performed automatically by a multipurpose autosampler (MPS2). The operating conditions including extraction time, derivatization time, ionic strength, pH, and incubation temperature were optimized. Calibration responses of nine metabolites of PAHs over a concentration range of 0.1-100 microg L(-1) with a correlation coefficient of 0.999 were obtained. The detection limits of the nine metabolites in mini pore water, minimal salts medium and soil extract culture medium were in the range of 0.001-0.013, 0.002-0.024 and 0.002-0.134 microg L(-1), respectively, while the respective quantification limits were 0.003-0.044, 0.005-0.081 and 0.008-0.447 microg L(-1). The reliability was confirmed by the traditional solid-phase extraction method. The proposed method could be used to analyze the metabolites of PAHs degraded by microorganisms such as algae and to determine the biodegradation pathways of PAHs. PMID:17976631

  19. Headspace solid-phase microextraction gas chromatography-mass spectrometry method for the identification of cosmetic ingredients causing delamination of packagings.

    PubMed

    Ortiz, Gustavo; Tena, Mara Teresa

    2006-01-01

    A headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) method using a 75 microm Carboxen polydimethylsiloxane fibre was used to identify volatile compounds of cosmetic formulations responsible for causing loss of adhesion between layers of multilayer packagings. To obtain the sample, the sachet with the product was kept in an oven at 40 degrees C in order to favour the migration of the aggressive compounds to the inner layers. Then the sachet was manually delaminated and the aluminium/polyester and polyethylene layers were analysed. The cosmetic product was also analysed by HS-SPME-GC-MS. Several compounds used in the cosmetic industry such as perfumes or fixing agents were detected in the inner layers of the laminated material, showing the migration of them through the layer in contact with the product (polyethylene). Phenoxy ethanol, beta-linalool, menthol and p-propenylanisole are suspected to be responsible for the loss of adhesion. In order to provide a complete overview of the cause of the aforementioned phenomenon, the packaging material was exposed to the cosmetic products in order to measure the decrease of the adhesion strength with time. It was observed that the product with a higher phenoxy ethanol concentration caused a higher loss of adhesion strength. The results obtained showed that this method is suitable for identifying aggressive compounds in cosmetic products, as well as for giving prior information about which products may be problematic for packaging in sachets. PMID:16246353

  20. Lipid fatty acid profile analyses in liver and serum in rats with nonalcoholic steatohepatitis using improved gas chromatography-mass spectrometry methodology.

    PubMed

    Wu, Xianli; Tong, Yudong; Shankar, Kartik; Baumgardner, January N; Kang, Jie; Badeaux, Jamie; Badger, Thomas M; Ronis, Martin J J

    2011-01-26

    Fatty acids (FAs) are essential components of lipids and exhibit important biological functions. The analyses of FAs are routinely carried out by gas chromatography-mass spectrometry after multistep sample preparation. In this study, several key experimental factors were carefully examined, validated, and optimized to analyze free fatty acid (FFA) and FA profiles of triglycerides and phospholipids in serum or tissue samples. These factors included (1) methylation/transesterification reagents, (2) validation of internal standards, and (3) final step concentration of FA methyl esters. This new method was utilized to analyze FFAs and the FA profiles of triglycerides and phospholipids in the serum and liver from a recently established rat model of nonalcoholic steatohepatitis (NASH). In this model, rats were fed a 220 kcal kg (-3/4) day (-1) diet containing either 5 or 70% corn oil for 21 days using total enteral nutrition. FA compositions of the serum and liver were found to shift from a pattern dominated by saturated and monounsaturated FAs (C16:0/18:1) to one dominated by polyunsaturated C18:2 derived from dietary linoleic acid. Alteration of FA composition in liver after overfeeding of high polyunsaturated fat diets may contribute to the progression of pathological changes from steatosis to inflammation, necrosis, and fibrosis observed in NASH. PMID:21162572

  1. Determination of volatile organic compounds in the dried leaves of Salvia species by solid-phase microextraction coupled to gas chromatography mass spectrometry.

    PubMed

    Cozzolino, Rosaria; Ramezani, Sadrollah; Martignetti, Antonella; Mari, Angela; Piacente, Sonia; De Giulio, Beatrice

    2016-04-01

    Salvia spp. are used throughout the world both for food and pharmaceutical purposes. In this study, a method involving headspace solid-phase microextraction combined with gas chromatography-mass spectrometry was developed, to establish the volatiles profile of dried leaves of four Iranian Salvia spp.: Salvia officinalis L., Salvia leriifolia Benth, Salvia macrosiphon Boiss. and two ecotypes of Salvia reuterana Boiss. A total of 95 volatiles were identified from the dried leaves of the five selected samples. Specifically, α-thujone was the main component of S. officinalis L. and S. macrosiphon Boiss. (34.40 and 17.84%, respectively) dried leaves, S. leriifolia Benth was dominated by β-pinene (27.03%), whereas α-terpinene was the major constituent of the two ecotypes of S. reuterana Boiss. (21.67 and 13.84%, respectively). These results suggested that the proposed method can be considered as a reliable technique for isolating volatiles from aromatic plants, and for plant differentiation based on the volatile metabolomic profile. PMID:26305878

  2. Peak assignment in multi-capillary column-ion mobility spectrometry using comparative studies with gas chromatography-mass spectrometry for VOC analysis.

    PubMed

    Jünger, Melanie; Bödeker, Bertram; Baumbach, Jörg Ingo

    2010-01-01

    Over the past years, ion mobility spectrometry (IMS) as a well established method within the fields of military and security has gained more and more interest for biological and medical applications. This highly sensitive and rapid separation technique was crucially enhanced by a multi-capillary column (MCC), pre-separation for complex samples. In order to unambiguously identify compounds in a complex sample, like breath, by IMS, a reference database is mandatory. To obtain a first set of reference data, 16 selected volatile organic substances were examined by MCC-IMS and comparatively analyzed by the standard technique for breath research, thermal desorption-gas chromatography-mass spectrometry. Experimentally determined MCC and GC retention times of these 16 compounds were aligned and their relation was expressed in a mathematical function. Using this function, a prognosis of the GC retention time can be given very precisely according to a recorded MCC retention time and vice versa. Thus, unknown MCC-IMS peaks from biological samples can be assigned-after alignment via the estimated GC retention time-to analytes identified by GC/MS from equivalent accomplished data. One example of applying the peak assignment strategy to a real breath sample is shown in detail. PMID:19838827

  3. Response surface optimization for determination of volatile organic compounds in water samples by headspace-gas chromatography-mass spectrometry method.

    PubMed

    Missaoui, Ins; Sayedi, Lotfi; Jamoussi, Bassem; Ben Hassine, Bchir

    2009-04-01

    The determination of benzene, toluene, p-xylene, tetrachloroethene, chlorobenzene, and dibromomethane in water by headspace analysis combined with gas chromatography-mass spectrometry (HS-GC-MS) has been investigated. An optimization strategy for the analysis of the six volatile organic compounds (VOCs) is presented with the experimental design and response surface methodology aid. Thermostatting time, temperature, and salt quantity were optimized by using a central composite design, and quadratic models relating peak areas to the three factors were built. The mathematical models were tested on a number of simulated data set and had a coefficient of R2>0.98. The factor effects were visualized as three-dimensional response surfaces and contour plots. The optimal conditions were achieved in 36.8 min, at 90 degrees C, and with 6 g of NaCl. The method showed a good agreement between the experimental data and predictive values throughout the studied parameter space, and was suitable for optimization studies of the VOCs in water by the HS-GC-MS method. PMID:19406010

  4. In situ derivatization reaction and determination of ibuprofen in water samples using headspace generation-programmed temperature vaporization-gas chromatography-mass spectrometry.

    PubMed

    Prez Pavn, Jos Luis; Casas Ferreira, Ana Mara; Fernndez Laespada, Mara Esther; Moreno Cordero, Bernardo

    2009-09-25

    The aim of the present work is to propose a method for the determination of ibuprofen, as a typical representative of pharmaceutical compounds, in aqueous samples. To do so, an in situ derivatization reaction in aqueous medium was employed in the vial of a headspace sampler (HS), after which instrumental measurements were made with gas chromatography-mass spectrometry (GC-MS). As the injection system we propose a programmed temperature vaporizer (PTV) where, in solvent vent mode, better results can be obtained than with the conventional split and splitless injection modes. Since the derivatization reaction takes place in the HS vial, after the mixing of reagents and the sealing of the vial, the whole process takes place on-line, with no need for intermediate steps. The simplicity and speed of the method--analysis throughput: 10.5 min--together with the limit of detection obtained (0.23 microg/L), bearing in mind that no preconcentration step or later clean-up step are required, make this a good method for the analysis of ibuprofen in aqueous samples of urban waste water. PMID:19700164

  5. Simultaneous determination of methamphetamine and amphetamine in human urine using pipette tip solid-phase extraction and gas chromatography-mass spectrometry.

    PubMed

    Kumazawa, Takeshi; Hasegawa, Chika; Lee, Xiao-Pen; Hara, Kenji; Seno, Hiroshi; Suzuki, Osamu; Sato, Keizo

    2007-06-28

    Methamphetamine and amphetamine were extracted from human urine samples using pipette tip solid-phase extraction (SPE) with MonoTip C18 tips (pipette tip volume, 200 microl), in which C18-bonded monolithic silica gel was fixed. A sample of human urine (0.5 ml) containing methamphetamine, amphetamine, and N-methylbenzylamine as internal standard (IS), was mixed with 25 microl of 1M sodium hydroxide solution. The mixture was extracted into the C18 phase of the SPE tip by 25 repeated aspirating/dispensing cycles using a manual micropipettor. Analytes retained in the C18 phase were then eluted with methanol by five repeated aspirating/dispensing cycles. After derivatization with trifluoroacetic anhydride, analytes were measured by gas chromatography/mass spectrometry with selected ion monitoring in the positive-ion electron impact mode. Recoveries of methamphetamine, amphetamine, and IS spiked into urine were more than 82.9, 82.2, and 78.2%, respectively. Regression equations for methamphetamine and amphetamine showed excellent linearity in the range of 0.25-200 ng/0.5 ml. Limit of detection was 0.04 ng/0.5 ml for methamphetamine and 0.05 ng/0.5 ml for amphetamine. Intra- and inter-day coefficients of variations for both stimulants were not greater than 10.8%. The data obtained from actual determination of methamphetamine and amphetamine in autopsy urine samples are also presented for validation of the method. PMID:17267160

  6. A rapid assay for the simultaneous determination of nicotine, cocaine and metabolites in meconium using disposable pipette extraction and gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Mozaner Bordin, Dayanne C; Alves, Marcela N R; Cabrices, Oscar G; de Campos, Eduardo G; De Martinis, Bruno Spinosa

    2014-01-01

    Drug abuse by pregnant women is considered a serious public health problem worldwide. Meconium is the first excretion in newborns and has been used as an alternative matrix to evaluate in utero drug exposure. Solid phase extraction (SPE) is widely employed to prepare and clean up samples in the field of forensic analysis. Most SPE products require large volumes of solvent, which culminates in longer sample processing times and increased cost per sample. Disposable pipette extraction (DPX) tips have been used as an alternative to traditional SPE cartridges. They combine efficient and rapid extraction with reduced solvent consumption. The purpose of this study was to develop and validate a method to determine nicotine, cotinine, cocaine, benzoylecgonine, cocaethylene and methyl ester anhydroecgonine in meconium using DPX and gas chromatography-mass spectrometry (GC-MS). Validation results indicated that extraction efficiency ranged 50-98%, accuracy 92-106%, intra-assay precision 4-12% and inter-assay precision 6-12%. Linear calibration curves resulted in R(2) values >0.99, limits of detection ranged from 2.5 to 15 ng/g and the limit of quantitation from 10 to 20 ng/g. The DPX-GC-MS method was shown to selectively analyze trace concentrations of drugs in meconium samples. Finally, the developed and validated method was applied to 50 meconium samples. PMID:24272386

  7. Identification of volatile butyl rubber thermal-oxidative degradation products by cryofocusing gas chromatography/mass spectrometry (cryo-GC/MS).

    SciTech Connect

    Smith, Jonell Nicole; White, Michael Irvin; Bernstein, Robert; Hochrein, James Michael

    2013-02-01

    Chemical structure and physical properties of materials, such as polymers, can be altered as aging progresses, which may result in a material that is ineffective for its envisioned intent. Butyl rubber formulations, starting material, and additives were aged under thermal-oxidative conditions for up to 413 total days at up to 124 %C2%B0C. Samples included: two formulations developed at Kansas City Plant (KCP) (%236 and %2310), one commercially available formulation (%2321), Laxness bromobutyl 2030 starting material, and two additives (polyethylene AC-617 and Vanax MBM). The low-molecular weight volatile thermal-oxidative degradation products that collected in the headspace over the samples were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). The majority of identified degradation species were alkanes, alkenes, alcohols, ketones, and aldehydes. Observations for Butyl %2310 aged in an oxygen-18 enriched atmosphere (18O2) were used to verify when the source of oxygen in the applicable degradation products was from the gaseous environment rather than the polymeric mixture. For comparison purposes, Butyl %2310 was also aged under non-oxidative thermal conditions using an argon atmosphere.

  8. Study of solvent sublation for concentration of trace phthalate esters in plastic beverage packaging and analysis by gas chromatography-mass spectrometry.

    PubMed

    Chang, Lin; Bi, Pengyu; Li, Xiaochen; Wei, Yun

    2015-06-15

    A novel trace analytical method based on solvent sublation (SS) and gas chromatography-mass spectrometry (GC-MS) was developed for the trace determination of twenty-two phthalate esters (PAEs) from plastic beverage packaging. In the solvent sublation section, the effects of solution pH, NaCl concentration, nitrogen flow rate, and sublation time on the sublation efficiency were investigated in detail, and the optimal conditions were obtained. The trace PAEs migrated from plastic beverage packaging to food simulants were separated and concentrated by solvent sublation, and then the trace target compounds in the concentrated solution were analyzed by GC-MS. According to the European Union Regulation, the food simulants including distilled water for the normal beverages and acetic acid solution (3%) for the acetic beverage of yogurt were prepared for migration tests. The trace analysis method showed good linearity, low limits of detection (LODs) of 1.6-183.5 ng/L, and satisfied recoveries (67.3-113.7%). PMID:25660867

  9. Analysis of polycyclic aromatic hydrocarbons in aqueous samples by large volume injection gas chromatography-mass spectrometry using the through oven transfer adsorption desorption interface.

    PubMed

    Aragn, lvaro; Toledano, Rosa M; Vzquez, Ana; Villn, Jess; Corts, Jos M

    2015-07-01

    A new procedure for the determination of 17 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) using the Through Oven Transfer Adsorption Desorption (TOTAD) interface with nitrogen for solvent elimination is developed and validated. Up to 75mL of aqueous samples were injected to be sure that good solvent elimination were achieved, although 500L were sufficient to achieve the required sensitivity.The performance of the developed method can be considered good: the relative standard deviation (RSD), (n=3) was lower than 13.8% for all the target analytes, the concentration of each PAH being 0.25?gL(-1), the limit of detection and limit of quantitation ranged from 21.5 to 211.0?ng?L(-1) and from 71.7 to 703.3ngL(-1) respectively, and the correlation coefficients (R(2)) were all higher than 0.9764 in the 1-16?gL(-1) range. PMID:25882400

  10. Optimization of a gas chromatography-mass spectrometry method with methyl chloroformate derivatization for quantification of amino acids in plant tissue.

    PubMed

    Vancompernolle, Bram; Croes, Kim; Angenon, Geert

    2016-04-01

    Rapid, easy and reliable quantification of amino acids is crucial in research on plant amino acid metabolism and nutritional improvement of crops via enrichment of essential amino acids. A recently reported analysis method, based on solid phase extraction (SPE), derivatization with methyl chloroformate and gas chromatography-mass spectrometry was optimized and tested on three-week-old Arabidopsis thaliana leaf tissues. Optimization of the SPE cleanup yielded recovery rates of minimum 95% for all amino acids (except arginine). Variations in accuracy and precision did not exceed 12.5%, except for cysteine, histidine and tryptophane, which were excluded from analysis. Quantification of overlapping peaks for isoleucine/threonine and proline/asparagine was possible by selection of two specific fragment ions for each amino acid. Of the 16 selected amino acids, 14 were quantified successfully in at least 75% of the samples, while methionine and tyrosine were only quantifiable in 6% and 42%, respectively. A case study on the aspartate super pathway confirmed the applicability of the optimized method on wild type and genetically modified plants: external supplementation of methionine or lysine yielded a 146-fold or 27-fold increase in the respective absolute amino acid levels compared with the control treatment. Induced expression of dhdps-r1 (a mutated lysine biosynthesis gene encoding a feedback insensitive enzyme) caused an 83-fold increase in absolute lysine levels. PMID:26994331

  11. Graphene oxide-based dispersive solid-phase extraction combined with in situ derivatization and gas chromatography-mass spectrometry for the determination of acidic pharmaceuticals in water.

    PubMed

    Naing, Nyi Nyi; Li, Sam Fong Yau; Lee, Hian Kee

    2015-12-24

    A fast and low-cost sample preparation method of graphene based dispersive solid-phase extraction combined with gas chromatography-mass spectrometric (GC-MS) analysis, was developed. The procedure involves an initial extraction with water-immiscible organic solvent, followed by a rapid clean-up using amine functionalized reduced graphene oxide as sorbent. Simple and fast one-step in situ derivatization using trimethylphenylammonium hydroxide was subsequently applied on acidic pharmaceuticals serving as model analytes, ibuprofen, gemfibrozil, naproxen, ketoprofen and diclofenac, before GC-MS analysis. Extraction parameters affecting the derivatization and extraction efficiency such as volume of derivatization agent, effect of desorption solvent, effect of pH and effect of ionic strength were investigated. Under the optimum conditions, the method demonstrated good limits of detection ranging from 1 to 16ngL(-1), linearity (from 0.01 to 50 and 0.05 to 50μgL(-1), depending on the analytes) and satisfactory repeatability of extractions (relative standard deviations, below 13%, n=3). PMID:26684593

  12. Determination of eight pharmaceuticals in an aqueous sample using automated derivatization solid-phase microextraction combined with gas chromatography-mass spectrometry.

    PubMed

    Huang, Siming; Zhu, Fang; Jiang, Ruifen; Zhou, Shichun; Zhu, Derong; Liu, Hong; Ouyang, Gangfeng

    2015-05-01

    An automated aqueous derivatization solid-phase microextraction (SPME) coupled with a gas chromatography/mass spectrometry (GC/MS) method was developed for simultaneous determination of eight pharmaceuticals in water samples. Dimethyl sulfate and tetrabutylammonium hydrogen sulfate were selected as derivatization and activation reagents for the esterification reaction. An experimental design approach, central composition design (CCD), was employed to investigate and optimize the operative factors influencing the extraction efficiency, including extraction time, extraction temperature and ionic strength. The other parameters such as type of fiber coating, pH and derivatization conditions were also evaluated. SPME was finally carried out in headspace mode at 80C for 60min with the presence of 3.00g Na2SO4, using a home-made 44?m PDMS fiber. Wide linear ranges and low limits of detection (0.06-1.24ng L(-1)) were obtained under the optimized conditions. The relative standard deviations (RSDs) and recoveries ranged from 0.5% to 12.3% and 85% to 110%, respectively. The proposed method was successfully applied to the analysis of the real surface water samples from the Pearl River Estuary. PMID:25703003

  13. Acetone-activated polyimide electrospun nanofiber membrane for thin-film microextraction and thermal desorption-gas chromatography-mass spectrometric analysis of phenols in environmental water.

    PubMed

    Li, Shenghong; Wu, Dapeng; Yan, Xiaohui; Guan, Yafeng

    2015-09-11

    In this work, a polyimide nanofiber membrane was electrospun and applied as sorbent for thin film microextraction (TFME). After TFME of phenols in water samples, direct thermal desorption of the sorbent at 300C followed by gas chromatography-mass spectrometric (TD-GC-MS) analysis was carried out. The extraction efficiency of TFME was enhanced by 6-12 times for phenols after activation with acetone. The positive effect of acetone activation was correlated to the increased hydrophilicity of the membrane. Extraction parameters, including mass of nanofiber membrane, pH value, NaCl concentration and extraction time, were optimized. Under optimal conditions, the LODs and LOQs for analysis of phenols in spiked purified water were 0.0006-0.008 and 0.002-0.025?gL(-1), respectively. The linearity range was more than two orders of magnitude (R>0.99). The RSDs of intra-batch and inter-batch were 4.3-7.4% and 2.7-10.6% (n=3). Finally the method was applied to real samples, including tap water, sea water, and waste water. These results indicate that the polyimide nanofiber membrane is a promising candidate as TFME sorbent for determination of polar analytes in water samples coupled with TD-GC-MS. PMID:26277026

  14. Determination of Wastewater Compounds in Whole Water by Continuous Liquid-Liquid Extraction and Capillary-Column Gas Chromatography/Mass Spectrometry

    USGS Publications Warehouse

    Zaugg, Steven D.; Smith, Steven G.; Schroeder, Michael P.

    2006-01-01

    A method for the determination of 69 compounds typically found in domestic and industrial wastewater is described. The method was developed in response to increasing concern over the impact of endocrine-disrupting chemicals on aquatic organisms in wastewater. This method also is useful for evaluating the effects of combined sanitary and storm-sewer overflow on the water quality of urban streams. The method focuses on the determination of compounds that are indicators of wastewater or have endocrine-disrupting potential. These compounds include the alkylphenol ethoxylate nonionic surfactants, food additives, fragrances, antioxidants, flame retardants, plasticizers, industrial solvents, disinfectants, fecal sterols, polycyclic aromatic hydrocarbons, and high-use domestic pesticides. Wastewater compounds in whole-water samples were extracted using continuous liquid-liquid extractors and methylene chloride solvent, and then determined by capillary-column gas chromatography/mass spectrometry. Recoveries in reagent-water samples fortified at 0.5 microgram per liter averaged 72 percent ? 8 percent relative standard deviation. The concentration of 21 compounds is always reported as estimated because method recovery was less than 60 percent, variability was greater than 25 percent relative standard deviation, or standard reference compounds were prepared from technical mixtures. Initial method detection limits averaged 0.18 microgram per liter. Samples were preserved by adding 60 grams of sodium chloride and stored at 4 degrees Celsius. The laboratory established a sample holding-time limit prior to sample extraction of 14 days from the date of collection.

  15. Quantitative Analysis of Tetramethylenedisulfotetramine ("Tetramine") Spiked into Beverages by Liquid Chromatography Tandem Mass Spectrometry with Validation by Gas Chromatography Mass Spectrometry

    SciTech Connect

    Owens, J; Hok, S; Alcaraz, A; Koester, C

    2008-11-13

    Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD{sub 50} = 0.1 mg/kg) used in hundreds of deliberate food poisoning events in China. Here we describe a method for quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water and cleaned up by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography mass spectrometry (GC/MS) operated in SIM mode for ions m/z 212, 240, and 360. The limit of quantitation was 0.10 {micro}g/mL by LC/MS/MS versus 0.15 {micro}g/mL for GC/MS. Fortifications of the beverages at 2.5 {micro}g/mL and 0.25 {micro}g/mL were recovered ranging from 73-128% by liquid-liquid extraction for GC/MS analysis, 13-96% by SPE and 10-101% by liquid-liquid extraction for LC/MS/MS analysis.

  16. Determination of dissolved-phase pesticides in surface water from the Yakima River basin, Washington, using the Goulden large-sample extractor and gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Foster, G.D.; Gates, P.M.; Foreman, W.T.; McKenzie, S.W.; Rinella, F.A.

    1993-01-01

    Concentrations of pesticides in the dissolved phase of surface water samples from the Yakima River basin, WA, were determined using preconcentration in the Goulden large-sample extractor (GLSE) and gas chromatography/ mass spectrometry (GC/MS) analysis. Sample volumes ranging from 10 to 120 L were processed with the GLSE, and the results from the large-sample analyses were compared to those derived from 1-L continuous liquid-liquid extractions. Few of the 40 target pesticides were detected in 1-L samples, whereas large-sample preconcentration in the GLSE provided detectable levels for many of the target pesticides. The number of pesticides detected in GLSE processed samples was usually directly proportional to sample volume, although the measured concentrations of the pesticides were generally lower at the larger sample volumes for the same water source. The GLSE can be used to provide lower detection levels relative to conventional liquid-liquid extraction in GC/MS analysis of pesticides in samples of surface water. ?? 1993 American Chemical Society.

  17. Determination of atrazine and its major degradation products in soil pore water by solid-phase extraction, chemical derivatization, and gas chromatography/mass spectrometry

    USGS Publications Warehouse

    Carter, D.S.

    1996-01-01

    This report describes a method for the determination of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine, and hydroxyatrazine from soil pore waters by use of solid-phase extractionfollowed by chemical derivatization and gas chromatography/mass spectrometry. The analytes are isolated from the pore-water matrix byextraction onto a graphitized carbon-black cartridge. The cartridge is dried under vacuum, and adsorbed analytes are removed by elution with ethyl acetate followed by dichloromethane/methanol (7:3, volume/volume). Water is removed from the ethyl acetate fraction on an anhydrous sodium sulfate column. The combined fractions are solvent exchanged into acetonitrile, evaporated by use of a nitrogen stream, and derivatized by use of N- methyl-N-(tert-butyldimethylsilyl)- trifluoroacetamide. The derivatized extracts are analyzed by capillary-column gaschromatography/electron-impact mass spectrometry in the scan mode. Estimated method detection limits range from 0.03 to 0.07 micrograms per liter. The mean recoveries of all analytes and surrogates determined at 0.74 to 0.82 micrograms per liter in reagent water in soil pore water were 94 percent and 98 percent, respectively. The mean recoveries of all analytes and surrogates determined at 7.4 to 8.2 micrograms per liter in reagent water and in soil pore water were 96 percent and 97 percent,respectively. Recoveries were 90 percent or higher, regardless of analyte concentration or matrix composition, for all compounds excepthydroxyatrazine, whose recoveries were slightly lower (77 percent) at the low concentration.

  18. Development and validation of a gas chromatography/mass spectrometry procedure for confirmation of para-toluenesulfonamide in edible fish fillet tissue

    USGS Publications Warehouse

    Idowu, O.R.; Kijak, P.J.; Meinertz, J.R.; Schmidt, L.J.

    2004-01-01

    Chloramine-T is a disinfectant being developed as a treatment for bacterial gill disease in cultured fish. As part of the drug approval process, a method is required for the confirmation of chloramine-T residues in edible fish tissue. The marker residue that will be used to determine the depletion of chloramine-T residues from the edible tissue of treated fish is para-toluenesulfonamide (p-TSA), a metabolite of chloramine-T. The development and validation of a procedure for the confirmation of p-TSA is described. Homogenized fish tissue is dried by mixing with anhydrous sodium sulfate, and the mixture is extracted with methylene chloride. The extract is passed through a silica gel solid-phase extraction column, from which p-TSA is subsequently eluted with acetonitrile. The acetonitrile extract is evaporated, and the oily residue is dissolved in hexane. The hexane solution is shaken with fresh acetonitrile. The acetonitrile solution is evaporated and the residue is redissolved in dilute potassium hydroxide solution. The aqueous solution is extracted with methylene chloride to further remove more of the fat co-extractive. The aqueous solution is reacted with pentafluorobenzyl bromide in presence of tetrabutylammonium hydrogensulfate. The resulting di-(pentafluorobenzyl) derivative of p-TSA is analyzed by gas chromatography/mass spectrometry. This method permits the confirmation of p-TSA in edible fish tissue at 20 ppb.

  19. Precautions for in-injection port thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) as applied to aerosol filter samples

    NASA Astrophysics Data System (ADS)

    Ho, Steven Sai Hang; Chow, Judith C.; Watson, John G.; Ting Ng, Louisa Pan; Kwok, Yuk; Ho, K. F.; Cao, Junji

    2011-03-01

    In-injection port thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) allows for analysis for >130 non-polar organic compounds on small quartz-fiber filter samples without extraction chemicals. TD-GC/MS has been applied to samples from long-term U.S. networks since it is cost effective and less labor intensive. However, analysis of large numbers of samples results in sensitivity reductions over time. Instrument sensitivity and reproducibility were examined after 100, 200, and 500 sample analyses. Analyses of standards between batches of heavily loaded samples from China and Japan showed signal decreases of 28-78% for major organic classes. In the GC injection port, residues can accumulate on the gold-plated seal resulting in analyte adsorption as well as elevating signal background. Decreases in signal response were 28-43% for n-alkanes, 33-45% for hopanes and steranes, 28-56% for PAHs, and 38-78% for phthalates when the gold-plated seal was not replaced after 500 TD-GC/MS sample analyses. Limits of detection (LODs) also increased by 14-76% for the targeted non-polar organic compounds. Residues trapped in the capillary column head can cause peak broadening and overlap. The GC/MS system, including the injection port and gold seal, the column head (where the eluted sample is pre-concentrated), and the ion source should be cleaned after every batch of 50-100 samples.

  20. Total organic carbon and gas chromatography-mass spectroscopy methods to determine total carbon and hydrocarbons in mercuric iodide single crystals

    NASA Astrophysics Data System (ADS)

    Steinberg, S.; Kaplan, I.; Schieber, M.; Ortale, C.; Skinner, N.; van den Berg, L.

    1989-11-01

    Total organic carbon was determined by measuring the CO2 produced by combustion in a sealed quartz vessel. The CO2 was quantified by nondispersive IR and by titration using commercial detectors. The total organic carbon was found to be around 10-100 ?g/g in both starting materials and in single crystals. Gas chromatography-mass spectroscopy (GC/MS) measurements were made on hexane extracts of mercuric iodide (HgI2) dissolved in potassium iodide solution. Hydrocarbons starting with C10 (DIENE) and up to C26 were found. In addition, phthalates, such as diethyl and dioctyl phthalate were also found. Some of the organic compounds, for example, such hydrocarbons as branched nC16, nC20, nC21, nC22, nC23, and nC24, were present in some HgI2 materials in quantities of the order of weight ppm, but were eliminated in the purification process and were not found in the single crystals. Other organic compounds such as the phthalates were not always eliminated and were identified in the single crystals. In general, the GC/MS could identify only hydrocarbons of C10 and higher which account for only a few percent of the total organic carbon determined by oxidation.

  1. Solidification of floating organic drop liquid-phase microextraction cell fishing with gas chromatography-mass spectrometry for screening bioactive components from Amomum villosum Lour.

    PubMed

    Xue, Xue; Yang, Depo; Wang, Dongmei; Xu, Xinjun; Zhu, Longping; Zhao, Zhimin

    2015-04-01

    In this study, a novel solidification of floating organic drop liquid-phase microextraction cell fishing with gas chromatography-mass spectrometry (SFOD-LPME-CF-GC-MS) method was established and used to screen, isolate and analyze bioactive components from Amomum villosum Lour. extract. Through comparision of its effect on the models of normal cell and inflammatory cells, anti-inflammatory active components of essential oil from A. villosum Lour. were readily screened, and the components obtained are in agreement with related pharmacological articles. SFOD-LPME-CF-GC-MS was used to analyze the interaction of A. villosum Lour. extracts with normal and lipopolysaccharide-stimulated RAW264.7 macrophage cells. The effect of A. villosum Lour. essential oil extracts in the LPS-stimulated RAW264.7 model were also assessed in terms of cytotoxicity and nitric oxide production as an indication of bioactivity. Three potentially bioactive components were identified, demonstrating that SFOD-LPME-CF-GC-MS can be used successfully in the drug-screening process. This approach avoids the requirement for protein precipitation, but more importantly, generates a high concentration ratio, allowing analysis of trace components in traditional Chinese medicines. SFOD-LPME-CF-GC-MS is a simple, fast, effective and reliable method for the screening and analysis of bioactive components, and it can be extended to screen other bioactive components from TCMs. PMID:25251881

  2. Gas-Chromatography Mass-Spectrometry (GC-MS) Based Metabolite Profiling Reveals Mannitol as a Major Storage Carbohydrate in the Coccolithophorid Alga Emiliania huxleyi.

    PubMed Central

    Obata, Toshihiro; Schoenefeld, Steffi; Krahnert, Ina; Bergmann, Susan; Scheffel, Andr; Fernie, Alisdair R.

    2013-01-01

    Algae are divergent organisms having a wide variety of evolutional histories. Although most of them share photosynthetic activity, their pathways of primary carbon metabolism are rather diverse among species. Here we developed a method for gas chromatography-mass spectroscopy (GC-MS) based metabolite profiling for the coccolithophorid alga Emiliania huxleyi, which is one of the most abundant microalgae in the ocean, in order to gain an overview of the pathway of primary metabolism within this alga. Following method optimization, twenty-six metabolites could be detected by this method. Whilst most proteogenic amino acids were detected, no peaks corresponding to malate and fumarate were found. The metabolite profile of E. huxleyi was, however, characterized by a prominent accumulation of mannitol reaching in excess of 14 nmol 106 cells?1. Similarly, the accumulation of the 13C label during short term H13CO3? feeding revealed a massive redistribution of label into mannitol as well as rapid but saturating label accumulation into glucose and several amino acids including aspartate, glycine and serine. These results provide support to previous work suggesting that this species adopts C3 photosynthesis and that mannitol functions as a carbon store in E. huxleyi. PMID:24957896

  3. Determination of the alkylpyrazine composition of coffee using stable isotope dilution-gas chromatography-mass spectrometry (SIDA-GC-MS).

    PubMed

    Pickard, Stephanie; Becker, Irina; Merz, Karl-Heinz; Richling, Elke

    2013-07-01

    A stable isotope dilution analysis based on gas chromatography-mass spectrometry analysis (SIDA-GC-MS) was developed for the quantitative analysis of 12 alkylpyrazines found in commercially available coffee samples. These compounds contribute to coffee flavor. The accuracy of this method was tested by analyzing model mixtures of alkylpyrazines. Comparisons of alkylpyrazine-concentrations suggested that water as extraction solvent was superior to dichloromethane. The distribution patterns of alkylpyrazines in different roasted coffees were quite similar. The most abundant alkylpyrazine in each coffee sample was 2-methylpyrazine, followed by 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, and 2,3,5-trimethylpyrazine, respectively. Among the alkylpyrazines tested, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 2-ethyl-3,5-dimethylpyrazine revealed the lowest concentrations in roasted coffee. By the use of isotope dilution analysis, the total concentrations of alkylpyrazines in commercially available ground coffee ranged between 82.1 and 211.6 mg/kg, respectively. Decaffeinated coffee samples were found to contain lower amounts of alkylpyrazines than regular coffee samples by a factor of 0.3-0.7, which might be a result of the decaffeination procedure. PMID:23745606

  4. Development of sample clean up methods for the analysis of Mycobacterium tuberculosis methyl mycocerosate biomarkers in sputum extracts by gas chromatographymass spectrometry

    PubMed Central

    Nicoara, Simona C.; Turner, Nicholas W.; Minnikin, David E.; Lee, Oona Y.-C.; O'Sullivan, Denise M.; McNerney, Ruth; Mutetwa, Reggie; Corbett, Liz E.; Morgan, Geraint H.

    2015-01-01

    A proof of principle gas chromatographymass spectrometry method is presented, in combination with clean up assays, aiming to improve the analysis of methyl mycocerosate tuberculosis biomarkers from sputum. Methyl mycocerosates are generated from the transesterification of phthiocerol dimycocerosates (PDIMs), extracted in petroleum ether from sputum of tuberculosis suspect patients. When a high matrix background is present in the sputum extracts, the identification of the chromatographic peaks corresponding to the methyl derivatives of PDIMs analytes may be hindered by the closely eluting methyl ether of cholesterol, usually an abundant matrix constituent frequently present in sputum samples. The purification procedures involving solid phase extraction (SPE) based methods with both commercial Isolute-Florisil cartridges, and purpose designed molecularly imprinted polymeric materials (MIPs), resulted in cleaner chromatograms, while the mycocerosates are still present. The clean-up performed on solutions of PDIMs and cholesterol standards in petroleum ether show that, depending on the solvent mix and on the type of SPE used, the recovery of PDIMs is between 64 and 70%, whilst most of the cholesterol is removed from the system. When applied to petroleum ether extracts from representative sputum samples, the clean-up procedures resulted in recoveries of 3668% for PDIMs, allowing some superior detection of the target analytes. PMID:25728371

  5. Dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry determination of polychlorinated biphenyls and polybrominated diphenyl ethers in milk.

    PubMed

    Liu, Xiujuan; Zhao, Aijun; Zhang, Aina; Liu, Huanqiang; Xiao, Wenjing; Wang, Chengjun; Wang, Xuedong

    2011-05-01

    An effective multi-residue pretreatment technique, solid-phase extraction (SPE) combined with dispersive liquid-liquid microextraction (DLLME), was proposed for the trace analysis of 14 polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk samples using gas chromatography-mass spectrometry (GC-MS). Interesting analytes in milk samples were extracted with hexane after protein precipitation. The hexane extracts were loaded on an LC-Florisil column to isolate analytes from the milk matrix. The elutes were dried and dissolved in acetone, which was used as the disperser solvent in subsequent DLLME procedures. The effects of several important parameters on the extraction efficiency were evaluated. Under the optimized conditions, a linear relationship was obtained in the range of 0.02-10.00 μg/L (PCBs) and 0.5-100.00 μg/L (PBDEs). The LOD (S/N=3) and relative standard deviations (RSDs, n=5) for all analytes were 0.01-0.4 μg/L and 0.6-8.5%, respectively. The recoveries of the standards added to raw bovine milk samples were 74.0-131.8%, and the repeatabilities of the analysis results were 1.12-17.41%. This method has been successfully applied to estimating PCBs and PBDEs in milk samples. PMID:21394909

  6. [Determination of 28 organochlorine and pyrethroid pesticides in pine nuts using solid-phase extraction and on-line gel permeation chromatography-gas chromatography/mass spectrometry].

    PubMed

    Kang, Qinghe; Wu, Yan; Gao, Kaiyang; Li, Zhibin

    2009-03-01

    An analytical method has been developed for the determination of 28 organochlorine pesticides and pyrethroid pesticides in pine nuts. The sample was extracted With acetonitrile-water (4:1, v/v) as the extraction solution by means of high-speed homogenization. The crude extract was purified by an Aluminium-N solid phase extraction column to remove most of the fat and sterols in the sample, then on-line gel permeation chromatography-gas chromatography/ mass spectrometry (GPC-GC/MS) analysis was performed. The recoveries for the most of pesticides in the sample spiked with the standards of 0.05 mg/kg were 70%-120%, and the relative standard deviations were less than 15%. The limits of detection of 28 organochlorine pesti- and pyrethroid pesticides were 0.002-0.05 mg/kg. The linear relationship and the recovery results were satisfactory. The method is rapid, accurate, highly senstive, and can be used for the simultaneous determination of pesticide residues in pine nuts. PMID:19626845

  7. Analysis of tramadol and O-desmethyltramadol in decomposed skeletal tissues following acute and repeated tramadol exposure by gas chromatography mass spectrometry.

    PubMed

    Wiebe, Treena R; Watterson, James H

    2014-09-01

    Decomposed bone and plasma samples of rats exposed to tramadol (TRAM) under different dosing patterns were analyzed. Wistar rats received TRAM as one acute dose (n=4, 45 mg/kg, i.p.) or three doses (n=4, 15 mg/kg, i.p.), 40 min apart. Perimortem heart blood was collected, rats were euthanized and placed outdoors to decompose to skeleton. Recovered bone was ground and subjected to methanolic extraction. Bone extracts and plasma samples underwent solid phase extraction and were analyzed using gas chromatography-mass spectrometry. Levels of TRAM and the primary metabolite O-desmethyltramadol (ODMT) were expressed as mass normalized response ratios (RR/m). Levels (RR/m) for TRAM and ODMT did not differ significantly between exposure types in any of the bone types examined or for the pooled bone comparisons (Mann-Whitney, p>0.05). However, ratios of analyte levels (RRTRAM/RRODMT) differed significantly between exposure patterns for tibial and skull bone as well as for pooled bone comparisons (Mann-Whitney, p<0.05). Levels of TRAM and ODMT, as well as ratios of analyte levels (RRTRAM/RRODMT), differed significantly in plasma between exposure patterns. Bone TRAM and ODMT levels were poorly correlated to corresponding plasma levels (TRAM: r=0.33-0.57; ODMT: r=-0.35-0.23). PMID:25112198

  8. The Occurrence of Propyl Lactate in Chinese Baijius (Chinese Liquors) Detected by Direct Injection Coupled with Gas Chromatography-Mass Spectrometry.

    PubMed

    Wu, Jihong; Zheng, Yang; Sun, Baoguo; Sun, Xiaotao; Sun, Jiyuan; Zheng, Fuping; Huang, Mingquan

    2015-01-01

    As one of the oldest distillates in the world, flavor compounds of Chinese Baijiu (Chinese liquor) were extremely complex. Propyl lactate was ?rstly detected by direct injection and gas chromatography-mass spectrometry (GC-MS) in 72 Chinese Baijius. The objectives were to detect the contents of propyl lactate and evaluate its contribution to the aroma of Chinese Baijiu based on odor activity values (OAVs). The levels of propyl lactate in these distillates were determined by internal standard method and selective ion monitoring (SIM), which ranged from 0.050 to 1.900 mg?L(-1) under investigation. Its detection threshold was determined by Three-Alternative Forced-Choice (3-AFC) and curve fitting (CF), which was 0.740 mg?L(-1) in 38% ethanol solution. The contribution of propyl lactate on the aroma of these distillate drinks was evaluated by their odor activity values (OAVs), which varied from 0.066 to 4.440. The OAVs of propyl lactate were found to exceed 1 in 13 Chinese Baijius, including 50 Jingzhi Guniang 5 years (4.440), 52 Jingzhi Guniang 10 years (3.024), Jingyanggang (2.568), Xianghe Ronghe Shaofang (2.313), and 1956 Laolang (1.431), which indicated that propyl lactate was one of odor-active components in these Chinese Baijius. PMID:26492228

  9. Thermal extraction-two-dimensional gas chromatography-mass spectrometry with heart-cutting for nitrogen heterocyclics in biomass burning aerosols.

    PubMed

    Ma, Yilin; Hays, Michael D

    2008-07-25

    A thermal extraction-two-dimensional gas chromatography-mass spectrometry (TE-GC-GC-MS) method with heart-cutting is developed for quantitatively assessing nitrogen (N)-bearing organic species (e.g., pyrrole, pyridine, nitriles, and amines) in aerosols emitted from agricultural fires. Pyrolysis of the constituents in the crop residue is a likely formation pathway for these compounds. An evaluation of the TE-GC-GC-MS method proficiency for them confirms low carryover (<1%), adequate recovery (84-100%), high reproducibility (<9% RSD), picogram method detection limits, and a linear dynamic range spanning four orders of magnitude. The 14 substances for which quantitative results are available are primarily heterocyclic aromatic N compounds that comprise 0.7% (w/w) of the total fine aerosol mass. The benefits of TE-GC-GC-MS versus conventional GC-MS methods for organic N species in aerosols may depend on the matrix and the target N analyte concentration in that matrix; for the biomass burning aerosol examined in this study, the former approach reduces the unresolved complex mixture and detects organic N species not seen with GC-MS. We show another advantage of TE-GC-GC-MS is that it adequately resolves the anhydro-sugar (e.g., levoglucosan), alkanoic acid, and substituted phenol molecules in the biomass burning aerosol without the use of methylation or trimethyl-silyl derivatizing agents. PMID:18571186

  10. Qualitative and Quantitative Analysis of Volatile Components of Zhengtian Pills Using Gas Chromatography Mass Spectrometry and Ultra-High Performance Liquid Chromatography.

    PubMed

    Liu, Cui-Ting; Zhang, Min; Yan, Ping; Liu, Hai-Chan; Liu, Xing-Yun; Zhan, Ruo-Ting

    2016-01-01

    Zhengtian pills (ZTPs) are traditional Chinese medicine (TCM) which have been commonly used to treat headaches. Volatile components of ZTPs extracted by ethyl acetate with an ultrasonic method were analyzed by gas chromatography mass spectrometry (GC-MS). Twenty-two components were identified, accounting for 78.884% of the total components of volatile oil. The three main volatile components including protocatechuic acid, ferulic acid, and ligustilide were simultaneously determined using ultra-high performance liquid chromatography coupled with diode array detection (UHPLC-DAD). Baseline separation was achieved on an XB-C18 column with linear gradient elution of methanol-0.2% acetic acid aqueous solution. The UHPLC-DAD method provided good linearity (R (2) ? 0.9992), precision (RSD < 3%), accuracy (100.68-102.69%), and robustness. The UHPLC-DAD/GC-MS method was successfully utilized to analyze volatile components, protocatechuic acid, ferulic acid, and ligustilide, in 13 batches of ZTPs, which is suitable for discrimination and quality assessment of ZTPs. PMID:26904360

  11. [Applications of multi-micro-volume pressure-assisted derivatization reaction device for analysis of polar heterocyclic aromatic amines by gas chromatography-mass spectrometry].

    PubMed

    Wang, Yiru; Chen, Fangxiang; Shi, Yamei; Tan, Connieal; Chen, Xi

    2013-01-01

    A multi-micro-volume pressure-assisted derivatization reaction device has been designed and made for the silylation derivatization of polar heterocyclic aromatic amines by N-(tert-butyldimethylsilyl )-N-methyl-trifluoroacetamide (MTBSTFA) with 1% catalyst tert-butyldimethylchlorosilane (TBDMCS) at a high temperature. The tert-butyldimethylsilyl derivatives then could be automatically analyzed by gas chromatography-mass spectrometry. Using the pressure-assisted device, the silylation reaction may occur at a temperature higher than the boiling points of the reagents, and several micro-volume samples can be simultaneously pretreated in the same device to shorten the sample-preparation time and to improve the repeatability. The derivatization conditions including the headspace volume of the vial, the evaporative surface area of the reagent, derivatization temperature and time have been discussed for the use of the pressure-assisted device. The experimental results proved that the device is an effective way for the simultaneous derivatization of several micro-volume samples at a high temperature. Compared with a common device, the derivative amounts were obviously increased when using the pressure-assisted device at 90 degrees C. Quantitative derivatization can be achieved even at 150 degrees C while there was no common device could be applied at such a high temperature due to the heavy losses of reagents by evaporation. However, no obviously higher reaction speed has been observed in such a circumstance with a higher temperature and a higher pressure using the pressure-assisted device. PMID:23667982

  12. Membrane assisted solvent extraction coupled to large volume injection-gas chromatography-mass spectrometry for trace analysis of synthetic musks in environmental water samples.

    PubMed

    Posada-Ureta, O; Olivares, M; Navarro, P; Vallejo, A; Zuloaga, O; Etxebarria, N

    2012-03-01

    This work describes the optimisation, validation and application of membrane assisted solvent extraction (MASE) together with a large volume injection (LVI) in a programmable temperature vaporisation (PTV) injector coupled to gas chromatography-mass spectrometry (GC-MS) for the quantification of ten synthetic musk fragrances (musks) in surface and wastewater samples. Regarding the MASE, musks were extracted from 150 mL of aqueous samples to 200 ?L of n-hexane hold in home-made low density polyethylene (LDPE) bags. The extraction took 240 min and the performance of the method made possible the direct analysis of the extracts by LVI-PTV-GC-MS without needing any further treatment and avoiding losses of analytes. During the optimisation of LVI-PTV set-up, the response surfaces of every analyte signal against the cryo-focussing temperature, injection speed and vent time were built. Finally, the figures of merit of the whole procedure allowed the analysis of most of the musks owing to the low method detection limits (between 4 and 25 ng L?) and good precisions (<20%). In fact, this method was successfully applied to the analysis of musks in surface and wastewater samples. Galaxolide and tonalide are the main two synthetic musks observed in most of the analysed environmental water samples. PMID:22265174

  13. Metabolic Profiling with Gas Chromatography-Mass Spectrometry and Capillary Electrophoresis-Mass Spectrometry Reveals the Carbon-Nitrogen Status of Tobacco Leaves Across Different Planting Areas.

    PubMed

    Zhao, Jieyu; Zhao, Yanni; Hu, Chunxiu; Zhao, Chunxia; Zhang, Junjie; Li, Lili; Zeng, Jun; Peng, Xiaojun; Lu, Xin; Xu, Guowang

    2016-02-01

    The interaction between carbon (C) and nitrogen (N) metabolism can reflect plant growth status and environmental factors. Little is known regarding the connections between C-N metabolism and growing regions under field conditions. To comprehensively investigate the relationship in mature tobacco leaves, we established metabolomics approaches based on gas chromatography-mass spectrometry (GC-MS) and capillary electrophoresis-time-of-flight-mass spectrometry (CE-TOF-MS). Approximately 240 polar metabolites were determined. Multivariate statistical analysis revealed that the growing region greatly influenced the metabolic profiles of tobacco leaves. A metabolic correlation network and related pathway maps were used to reveal the global overview of the alteration of C-N metabolism across three typical regions. In Yunnan, sugars and tricarboxylic acid (TCA) cycle intermediates were closely correlated with amino acid pools. Henan tobacco leaves showed positive correlation between the pentose phosphate pathway (PPP) intermediates and C-rich secondary metabolism. In Guizhou, the proline and asparagine had significant links with TCA cycle intermediates and urea cycle, and antioxidant accumulation was observed in response to drought. These results demonstrate that combined analytical approaches have great potential to detect polar metabolites and provide information on C-N metabolism related to planting regional characteristics. PMID:26784525

  14. Simultaneous analysis of phthalates, adipate and polycyclic aromatic hydrocarbons in edible oils using isotope dilution-gas chromatography-mass spectrometry.

    PubMed

    Oh, Min-Seok; Lee, Seon-Hwa; Moon, Myeong Hee; Lee, Dong Soo; Park, Hyun-Mee

    2014-01-01

    A method for simultaneous determination of 12 priority phthalates, adipate and polycyclic aromatic hydrocarbons (PAHs) in edible oils by isotope dilution-gas chromatography-mass spectrometry (ID-GC-MS) was developed for fast, accurate and trace analysis. The extraction and clean-up procedures were optimised, and using stable isotope-labelled internal standards for each analyte, relative standard deviations (RSDs) of 0.92-10.6% and spiked sample recoveries of 80.6-97.8% were obtained. Limits of detection for PAHs were in the range of 0.15-0.77 g/kg and those for phthalates were in the range of 4.6-10.0 g/kg. The calibration curves exhibited good linearities with regression coefficients of R(2) ? 0.99. Twelve edible oils were examined to evaluate the efficiency of this method. Among the 12 analytes, dibutyl phthalates (DBP), diethylhexyl phthalates (DEHP), diethylhexyl adipate (DEHA), benzo[a]anthracene (B[a]A), chrysene (Chry) and benzo[b]fluoranthene (B[b]F) were detected in the range of 1.17-806 g/kg. PMID:25029399

  15. Dispersive microextraction based on "magnetic water" coupled to gas chromatography/mass spectrometry for the fast determination of organophosphorus pesticides in cold-pressed vegetable oils.

    PubMed

    Zhao, Qin; Lu, Qian; Yu, Qiong-Wei; Feng, Yu-Qi

    2013-06-01

    This article presents a novel application of dispersive microextraction based on "magnetic water" (m-water) for the purification of organophosphorus pesticides (methamidophos, omethoate, monocrotophos) from cold-pressed vegetable oils. In the present study, a trace amount of water (extractant) was adsorbed on bare Fe?O? by hydrophilic interaction to form m-water. Rapid extraction can be achieved while the m-water is dispersed in the sample solution with the aid of a vigorous vortex. After extraction, the analyte-adsorbed m-water can be readily isolated from the sample solution by a magnet, which could greatly simplify the operation and reduce the whole pretreatment time. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for pesticide analysis was established by coupling with gas chromatography/mass spectrometry (GC/MS). The linearity range of the proposed method was 2-100 ng/g with satisfactory correlation coefficients (R) of 0.9997-0.9998, and the limits of quantification (LOQ) for the target compounds were in the range of 0.70-1.27 ng/g. In addition, the reproducibility was obtained by evaluating the intra- and interday precisions with relative standard deviations (RSDs) less than 7.2% and 6.5%, respectively. Finally, the established "magnetic water" microextraction method was successfully applied for the determination of pesticide residues in several kinds of cold-pressed vegetable oils. PMID:23687955

  16. Two-dimensional gas chromatography/mass spectrometry, physical property modeling and automated production of component maps to assess the weathering of pollutants.

    PubMed

    Antle, Patrick M; Zeigler, Christian D; Livitz, Dimitri G; Robbat, Albert

    2014-10-17

    Local conditions influence how pollutants will weather in subsurface environments and sediment, and many of the processes that comprise environmental weathering are dependent upon these substances' physical and chemical properties. For example, the effects of dissolution, evaporation, and organic phase partitioning can be related to the aqueous solubility (SW), vapor pressure (VP), and octanol-water partition coefficient (KOW), respectively. This study outlines a novel approach for estimating these physical properties from comprehensive two-dimensional gas chromatography-mass spectrometry (GCGC/MS) retention index-based polyparameter linear free energy relationships (LFERs). Key to robust correlation between GC measurements and physical properties is the accurate and precise generation of retention indices. Our model, which employs isovolatility curves to calculate retention indices, provides improved retention measurement accuracy for families of homologous compounds and leads to better estimates of their physical properties. Results indicate that the physical property estimates produced from this approach have the same error on a logarithmic-linear scale as previous researchers' log-log estimates, yielding a markedly improved model. The model was embedded into a new software program, allowing for automated determination of these properties from a single GCGC analysis with minimal model training and parameter input. This process produces component maps that can be used to discern the mechanism and progression of how a particular site weathers due to dissolution, organic phase partitioning, and evaporation into the surrounding environment. PMID:25223613

  17. Diagnosis of 21-hydroxylase deficiency by urinary metabolite ratios using gas chromatography-mass spectrometry analysis: Reference values for neonates and infants.

    PubMed

    Kamrath, Clemens; Hartmann, Michaela F; Boettcher, Claudia; Zimmer, Klaus-Peter; Wudy, Stefan A

    2016-02-01

    One major issue of newborn screening programs for 21-hydroxylase deficiency (21OHD) is the high rate of false-positive results, especially in preterm neonates. Urinary steroid metabolite analysis using gas chromatography-mass spectrometry (GC-MS) is suitable as a confirmatory diagnostic tool. The objective of this study was to analyze retrospectively diagnostic metabolite ratios in neonates and infants with and without 21OHD using GC-MS with emphasis on glucocorticoid metabolism, and to develop reference values for the steroid metabolite ratios for the diagnosis of 21OHD. We retrospectively analyzed urinary steroid hormone metabolites determined by GC-MS of 95 untreated neonates and infants with 21OHD (1-148 days), and 261 neonates and infants (100 preterms) without 21OHD (0-217 days). Metabolites of 17?-hydroxyprogesterone showed specificities below 98%, whereas the 21-deoxycortisol metabolite pregnanetriolone clearly separated 21OHD from non-21OHD subjects. The best diagnostic ratio for 21OHD was pregnanetriolone to 6?-hydroxy-tetrahydrocortisone. The lowest value of this ratio in the 21OHD group (0.47) was at least eight times higher than the highest values in the non-21OHD group (0.055). We have given appropriate reference values for steroid metabolite ratios in the largest 21OHD cohort so far described. Consideration of glucocorticoid metabolism, especially the use of typical neonatal 6?-hydroxylates metabolites, leads to improvement of diagnostic metabolite ratios. PMID:26493852

  18. Comprehensive characterisation of flame retardants in textile furnishings by ambient high resolution mass spectrometry, gas chromatography-mass spectrometry and environmental forensic microscopy.

    PubMed

    Ionas, Alin C; Ballesteros Gmez, Ana; Uchida, Natsuyo; Suzuki, Go; Kajiwara, Natsuko; Takata, Kyoko; Takigami, Hidetaka; Leonards, Pim E G; Covaci, Adrian

    2015-10-01

    The presence and levels of flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and organophosphate flame retardants (PFRs), was determined in textile home furnishings, such as carpets and curtains from stores in Belgium. A comprehensive characterisation of FRs in textile was done by ambient high resolution mass spectrometry (qualitative screening), gas chromatography-mass spectrometry (GC-MS) (quantitation), and environmental forensic microscopy (surface distribution). Ambient ionisation coupled to a time-of-flight (TOF) high resolution mass spectrometer (direct probe-TOF-MS) was investigated for the rapid screening of FRs. Direct probe-TOF-MS proved to be useful for a first screening step of textiles to detect FRs below the levels required to impart flame retardancy and to reduce, in this way, the number of samples for further quantitative analysis. Samples were analysed by GC-MS to confirm the results obtained by ambient mass spectrometry and to obtain quantitative information. The levels of PBDEs and PFRs were typically too low to impart flame retardancy. Only high levels of BDE-209 (11-18% by weight) were discovered and investigated in localised hotspots by employing forensic microscopy techniques. Most of the samples were made of polymeric materials known to be inherently flame retarded to some extent, so it is likely that other alternative and halogen-free FR treatments/solutions are preferred for the textiles on the Belgian market. PMID:26398896

  19. Microwave-assisted one-step extraction-derivatization for rapid analysis of fatty acids profile in herbal medicine by gas chromatography-mass spectrometry.

    PubMed

    Liu, Rui-Lin; Zhang, Jing; Mou, Zhao-Li; Hao, Shuang-Li; Zhang, Zhi-Qi

    2012-11-01

    A rapid and practical microwave-assisted one-step extraction-derivatization (MAED) method was developed for gas chromatography-mass spectrometry analysis of fatty acids profile in herbal medicine. Several critical experimental parameters for MAED, including reaction temperature, microwave power and the amount of derivatization reagent (methanol), were optimized with response surface methodology. The results showed that the chromatographic peak areas of total fatty acids and total unsaturated fatty acids content obtained with MAED were markedly higher than those obtained by the conventional Soxhlet or microwave extraction and then derivatization method. The investigation of kinetics and thermodynamics of the derivatization reaction revealed that microwave assistance could reduce activation energy and increase the Arrhenius pre-exponential factor. The MAED method simplified the sample preparation procedure, shortened the reaction time, but improved the extraction and derivatization efficiency of lipids and reduced ingredient losses, especially for the oxidization and isomerization of unsaturated fatty acids. The simplicity, speed and practicality of this method indicates great potential for high throughput analysis of fatty acids in natural medicinal samples. PMID:22968083

  20. Determination of aromatic amines in hair dye and henna samples by ion-pair extraction and gas chromatography-mass spectrometry.

    PubMed

    Akyz, Mehmet; Ata, Sevket

    2008-05-12

    A gas chromatography-mass spectrometry (GC-MS) method has been proposed for the determination of carcinogenic and toxic aromatic amines in hair dye, henna and dyed hair samples. The method includes ion-pair extraction of aromatic amines from aqueous samples with bis-2-ethylhexylphosphate (BEHPA) released after solving the samples in acidic solution followed by sonication, derivatisation of compounds with isobutyl chloroformate (IBCF) and their GC-MS analysis in both electron impact (EI) and positive and negative ion chemical ionisation (PNICI) mode as their isobutyloxycarbonyl (isoBOC) derivatives. The obtained recoveries of aromatic amines ranged from 92.2 to 98.4% and the precision of this method, as indicated by the relative standard deviations (RSDs) was within the range of 0.7-4.2%. The detection limits obtained from calculations by using GC-MS results based on signal-to-noise ratio (S/N)=3 were within the range from 0.02 to 0.20 ng/g. In the present study, the commercially available 54 permanent hair dye, 35 modified or natural henna and 15 dyed hair samples were analysed for the aromatic amines by the proposed method and the method was shown to be suitable to determine the aromatic amine ingredients and metabolites of these commercial products. PMID:18280687

  1. Rapid Monitoring and Determination of Class 1 Residual Solvents in Pharmaceuticals Using Dispersive Liquid-Liquid Microextraction and Gas Chromatography-Mass Spectrometry.

    PubMed

    Heydari, Rouhollah; Azizi, Saber

    2015-07-01

    A simple and rapid dispersive liquid-liquid microextraction (DLLME) method coupled with gas chromatography-mass spectrometry (GC-MS) for monitoring and determination of class 1 residual solvents, benzene (Bz), carbon tetrachloride (CT), 1,2-dichloroethane (1,2-DCE), 1,1-dichloroethene (1,1-DCE), 1,1,1-trichloroethane (1,1,1-TCE), in pharmaceuticals was developed and evaluated. The parameters affecting the extraction efficiency of analytes such as type and volume of extraction solvent, type and volume of dispersive solvent and ionic strength were investigated and optimized. 1-Octanol and methanol proved to be the most suitable extraction and dispersive solvents, respectively. The method showed linearity for 1,1-DCE, 1,1,1-TCE, CT, Bz and 1,2-DCE in the ranges of 0.001-80, 0.005-80, 0.002-80, 0.0001-40 and 0.001-80 g/mL, respectively. The relative recoveries were in the range of 84-92, 87-98, 83-94, 89-98 and 87-96% for 1,1-DCE, 1,1,1-TCE, CT, Bz and 1,2-DCE, respectively. The obtained results showed that the proposed method can be used to monitor and determine class 1 residual solvents in pharmaceuticals. PMID:25398952

  2. Simultaneous quantification of Aroclor mixtures in soil samples by gas chromatography/mass spectrometry with solid phase microextraction using partial least-squares regression.

    PubMed

    Zhang, Mengliang; Harrington, Peter de B

    2015-01-01

    Multivariate partial least-squares (PLS) method was applied to the quantification of two complex polychlorinated biphenyls (PCBs) commercial mixtures, Aroclor 1254 and 1260, in a soil matrix. PCBs in soil samples were extracted by headspace solid phase microextraction (SPME) and determined by gas chromatography/mass spectrometry (GC/MS). Decachlorinated biphenyl (deca-CB) was used as internal standard. After the baseline correction was applied, four data representations including extracted ion chromatograms (EIC) for Aroclor 1254, EIC for Aroclor 1260, EIC for both Aroclors and two-way data sets were constructed for PLS-1 and PLS-2 calibrations and evaluated with respect to quantitative prediction accuracy. The PLS model was optimized with respect to the number of latent variables using cross validation of the calibration data set. The validation of the method was performed with certified soil samples and real field soil samples and the predicted concentrations for both Aroclors using EIC data sets agreed with the certified values. The linear range of the method was from 10?gkg(-1) to 1000?gkg(-1) for both Aroclor 1254 and 1260 in soil matrices and the detection limit was 4?gkg(-1) for Aroclor 1254 and 6?gkg(-1) for Aroclor 1260. This holistic approach for the determination of mixtures of complex samples has broad application to environmental forensics and modeling. PMID:25216382

  3. A peaklet-based generic strategy for the untargeted analysis of comprehensive two-dimensional gas chromatography mass spectrometry data sets.

    PubMed

    Egert, Bjrn; Weinert, Christoph H; Kulling, Sabine E

    2015-07-31

    Comprehensive two-dimensional gas chromatography mass spectrometry (GCGC-MS) is a well-established key technology in analytical chemistry and increasingly used in the field of untargeted metabolomics. However, automated processing of large GCGC-MS data sets is still a major bottleneck in untargeted, large-scale metabolomics. For this reason we introduce a novel peaklet-based alignment strategy. The algorithm is capable of an untargeted deterministic alignment exploiting a density based clustering procedure within a time constrained similarity matrix. Exploiting minimal (1)D and (2)D retention time shifts between peak modulations, the alignment is done without the need for peak merging which also eliminates the need for linear or nonlinear retention time correction procedures. The approach is validated in detail using data of urine samples from a large human metabolomics study. The data was acquired by a Shimadzu GCMS-QP2010 Ultra GCGC-qMS system and consists of 512 runs, including 312 study samples and 178 quality control sample injections, measured within a time period of 22 days. The final result table consisted of 313 analytes, each of these being detectable in at least 75% of the study samples. In summary, we present an automated, reliable and fully transparent workflow for the analysis of large GCGC-qMS metabolomics data sets. PMID:26074098

  4. Trace-level determination of polar flavour compounds in butter by solid-phase extraction and gas chromatography-mass spectrometry.

    PubMed

    Adahchour, M; Vreuls, R J; van der Heijden, A; Brinkman, U A

    1999-06-01

    Volatile compounds are responsible for the aromas of butter. A simple technique for the determination of these components is described which is based on solid-phase extraction (SPE) after melting of the butter and separation of the aqueous phase from the fat. Volatile flavours present in the water fraction are collected by off-line SPE on cartidges packed with a copolymer sorbent. After desorption with 500 microliters of methyl acetate, 1-microliter aliquots are quantified and/or identified by gas chromatography-mass spectrometry. The procedure was tested with respect to recovery, linearity and limit of detection in real-life samples using five polar model analytes. It allows the characterisation of polar flavour compounds in butter prior to and after heat treatment at 170 degrees C. From the five model compounds, vanillin, traces of diacetyl and maltol were found to be present in the butter samples. After heat treatment 500-1000-fold increased concentration of maltol, and substantial amounts of furaneol were detected. PMID:10399332

  5. Identification and characterization of vinylpyrrolidone-vinylimidazolium chloride copolymers in cosmetic products by pyrolysis-gas chromatography-mass spectrometry method.

    PubMed

    Gmahl, E; Ruess, W

    1993-04-01

    Synopsis Commercially available copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium chloride, known as 'Luviquat' types in the cosmetic industry, were analysed for their composition using a combination of pyrolysis-gas chromatography-mass spectrometry method. This is a report on the determined pyrolytic products and the fast identification of the analysed polymers both in raw materials and cosmetic products. Calibration with defined material ensures the determination of monomer ratios with good reproducibility. Rsum Les copolymres de chlorure de 1-vinyle-2-pyrolidone et de 1-vinyle-3-methylimidazolium disponibles dans le commerce, connus dans l'industrie cosmtique sous la dnomination de copolymres de vinyle, ont t analyss laide d'une mthode combinant la pyrolyse, la spectromtrie de mass et la chromatographie en phase gazeuse. Cet article constitue un rapport sur les produits dtermins par pyrolyse et sur la rapidit d'identification des polymres analyss la fois dans des matires premires et dans des produits cosmtiques. Le calibrage avec un matriel dfini assure une bonne dtermination des taux de monomres dots d'une reproductibilit. PMID:19272122

  6. Determination of nicotine and other minor alkaloids in international cigarettes by solid-phase microextraction and gas chromatography/mass spectrometry.

    PubMed

    Wu, Weijia; Ashley, David L; Watson, Clifford H

    2002-10-01

    Nicotine, nornicotine, anabasine, and anatabine are the most abundant alkaloids in tobacco. Along with the addictiveness of nicotine, other properties, including their occurrence in tobacco at relatively high concentrations, and as the primary precursors for the highly carcinogenic tobacco-specific nitrosoamines, make these chemicals important from a public health standpoint Therefore, developing a fast and accurate quantitative method to screen large numbers of cigarette samples for these alkaloids was important. This report describes the first use of headspace analysis using solid-phase microextraction combined with gas chromatography/mass spectrometry for the unambiguous detection of tobacco alkaloids. Detection and confirmation of each analyte isestablished by both chromatographic retention times and the ratio of reconstructed ion chromatogram peak areas from characteristic quantitation ion and confirmation ion. Twenty-eight cigarette brands from 14 countries were analyzed. Surprisingly, the minor alkaloids' response factors varied considerably among different styles of cigarettes. Accurate quantification was achieved using a three-point standard addition protocol. The standard addition approach was essential to obtain accurate measurements by minimizing matrix effects that would otherwise have contributed to quantitation bias. Significant differences in the alkaloid profiles were measured in the different cigarette brands. These results strongly suggest that such differences reflect variations associated with blend compositions, tobacco quality, and manufacturing practices. PMID:12380807

  7. Combination of direct infusion mass spectrometry and gas chromatography mass spectrometry for toxicometabolomic study of red blood cells and serum of mice Mus musculus after mercury exposure.

    PubMed

    Garca-Sevillano, M A; Garca-Barrera, T; Navarro, F; Abril, N; Pueyo, C; Lpez-Barea, J; Gmez-Ariza, J L

    2015-03-15

    Although mercury (Hg) is an important environmental and occupational pollutant, its toxicological effects, especially in serum and red blood cells (RBCs), have been scarcely studied. A toxicometabolomics workflow based on high resolution mass spectrometry approaches has been applied to investigate the toxicological effects of Hg in Mus musculus mice after subcutaneous injection for 10 days, which produced inflammation and vacuolization, steatosis and karyolysis in the hepatic tissue. To this end, direct infusion mass spectrometry (DIMS) of polar and lipophilic extracts from serum and RBCs, using positive and negative mode of acquisition (ESI+/ESI-), and gas chromatography-mass spectrometry were used. A quantitative analysis of reversible oxidized thiols in serum proteins demonstrated a strong oxidative stress induction in the liver of Hg-exposed mice. Endogenous metabolites alterations were identified by partial least squares-discriminant analysis (PLS-DA). Mercury-exposed mice show perturbations in energy metabolism, amino acid metabolism, membrane phospholipid breakdown and oxidative stress-related metabolites in serum along the exposure. This work reports for the first time the effects of Hg-exposure on RBCs metabolic pathways, and reveals disturbances in glycolysis, membrane turnover, glutathione and ascorbate metabolisms. PMID:25660718

  8. Quantification of 11-Carboxy-Delta-9-Tetrahydrocannabinol (THC-COOH) in Meconium Using Gas Chromatography/Mass Spectrometry (GC/MS).

    PubMed

    Peat, Judy; Davis, Brehon; Frazee, Clint; Garg, Uttam

    2016-01-01

    Maternal substance abuse is an ongoing concern and detecting drug use during pregnancy is an important component of neonatal care when drug abuse is suspected. Meconium is the preferred specimen for drug testing because it is easier to collect than neonatal urine and it provides a much broader time frame of drug exposure. We describe a method for quantifying 11-carboxy-delta-9-tetrahydrocannabinol (THC-COOH) in meconium. After adding a labeled internal standard (THC-COOH D9) and acetonitrile, samples are sonicated to release both free and conjugated THC-COOH. The acetonitrile/aqueous layer is removed and mixed with a strong base to hydrolyze the conjugated THC-COOH. The samples are then extracted with an organic solvent mixture as part of a sample "cleanup." The organic solvent layer is discarded and the remaining aqueous sample is acidified. Following extraction with a second organic mixture, the organic layer is removed and concentrated to dryness. The resulting residue is converted to a trimethylsilyl (TMS) derivative and analyzed using gas chromatography/mass spectrometry (GC/MS) in selective ion monitoring (SIM) mode. PMID:26660178

  9. Development of a stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry method for determining synthetic musks in water samples.

    PubMed

    Ramrez, Noelia; Marc, Rosa Maria; Borrull, Francesc

    2011-01-01

    This study presents the development of an analytical method for determining 9 synthetic musks in water matrices. The developed method is based on stir bar sorptive extraction (SBSE), coated with polydimethylsiloxane, and coupled with a thermal desorption-gas chromatography-mass spectrometry system (TD-GC-MS). SBSE can efficiently trap and desorb the analytes providing low limits of detection (between 0.02 ng L? and 0.3 ng L?). Method validation showed good linearity, repeatability and reproducibility for all compounds. Furthermore, the limited manipulation of the sample required in this method implies a significant decrease of the risk of external contamination of the samples. The performance of the method in real samples was evaluated by analysing biological wastewater treatment plant (WWTP) influent and effluent samples, reverse osmosis treatment plant effluents and river waters. The most abundant musk was galaxolide with values up to 2069 ng L? and 1432 ng L? in the influent and effluent of urban WWTP samples, respectively. Cashmeran, Pantolide and Tonalide were also detected in all the matrices with values up to 94 ng L?, 26 ng L? and 88 ng L?, respectively. Although in Europe the use of nitromusks in cosmetics is prohibited, musk xylene and musk ketone were detected both in the WWTP and in the river samples. As far as we know, this is the first time than a SBSE method coupled with TD is applied for the determination of synthetic musks in water samples. PMID:21130460

  10. Simultaneous determination of 2-naphthol and 1-hydroxypyrene in fish and shellfish contaminated with crude oil by gas chromatography-mass spectrometry.

    PubMed

    Lim, Hyun-Hee; Shin, Ho-Sang

    2013-06-01

    This paper describes a gas chromatography-mass spectrometric method of l-hydroxypyrene (1-HOP) and 2-naphthol (2-NAP) in fish and shellfish. Alkali hydrolysis method in this study was chosen and optimized to the reaction condition for 90 min at 90°C in a 2.0M KOH solution. For five independent determinations at 0.2 and 1.0 μg/kg, the coefficient of variation was less than 5.1%. This method was used to assess the long-term influence of spilled crude oil on marine ecosystems and analyze fifty-two shellfish samples taken in the near of the accident region of the Hebei Spirit oil spill. 2-NAP and 1-HOP were detected in the mean concentration range of 0.09-12.42 and 0.03-0.06 μg/kg, respectively. 2-NAP was detected in a high concentration range in shellfishes gathered in 2 months after the accident and it decreased rapidly to 6 months after that. The results showed that 2-NAP might be an important biomarker in biota contaminated with crude oil. PMID:23411178

  11. Determination of dimethyl sulfoxide and dimethyl sulfone in urine by gas chromatography-mass spectrometry after preparation using 2,2-dimethoxypropane.

    PubMed

    Takeuchi, Akito; Yamamoto, Shinobu; Narai, Rie; Nishida, Manami; Yashiki, Mikio; Sakui, Norihiro; Namera, Akira

    2010-05-01

    A method for routinely determination of dimethyl sulfoxide (DMSO) and dimethyl sulfone (DMSO(2)) in human urine was developed using gas chromatography-mass spectrometry. The urine sample was treated with 2,2-dimethoxypropane (DMP) and hydrochloric acid for efficient removal of water, which causes degradation of the vacuum level in mass spectrometer and shortens the life-time of the column. Experimental DMP reaction parameters, such as hydrochloric acid concentration, DMP-urine ratio, reaction temperature and reaction time, were optimized for urine. Hexadeuterated DMSO was used as an internal standard. The recoveries of DMSO and DMSO(2) from urine were 97-104 and 98-116%, respectively. The calibration curves showed linearity in the range of 0.15-54.45 mg/L for DMSO and 0.19-50.10 mg/L for DMSO(2). The limits of detection of DMSO and DMSO(2) were 0.04 and 0.06 mg/L, respectively. The relative standard deviations of intra-day and inter-day were 0.2-3.4% for DMSO and 0.4-2.4% for DMSO(2). The proposed method may be useful for the biological monitoring of workers exposed to DMSO in their occupational environment. PMID:19688817

  12. Qualitative and Quantitative Analysis of Volatile Components of Zhengtian Pills Using Gas Chromatography Mass Spectrometry and Ultra-High Performance Liquid Chromatography

    PubMed Central

    Liu, Cui-ting; Zhang, Min; Yan, Ping; Liu, Hai-chan; Liu, Xing-yun; Zhan, Ruo-ting

    2016-01-01

    Zhengtian pills (ZTPs) are traditional Chinese medicine (TCM) which have been commonly used to treat headaches. Volatile components of ZTPs extracted by ethyl acetate with an ultrasonic method were analyzed by gas chromatography mass spectrometry (GC-MS). Twenty-two components were identified, accounting for 78.884% of the total components of volatile oil. The three main volatile components including protocatechuic acid, ferulic acid, and ligustilide were simultaneously determined using ultra-high performance liquid chromatography coupled with diode array detection (UHPLC-DAD). Baseline separation was achieved on an XB-C18 column with linear gradient elution of methanol-0.2% acetic acid aqueous solution. The UHPLC-DAD method provided good linearity (R2 ≥ 0.9992), precision (RSD < 3%), accuracy (100.68–102.69%), and robustness. The UHPLC-DAD/GC-MS method was successfully utilized to analyze volatile components, protocatechuic acid, ferulic acid, and ligustilide, in 13 batches of ZTPs, which is suitable for discrimination and quality assessment of ZTPs. PMID:26904360

  13. Analysis of the volatile organic matter of engine piston deposits by direct sample introduction thermal desorption gas chromatography/mass spectrometry.

    PubMed

    Diaby, M; Kinani, S; Genty, C; Bouchonnet, S; Sablier, M; Le Negrate, A; El Fassi, M

    2009-12-01

    This article establishes an alternative method for the characterization of volatiles organic matter (VOM) contained in deposits of the piston first ring grooves of diesel engines using a ChromatoProbe direct sample introduction (DSI) device coupled to gas chromatography/mass spectrometry (GC/MS) analysis. The addition of an organic solvent during thermal desorption leads to an efficient extraction and a good chromatographic separation of extracted products. The method was optimized investigating the effects of several solvents, the volume added to the solid sample, and temperature programming of the ChromatoProbe DSI device. The best results for thermal desorption were found using toluene as an extraction solvent and heating the programmable temperature injector from room temperature to 300 degrees C with a temperature step of 105 degrees C. With the use of the optimized thermal desorption conditions, several components have been positively identified in the volatile fraction of the deposits: aromatics, antioxidants, and antioxidant degradation products. Moreover, this work highlighted the presence of diesel fuel in the VOM of the piston deposits and gave new facts on the absence of the role of diesel fuel in the deposit formation process. Most importantly, it opens the possibility of quickly performing the analysis of deposits with small amounts of samples while having a good separation of the volatiles. PMID:19894696

  14. Ultrasonic nebulization extraction coupled with headspace single drop microextraction and gas chromatography-mass spectrometry for analysis of the essential oil in Cuminum cyminum L.

    PubMed

    Wang, Lu; Wang, Ziming; Zhang, Huihui; Li, Xueyuan; Zhang, Hanqi

    2009-08-01

    A novel method for analysis of essential oil in Cuminum cyminum L. using simultaneous ultrasonic nebulization extraction and headspace single drop microextraction (UNE-HS-SDME) followed by gas chromatography-mass spectrometry was developed. Experimental parameters, including the kind of suspended solvent, microdrop volume, sample amount, extraction time, enrichment time and salt concentration were examined and optimized. Compared with hydrodistillation (HD), UNE-HS-SDME provides the advantages of a small amount of sample (50 mg), time-saving (20 min), simplicity, cheapness and low toxicity. In addition, UNE-HS-SDME also provided higher enrichment efficiency and sensitivity compared with stirring extraction (SE)-HS-SDME, ultrasonic assistant extraction (UAE) and UNE. Some constituents in the essential oil, were identified and the detection limits for beta-pinene, p-cymene and gamma-terpinene range from 6.67 pLL(-1) to 14.8 pLL(-1). The results indicated that the UNE-HS-SDME is simple and highly efficient extraction and enrichment technique. PMID:19576388

  15. Selection of Taste Markers Related to Lactic Acid Bacteria Microflora Metabolism for Chinese Traditional Paocai: A Gas Chromatography-Mass Spectrometry-Based Metabolomics Approach.

    PubMed

    Zhao, Nan; Zhang, Chuchu; Yang, Qin; Guo, Zhuang; Yang, Bo; Lu, Wenwei; Li, Dongyao; Tian, Fengwei; Liu, Xiaoming; Zhang, Hao; Chen, Wei

    2016-03-23

    Traditional paocai brine (PB) is continuously propagated by back-slopping and contains numerous lactic acid bacteria (LAB) strains. Although PB is important for the quality of paocai (Chinese sauerkraut), the taste features, taste-related compounds of PB-paocai and the effects of LAB communities from PB on the taste compounds remain unclear. An electronic tongue was used to evaluate the taste features of 13 PB-paocai samples. Umami, saltiness, bitterness, sweetness, and aftertaste astringency were the main taste features of PB-paocai. A total of 14 compounds were identified as discriminant taste markers for PB-paocai via gas chromatography-mass spectrometry (GC-MS)-based multimarker profiling. A LAB co-culture (Lactobacillus plantarum, Lactobacillus buchneri, and Pediococcus ethanoliduran) from PB could significantly increase glutamic acid (umami), sucrose (sweetness), glycine (sweetness), lactic acid (sourness), and γ-aminobutyric acid in PB-paocai, which would endow it with important flavor features. Such features could then facilitate starter screening and fermentation optimization to produce paocai-related foods with better nutritional and sensory qualities. PMID:26915389

  16. Quantitative solid phase microextraction - gas chromatography mass spectrometry analysis of the pesticides lindane, heptachlor and two heptachlor transformation products in groundwater.

    PubMed

    McManus, Sarah-Louise; Coxon, Catherine E; Richards, Karl G; Danaher, Martin

    2013-04-01

    This paper describes the development and validation of a method for the determination of lindane, heptachlor and two heptachlor transformation products (exo- and endo-heptachlor epoxide) in groundwater. Samples were extracted using a simple solid phase microextraction (SPME) method with a polyacrylate fibre prior to detection by gas chromatography mass spectrometry in electron impact ionisation mode (GC-EI-MS). The linearity of the method ranged from 0.015 to 5.0 μg L(-1), with correlation coefficients greater than 0.99. Recoveries ranged from 96 to 101% at several fortification levels with all coefficients of variation (CV%) less than 10.5%. The method was validated to the permitted limits laid down in the European Union drinking water directive (98/83/EC). The limit of quantitation (LOQ) was 0.015 μg L(-1) in groundwater samples. Samples had to be analysed within 24h of collection otherwise degradation occurred and disposable SPME polyacrylate fibres lasted up to 51 injections. Both endo-heptachlor epoxide and lindane were detected in groundwater samples with concentrations ranging between 0.033 and 0.048 μg L(-1). PMID:23466207

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

    PubMed

    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, Mller-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% Mller-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. PMID:25000414

  18. Nanoscale-supported heteropoly acid as a new fiber coating for solid-phase microextraction coupled with gas chromatography-mass spectrometry.

    PubMed

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

    2015-02-13

    In the present study, 12-tungstophosphoric (PW) acid as heteropoly acid, supported on silica-coated ?-Fe2O3 nanoparticles (NPs), was used as a new fiber coating for solid-phase microextraction (SPME). The ?-Fe2O3@SiO2-PW nanocomposite with high surface area was synthesized and characterized by SEM and FT-IR. The prepared nanocomposite was immobilized on a stainless steel wire for fabrication of the SPME fiber. The fiber was evaluated for the extraction of some phenolic compounds (PCs) from water sample in combination with gas chromatography-mass spectrometry (GC-MS). A one-at-a-time optimization strategy was applied for optimizing the important extraction parameters such as extraction temperature, extraction time, ionic strength, stirring rate, pH, and desorption temperature and time. In optimum conditions, the repeatability for one fiber (n=3), expressed as relative standard deviation (R.S.D. %), was between 4.8% and 9.6% for the test compounds. The detection limits for the studied compounds were between 0.004 and 0.05 pg mL(-1). The developed method offers the advantage of being simple to use, with shorter analysis time, lower cost of equipment, thermal stability of fiber and high relative recovery in comparison to conventional methods of analysis. PMID:25618361

  19. Enzymatic Digestion and Selective Quantification of Underivatised Delta-9-Tetrahydrocannabinol and Cocaine in Human Hair Using Gas Chromatography-Mass Spectrometry

    PubMed Central

    Breidi, Salah Eddine; Barker, James; Petrczi, Andrea; Naughton, Declan P.

    2012-01-01

    Gas chromatography-mass spectrometric (GC-MS) methods for drug analysis routinely employ derivatising reagents. The aim of this paper was to develop a method for the analysis of two recreational drugs, delta-9-tetrahydrocannabinol (?9-THC) and cocaine in hair samples using GC-MS, without prior derivatisation, thus allowing the sample to be reanalysed in its original form. An enzymatic digestion technique was also developed. Ten hair samples, that were known positive for either ?9-THC and/or cocaine, were enzymatically digested, extracted, and then analysed by GC-MS. All samples measured contained ?9-THC and one sample contained cocaine. The limits of detection (LOD) and quantification (LOQ) were 0.02?ng/mg and 0.05?ng/mg, respectively, for cocaine and 0.015?ng/mg and 0.02?ng/mg, respectively, for ?9-THC. The wide detection window, ease of direct analysis by GC-MS, lower detection limits of underivatised samples, and the stability of drugs using this technique may offer an improved method of analysis. PMID:22567573

  20. Stir bar sorptive extraction with gas chromatography-mass spectrometry for the determination of resveratrol, piceatannol and oxyresveratrol isomers in wines.

    PubMed

    Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

    2013-11-01

    A simple and highly sensitive procedure based on stir bar sorptive extraction coupled to gas chromatography-mass spectrometry by means of a thermal desorption unit (SBSE-TD-GC-MS) has been optimized for the determination of cis/trans isomers of resveratrol, piceatannol and oxyresveratrol in wine samples. Quantification of the cis-isomers was carried out by generating the standards from the corresponding trans-species once they had been preconcentrated on the SBSE extracting phase. The optimization of the acetylation derivatization, SBSE extraction and thermal desorption steps was investigated using Plackett-Burman designs, taking into account the high number of variables to be considered. The use of bisphenol F as internal standard allowed quantification of the samples against aqueous standards. Repeatability, expressed as relative standard deviation of 10 successive analyses was between 5% and 9%, confirming the high precision attained under the optimized conditions. Satisfactory recovery values of between 79% and 109% were obtained for spiked samples in the 0.2-1.0 μgL(-1) concentration range, depending on the compound. The main compound determined in the analyzed samples was trans-resveratrol, with concentrations in the range of 3-230 μgL(-1), depending on the type of wine. PMID:24075014

  1. Determination of atranol and chloroatranol in perfumes using simultaneous derivatization and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Lpez-Nogueroles, Marina; Chisvert, Alberto; Salvador, Amparo

    2014-05-15

    A new analytical method based on simultaneous derivatization and dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography-mass spectrometry (GC-MS), for the determination of the allergenic compounds atranol and chloroatranol in perfumes, is presented. Derivatization of the target analytes by means of acetylation with anhydride acetic in carbonate buffer was carried out. Thereby volatility and detectability were increased for improved GC-MS sensitivity. In addition, extractability by DLLME was also enhanced due to a less polar character of the solutes. A liquid-liquid extraction was performed before DLLME to clean up the sample and to obtain an aqueous sample solution, free of the low polar matrix from the essential oils, as donor phase. Different parameters, such as the nature and volume of both the extraction and disperser solvents, the ionic strength of the aqueous donor phase or the effect of the derivatization reagent volume, were optimized. Under the selected conditions (injection of a mixture of 750?L of acetone as disperser solvent, 100?L of chloroform as extraction solvent and 100?L of anhydride acetic as derivatization reagent) the figures of merit of the proposed method were evaluated. Limits of detection in the low ngmL(-1) range were obtained. Matrix effect was observed in real perfume samples and thus, standard addition calibration is recommended. PMID:24793850

  2. Ion and gas chromatography mass spectrometry investigations of organophosphates in lithium ion battery electrolytes by electrochemical aging at elevated cathode potentials

    NASA Astrophysics Data System (ADS)

    Weber, Waldemar; Wagner, Ralf; Streipert, Benjamin; Kraft, Vadim; Winter, Martin; Nowak, Sascha

    2016-02-01

    The electrochemical aging of commercial non-aqueous lithium hexafluorophosphate (LiPF6)/organic carbonate solvent based lithium ion battery electrolyte has been investigated in view of the formation of ionic and non-ionic alkylated phosphates. Subject was a solvent mixture of ethylene carbonate/ethyl methyl carbonate EC:EMC (1:1, by wt.) with 1 M LiPF6 (LP50 Selectilyte™, BASF). The analysis was carried out by ion chromatography coupled with electrospray ionization mass spectrometry (ESI-MS) for ionic compounds and (headspace) gas chromatography mass spectrometry ((HS)-GC-MS) for non-ionic compounds. The electrochemical aging was performed by galvanostatic charge/discharge cycling and potentiostatic experiments with LiNi0.5Mn1.5O4 (LMNO) as cathode material at increased cut-off potentials (>4.5 V vs. Li/Li+). A strong dependence of the formation of organophosphates on the applied electrode potential was observed and investigated by quantitative analysis of the formed phosphates. In addition, new possible "fingerprint" compounds for describing the electrolyte status were investigated and compared to existing compounds.

  3. Evaluation of the metabolic chiral inversion of d-selenomethionine in rats by stable isotope dilution gas chromatography-mass spectrometry.

    PubMed

    Matsukawa, Takehisa; Hasegawa, Hiroshi; Goto, Hitomi; Shinohara, Yoshihiko; Shinohara, Atsuko; Omori, Yuki; Ichida, Kimiyoshi; Yokoyama, Kazuhito

    2015-12-10

    The stereoselective pharmacokinetics of selenomethionine enantiomers in rats has been studied to evaluate the chiral inversion of D-selenomethionine to the L-enantiomer. After bolus intravenous administration of D- or L-selenomethionine to rats, the plasma concentrations of these two enantiomers were determined by stereoselective gas chromatography-mass spectrometry with selected ion monitoring. This method involved derivatization of selenomethionine enantiomers with HCl in methanol to form methyl ester followed by N-acylation with (+)-?-methoxy-?-trifluoromethylphenylacetyl chloride to form the diastereomeric amide, and separation of the diastereomer on GC with an achiral column. Plasma concentrations of administered D- and L-selenomethionine declined with terminal half-lives of 96 17 min and 91 6 min, respectively. L-Selenomethionine appeared rapidly in plasma after administration of D-selenomethionine, whereas D-selenomethionine was not detected in plasma after administration of L-selenomethionine. The fraction of conversion of D-selenomethionine to L-selenomethionine was estimated to be 61.3 14.5%. The present method evaluates the stereoselective pharmacokinetics of selenomethionine enantiomers, including the estimation of the metabolic chiral inversion. PMID:26001566

  4. Development of sample clean up methods for the analysis of Mycobacterium tuberculosis methyl mycocerosate biomarkers in sputum extracts by gas chromatography-mass spectrometry.

    PubMed

    Nicoara, Simona C; Turner, Nicholas W; Minnikin, David E; Lee, Oona Y-C; O'Sullivan, Denise M; McNerney, Ruth; Mutetwa, Reggie; Corbett, Liz E; Morgan, Geraint H

    2015-04-01

    A proof of principle gas chromatography-mass spectrometry method is presented, in combination with clean up assays, aiming to improve the analysis of methyl mycocerosate tuberculosis biomarkers from sputum. Methyl mycocerosates are generated from the transesterification of phthiocerol dimycocerosates (PDIMs), extracted in petroleum ether from sputum of tuberculosis suspect patients. When a high matrix background is present in the sputum extracts, the identification of the chromatographic peaks corresponding to the methyl derivatives of PDIMs analytes may be hindered by the closely eluting methyl ether of cholesterol, usually an abundant matrix constituent frequently present in sputum samples. The purification procedures involving solid phase extraction (SPE) based methods with both commercial Isolute-Florisil cartridges, and purpose designed molecularly imprinted polymeric materials (MIPs), resulted in cleaner chromatograms, while the mycocerosates are still present. The clean-up performed on solutions of PDIMs and cholesterol standards in petroleum ether show that, depending on the solvent mix and on the type of SPE used, the recovery of PDIMs is between 64 and 70%, whilst most of the cholesterol is removed from the system. When applied to petroleum ether extracts from representative sputum samples, the clean-up procedures resulted in recoveries of 36-68% for PDIMs, allowing some superior detection of the target analytes. PMID:25728371

  5. Determination of aromatic amines in human urine using comprehensive multi-dimensional gas chromatography mass spectrometry (GCxGC-qMS).

    PubMed

    Lamani, Xolelwa; Horst, Simeon; Zimmermann, Thomas; Schmidt, Torsten C

    2015-01-01

    Aromatic amines are an important class of harmful components of cigarette smoke. Nevertheless, only few of them have been reported to occur in urine, which raises questions on the fate of these compounds in the human body. Here we report on the results of a new analytical method, in situ derivatization solid phase microextraction (SPME) multi-dimensional gas chromatography mass spectrometry (GCxGC-qMS), that allows for a comprehensive fingerprint analysis of the substance class in complex matrices. Due to the high polarity of amino compounds, the complex urine matrix and prevalence of conjugated anilines, pretreatment steps such as acidic hydrolysis, liquid-liquid extraction (LLE), and derivatization of amines to their corresponding aromatic iodine compounds are necessary. Prior to detection, the derivatives were enriched by headspace SPME with the extraction efficiency of the SPME fiber ranging between 65 % and 85 %. The measurements were carried out in full scan mode with conservatively estimated limits of detection (LOD) in the range of several ng/L and relative standard deviation (RSD) less than 20 %. More than 150 aromatic amines have been identified in the urine of a smoking person, including alkylated and halogenated amines as well as substituted naphthylamines. Also in the urine of a non-smoker, a number of aromatic amines have been identified, which suggests that the detection of biomarkers in urine samples using a more comprehensive analysis as detailed in this report may be essential to complement the approach of the use of classic biomarkers. PMID:25142049

  6. Improvement of a headspace solid phase microextraction-gas chromatography/mass spectrometry method for the analysis of wheat bread volatile compounds.

    PubMed

    Raffo, Antonio; Carcea, Marina; Castagna, Claudia; Magr, Andrea

    2015-08-01

    An improved method based on headspace solid phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME/GC-MS) was proposed for the semi-quantitative determination of wheat bread volatile compounds isolated from both whole slice and crust samples. A DVB/CAR/PDMS fibre was used to extract volatiles from the headspace of a bread powdered sample dispersed in a sodium chloride (20%) aqueous solution and kept for 60min at 50C under controlled stirring. Thirty-nine out of all the extracted volatiles were fully identified, whereas for 95 other volatiles a tentative identification was proposed, to give a complete as possible profile of wheat bread volatile compounds. The use of an array of ten structurally and physicochemically similar internal standards allowed to markedly improve method precision with respect to previous HS-SPME/GC-MS methods for bread volatiles. Good linearity of the method was verified for a selection of volatiles from several chemical groups by calibration with matrix-matched extraction solutions. This simple, rapid, precise and sensitive method could represent a valuable tool to obtain semi-quantitative information when investigating the influence of technological factors on volatiles formation in wheat bread and other bakery products. PMID:26118802

  7. Gas chromatography-mass spectrometry following microwave distillation and headspace solid-phase microextraction for fast analysis of essential oil in dry traditional Chinese medicine.

    PubMed

    Li, Ning; Deng, Chunhui; Li, Yan; Ye, Hao; Zhang, Xiangmin

    2006-11-10

    In this paper, a novel method based on gas chromatography-mass spectrometry (GC-MS) following microwave distillation-headspace solid-phase microextraction (MD-HS-SPME) was developed for the determination of essential oil in dry traditional Chinese medicine (TCM). TCM is dried before being preserved and used, there is too little water to absorb microwave energy and heat the TCM samples. In the work, carbonyl iron powders (CIP) was added and mixed with the dried TCM sample, which was used as microwave absorption solid medium for dry distillation of the TCM. At the same time, SPME was used for the extraction and concentration of essential oil after MD. The dry rhizomes of Atractylodes lancea DC was used as the model TCM, and used in the study. The MD-HS-SPME parameters including fiber coating, microwave power, irradiation time, and the amount of added CIP, were studied. To demonstrate the method feasibility, the conventional HS-SPME method was also used for the analysis of essential oil in the TCM. Experimental results show that more compounds were isolated and identified by MD-HS-SPME than those by HS-SPME. Compared to conventional HS-SPME, the advantages of the proposed method are: short extraction time and high extraction efficiency. All experimental results show that the proposed method is an alternative tool for fast analysis of essential oils in dry TCMs. PMID:16950328

  8. Analysis of dextromethorphan and dextrorphan in decomposed skeletal tissues by microwave assisted extraction, microplate solid-phase extraction and gas chromatography- mass spectrometry (MAE-MPSPE-GCMS).

    PubMed

    Fraser, Candice D; Cornthwaite, Heather M; Watterson, James H

    2015-08-01

    Analysis of decomposed skeletal tissues for dextromethorphan (DXM) and dextrorphan (DXT) using microwave assisted extraction (MAE), microplate solid-phase extraction (MPSPE) and gas chromatography-mass spectrometry (GC-MS) is described. Rats (n?=?3) received 100?mg/kg DXM (i.p.) and were euthanized by CO2 asphyxiation roughly 20?min post-dose. Remains decomposed to skeleton outdoors and vertebral bones were recovered, cleaned, and pulverized. Pulverized bone underwent MAE using methanol as an extraction solvent in a closed microwave system, followed by MPSPE and GC-MS. Analyte stability under MAE conditions was assessed and found to be stable for at least 60?min irradiation time. The majority (>90%) of each analyte was recovered after 15?min. The MPSPE-GCMS method was fit to a quadratic response (R(2) ?>?0.99), over the concentration range 10-10 000?ng?mL(-1) , with coefficients of variation <20% in triplicate analysis. The MPSPE-GCMS method displayed a limit of detection of 10?ng?mL(-1) for both analytes. Following MAE for 60?min (80?C, 1200?W), MPSPE-GCMS analysis of vertebral bone of DXM-exposed rats detected both analytes in all samples (DXM: 0.9-1.5?g?g(-1) ; DXT: 0.5-1.8?g?g(-1) ). PMID:25487525

  9. Characterization and chemical composition of fatty acids content of watermelon and muskmelon cultivars in Saudi Arabia using gas chromatography/mass spectroscopy

    PubMed Central

    Albishri, Hassan M.; Almaghrabi, Omar A.; Moussa, Tarek A. A.

    2013-01-01

    Background: The growth in the production of biodiesel, which is principally fatty acid methyl esters (FAME), has been phenomenal in the last ten years because of the general desire to cut down on the release of greenhouse gases into the atmosphere, and also as a result of the increasing cost of fossil fuels. Objective: Establish whether there is any relationship between two different species (watermelon and muskmelon) within the same family (Cucurbitaceae) on fatty acid compositions and enumerate the different fatty acids in the two species. Materials and Methods: Extraction of fatty acids from the two species and preparation the extract to gas chromatography/mass spectroscopy analysis to determine the fatty acids compositions qualitatively and quantitatively. Results: The analyzed plants (watermelon and muskmelon) contain five saturated fatty acids; tetrdecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid with different concentrations, while muskmelon contains an extra saturated fatty acid named eicosanoic acid. The watermelon plant contains five unsaturated fatty acids while muskmelon contains three only, the two plants share in two unsaturated fatty acids named 9-hexadecenoic acid and 9-octadecenoic acid, the muskmelon plant contains higher amounts of these two acids (2.04% and 10.12%, respectively) over watermelon plant (0.88% and 0.25%, respectively). Conclusion: The chemical analysis of watermelon and muskmelon revealed that they are similar in saturated fatty acids but differ in unsaturated fatty acids which may be a criterion of differentiation between the two plants. PMID:23661995

  10. Volatile composition in raspberry cultivars grown in the Pacific Northwest determined by stir bar sorptive extraction-gas chromatography-mass spectrometry.

    PubMed

    Malowicki, Sarah M M; Martin, Robert; Qian, Michael C

    2008-06-11

    Twenty-nine volatile compounds in 'Chilliwack', 'Tulameen', 'Willamette', 'Yellow Meeker', and 'Meeker' raspberries were quantified using stir bar sorptive extraction (SBSE) paired with gas chromatography-mass spectrometry (GC-MS). Good correlation coefficients were obtained with most aroma-active compounds in raspberry, with quantification limits of 1 microg/kg. However, poor recoveries were observed for raspberry ketone and zingerone. Quantitative data showed that volatile concentrations varied for different cultivars. Large variations for alpha-ionone, beta-ionone, geraniol, linalool, and ( Z)-3-hexenol were observed in different raspberry cultivars. In addition, the volatile compositions in 'Meeker' raspberry grown at different locations also varied. The chiral isomeric ratios of raspberry ketone, alpha-ionone, alpha-pinene, linalool, terpinen-4-ol, delta-octalactone, delta-decalactone, and 6-methyl-5-hepten-2-ol were studied using a CyclosilB column. alpha-Ionone, alpha-pinene, delta-octalactone, and delta-decalactone had strong chiral isomeric preference, with more than 96% for one isomeric form. Much weaker chiral isomeric preference was observed for terpinen-4-ol, while linalool was almost a racemic mixture. Both growing locations and cultivars affect the isomeric ratio of linalool with a range of 37-51% for ( R)-linalool. PMID:18473468

  11. Simultaneous detection and quantification of select nitromusks, antimicrobial agent, and antihistamine in fish of grocery stores by gas chromatography-mass spectrometry.

    PubMed

    Foltz, James; Abdul Mottaleb, M; Meziani, Mohammed J; Rafiq Islam, M

    2014-07-01

    Continually detected biologically persistent nitromusks; galaxolide (HHCB), tonalide (AHTN) and musk ketone (MK), antimicrobial triclosan (TCS), and antihistamine diphenhydramine (DPH) were examined for the first time in edible fillets originating from eight fish species grown in salt- and fresh-water. The sampled fish collected from local grocery stores were homogenized, extracted, pre-concentrated and analyzed by gas chromatography-mass spectrometry (GC-MS) using selected ion monitoring (SIM). The presence of the target compounds in fish extracts was confirmed based on similar mass spectral features and retention behavior with standards. Internal standard based calibration plots were used for quantification. The HHCB, AHTN, TCS and DPH were consistently observed with concentration of 0.163-0.892, 0.068-0.904, 0.189-1.182, and 0.942-7.472 ng g(-1), respectively. These values are at least 1-3 orders of magnitude lower than those obtained in environmental fish specimens. The MK was not detected in any fish. PMID:24377446

  12. Gas chromatography-mass spectrometry metabolite profiling of worker honey bee (Apis mellifera L.) hemolymph for the study of Nosema ceranae infection.

    PubMed

    Aliferis, Konstantinos A; Copley, Tanya; Jabaji, Suha

    2012-10-01

    Here, we are presenting a gas chromatography-mass spectrometry (GC/MS) approach for the study of infection of the worker honey bee (Apis mellifera L.) by the newly emerged obligate intracellular parasite Nosema ceranae based on metabolite profiling of hemolymph. Because of the severity of the disease, early detection is crucial for its efficient control. Results revealed that the parasite causes a general disturbance of the physiology of the honey bee affecting the mechanisms controlling the mobilization of energy reserves in infected individuals. The imposed nutritional and energetic stress to the host was depicted mainly in the decreased levels of the majority of carbohydrates and amino acids, including metabolites such as fructose, l-proline, and the cryoprotectants sorbitol and glycerol, which are implicated in various biochemical pathways. Interestingly, the level of glucose was detected at significantly higher levels in infected honey bees. Metabolomics analyses were in agreement with those of multiplex quantitative PCR analyses, indicating that it can be used as a complementary tool for the detection and the study of the physiology of the disease. PMID:22841888

  13. Determination of Neutral Monosaccharides as Per-O-methylated Derivatives Directly from a Drop of Whole Blood by Gas Chromatography-Mass Spectrometry.

    PubMed

    Ciucanu, Ionel; Pilat, Lumini?a; Ciucanu, Cristian Ionu?; ?i?u, Eugen

    2015-11-01

    A new analytical procedure was developed for the simultaneous quantification of neutral monosaccharides from a drop of whole blood using gas chromatography-mass spectrometry analysis (GC-MS) of their per-O-methylated derivatives. The per-O-methylation reaction with methyl iodide and solid sodium hydroxide in methyl sulfoxide was used for the first time for analysis of blood monosaccharides. A blood drop volume of 0.6 ?L was used without special purification. The elimination of the undesirable components was carried out during methylation in the presence of a strong base and by liquid extraction of the per-O-methylated monosaccharides. The neutral monosaccharides with an anomeric center gave four per-O-methylated isomers, which were well-separated using a capillary column. Identification was done by electron impact mass spectrometry fragmentation, retention times, and library searching. The limits of detection were determined for standards and varied from 2.0 to 2.3 ng mL(-1). Recoveries for human blood samples varied from 99.22% to 99.65%. The RSD values ranged from 1.92 to 2.37. The method is fast, sensitive, reproducible, and an alternative to current methods for quantitative analysis of blood monosaccharides. PMID:26444378

  14. Identification of urine organic acids for the detection of inborn errors of metabolism using urease and gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Lo, Stanley F; Young, Velta; Rhead, William J

    2010-01-01

    A patient suspected of an inborn error of metabolism will commonly have urine organic acid analysis performed as part of their workup. The traditional urine organic acid method involves extraction of the acidic fraction from urine samples using an organic solvent, derivatization of extracted compounds, and identification using gas chromatography-mass spectrometry (GC-MS). Unfortunately, the extraction step results in the loss of many neutral and positively charged compounds, which may be of interest to metabolic physicians and biochemical geneticists. By replacing the traditional extraction step with an enzymatic treatment of the sample with urease, an abundance of organic molecules are available for separation and quantitation by GC-MS. The urease method is a useful adjunct to newborn screening follow-up and it has the additional benefit of being able to identify many classes of biochemical compounds, such as amino acids, acylglycines, neurotransmitters, and carbohydrates. The method below describes the urease treatment, derivatization, and the organic acids, and other biochemical metabolites that can be identified. PMID:20077095

  15. Stir bar sorptive extraction coupled to gas chromatography-mass spectrometry for the determination of bisphenols in canned beverages and filling liquids of canned vegetables.

    PubMed

    Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

    2012-07-20

    This paper describes a method for the simultaneous determination of bisphenol A (BPA), bisphenol F (BPF), bisphenol Z (BPZ) and biphenol (BP), using stir bar sorptive extraction (SBSE) in combination with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Several parameters affecting both extraction and thermal desorption of the SBSE stages were carefully optimized by multivariate designs. SBSE was performed with two derivatization procedures, in situ acetylation and in tube silylation, and the results were compared with those obtained when the analytes were not derivatized. The proposed method, determining the analytes as acyl derivatives, was applied to analyze commercially canned beverages, as well as the filling liquids of canned vegetables, providing detection limits of between 4.7 and 12.5 ng L⁻¹, depending on the compound. The intraday and interday precisions were lower than 6% in terms of relative standard deviation. Recovery studies at two concentration levels, 0.1 and 1 μg L⁻¹, were performed providing recoveries in the 86-122% range. The samples analyzed contained higher concentrations of BPA than of the other analytes. PMID:22682950

  16. Determination of pyrimethanil and kresoxim-methyl in green groceries by headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    PubMed

    Navalón, Alberto; Prieto, Avismelsi; Araujo, Lilia; Vílchez, José Luis

    2002-11-01

    A method for determination of trace amounts of the fungicides pyrimethanil and kresoxim-methyl in green groceries, previous headspace solid-phase microextraction (HSSPME), was developed using gas chromatography-mass spectrometry and selected ion monitoring (GC-MS, SIM). Both fungicides were extracted with a fused-silica fiber coated with 85 microm polyacrylate. The effects of pH, ionic strength, extraction and desorption times as well as the extraction temperature were studied. The linear concentration range of application was 12.5-250 ng g(-1) for both compounds, with detection limits of 1.8-2.0 ng g(-1) for pyrimethanil and 2.8-3.1 ng g(-1) for kresoxim-methyl. SPME/GC-MS analysis yielded good reproducibility (RSD between 7.4 and 15.0%). It was applied to check the eventual existence of pyrimethanil and kresoxim-methyl above the detection limits on grapes, strawberries, tomatoes and ketchup samples. The method validation was completed with spiked matrix samples. It can be applied as a monitoring tool in grapes, strawberries, tomatoes and ketchup samples. PMID:12456089

  17. Determination of bisphenol A in water by micro liquid-liquid extraction followed by silylation and gas chromatography-mass spectrometry analysis.

    PubMed

    Gonzlez-Casado, A; Navas, N; del Olmo, M; Vlchez, J L

    1998-11-01

    A method for the determination of bisphenol A according to the European Union guideline, which establishes a limit of 0.1 ng/mL for organic pollutants in water, is proposed. The method involves a micro liquid-liquid extraction using dichloromethane followed by a silylation step. Identification and quantitation are performed with gas chromatography-mass spectrometry, using an HP-5MS column. The retention time is 7.02 min. Quantitation is carried out using single-ion monitoring (SIM) at m/z 73, 357, and 372. A clean-up is not necessary using SIM mode. Deuterated anthracene (2H10-anthracene) is used as an internal standard. The method is applied to the determination of bisphenol A at very low concentration levels (10.0-250.0 ng/L) in different types of natural water samples. The detection limit obtained is 0.4 ng/L. Recovery efficiencies are close to 100% in all cases. PMID:9812391

  18. Application of SiO(2) hollow fibers for sorptive microextraction and gas chromatography-mass spectrometry determination of organochlorine pesticides in herbal matrices.

    PubMed

    Li, Jia; Zhang, Hong-Fei; Shi, Yan-Ping

    2010-10-01

    A method involving simultaneous extraction and sample clean-up procedure: hollow fiber sorptive microextraction, coupled with gas chromatography-mass spectrometric detection for quantification of seven organochlorine pesticides in Radix et Rhizoma Rhei is described. SiO(2) hollow fiber with porous structure was synthesized for the first time. The internal diameter of SiO(2) hollow fiber is 380 microm and average wall thickness is 100 microm. Aggregated SiO(2) particles deposited on the surface of the hollow fiber in a regular array lead to porous structure. SiO(2) hollow fiber was applied to the determination of organochlorine pesticides in Radix et Rhizoma Rhei to avoid sample clean-up and minimize the matrix effects. Extraction solvent, extraction temperature and equilibration time were optimized. Fiber to fiber repeatability over the concentration ranges were less than 10%. Recoveries were satisfactory (between 63% and 115%) for most of organochlorine pesticides at spiking levels. Furthermore, the proposed method was also applied to determine seven organochlorine pesticides in 43 commercial Radix et Rhizoma Rhei samples, in which the selected pesticides were found in eight samples. The results have been further confirmed by solvent extraction methods according to China Pharmacopoeia (2005). PMID:20661729

  19. Monitoring multi-class pesticide residues in fresh grape by hollow fibre sorptive extraction combined with gas chromatography-mass spectrometry.

    PubMed

    Li, Jia; Zhang, Hong-Fei; Shi, Yan-Ping

    2011-07-15

    A fast and sensitive multi-residue analysis method is reported for simultaneous determination of 25 pesticides of chemical classes which are spiked into fresh grape. The sample pretreatment method involves extraction and clean-up in one step with SiO(2) hollow fibre from 1.0mL fresh grape slurry to minimise the matrix effects, and determination by gas chromatography-mass spectrometry with selective ion monitoring mode. The validation of the optimised method in terms of linearity, precision, recovery and repeatability showed that the proposed procedure is sensitive (the limits of detection were in the range of 0.0009-0.0084?gmL(-1) for 25 pesticides), precise and repeatable (average recoveries were between 61% and 108% with relative standard deviations from 4.0% to 12.4 %). The proposed method was also applied to the analysis of these groups of pesticides in fresh grape sample purchased from the local markets of Lanzhou (China), while no residues of the selected pesticides were detected in the sample. PMID:23140736

  20. Simultaneous determination of trace sterols in complicated biological samples by gas chromatography-mass spectrometry coupled with extraction using ?-sitosterol magnetic molecularly imprinted polymer beads.

    PubMed

    Zhang, Zhuomin; Tan, Wei; Hu, Yuling; Li, Gongke

    2011-07-15

    In this paper, an efficient and sensitive analytical method for the simultaneous determination of three trace sterols including ergosterol, stigmasterol and ?-sitosterol in complicated biological samples was developed by gas chromatography-mass spectrometry (GC-MS) coupled with extraction using novel ?-sitosterol magnetic molecularly imprinted polymer (mag-MIP) beads. Physical tests suggested that ?-sitosterol mag-MIP beads prepared by a rapid microwave synthesis method possessed the porous morphology, narrow size distribution, stable chemical and thermal property. Due to the greatly enlarging surface area and the strong recognition to the target molecules, ?-sitosterol mag-MIP beads have a higher enrichment factor for ?-sitosterol (?20-fold) and the higher selectivity for ?-sitosterol and its analogs than that of ?-sitosterol magnetic nonimprinted polymer (mag-NIP) beads. Under the optimum analytical conditions, all the target compounds achieved good chromatographic separation and sensitive detection without matrix interference. It was interesting that three target sterols were actually found in mushroom samples, and stigmasterol and ?-sitosterol were actually found in serum and watermelon samples. The recoveries of spiked sample tests were in range of 71.6-88.2% with RSDs of 2.4-10.0% (n=3). This method is reliable and applicable for the simultaneous determination of trace sterols in real biological samples based on the ?-sitosterol mag-MIP bead extraction. PMID:21632061

  1. Rapid determination of anilines in water samples by dispersive liquid-liquid microextraction based on solidification of floating organic drop prior to gas chromatography-mass spectrometry.

    PubMed

    Diao, Chun-Peng; Wei, Chao-Hai

    2012-05-01

    A rapid, sensitive and environmentally friendly method for the analysis of 14 anilines in water samples by dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) prior to gas chromatography-mass spectrometry (GC-MS) was developed and optimized. In the proposed method, cyclohexane was used as the extraction solvent as its toxicity was much lower than that of the solvent usually used in dispersive liquid-liquid microextraction (DLLME). In the optimized conditions, the method exhibited good analytical performance. Based on a signal-to-noise ratio of 3, limits of detection for anilines were in the range of 0.07 to 0.29 ?g L(-1), and the linear range was 0.5-200 ?g L(-1) with regression coefficients (r(2)) higher than 0.9977. It was efficient for qualitative and quantitative analysis of anilines in water samples. The relative standard deviations varied from 2.9 to 8.6% depending on different compounds indicating good precision. Tap water and river water were selected for evaluating the application to real water samples. The relative recoveries of anilines for the two real samples spiked with 10 ?g L(-1) anilines were in the scope of 78.2-114.6% and 77.3-115.6%, respectively. PMID:22434272

  2. Gas chromatography mass spectrometry determination of acaricides from honey after a new fast ultrasonic-based solid phase micro-extraction sample treatment.

    PubMed

    Rial-Otero, R; Gaspar, E M; Moura, I; Capelo, J L

    2007-03-30

    A method is reported for the determination of acaricides (amitraz, bromopropylate, coumaphos and fluvalinate) from honey by gas chromatography mass spectrometry after a new fast solid phase micro-extraction, SPME, procedure. Six different fibers were assessed for micro-extraction purpose studying the following variables: (i) SPME coating, (ii) extraction temperature, (iii) extraction time, (iv) desorption conditions and (v) agitation conditions. The new ultrasonic bath technology providing different sonication frequencies (35 and 130kHz) and different working modes (Sweep, Standard and Degas) was studied and optimized for speeding up the acaricide micro-extraction. The best extraction results were achieved with the polyacrylate fiber. The extraction process was done in 30min using the ultrasonic bath at 130kHz in the Standard mode. Quality parameters of the proposed method show a good precision (<11%) and detection and quantitation limits lower than 6 and 15ng/g, respectively, except for fluvalinate. Eleven Portuguese commercial honey samples were analyzed with the developed method in order to assess the performance of the method with real samples and to determine whether the concentration of acaricides in honey exceed their maximum residue levels (MRLs). Acaricide residues detected were lower than those established by the legislation. PMID:19071541

  3. Up-and-down-shaker-assisted dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry for the determination of fungicides in wine.

    PubMed

    Chu, Shang-Ping; Tseng, Wan-Chi; Kong, Po-Hsin; Huang, Chun-Kai; Chen, Jung-Hsuan; Chen, Pai-Shan; Huang, Shang-Da

    2015-10-15

    An up-and-down-shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME) method coupled with gas chromatography-mass spectrometry was developed for the determination of fungicides (cyprodinil, procymidone, fludioxonil, flusilazole, benalaxyl, and tebuconazole) in wine. The developed method requires 11 ?L of 1-octanol without the need for dispersive solvents. The total extraction time was approximately 3 min. Under optimum conditions, the linear range of the method was 0.05-100 ?g L(-1) for all fungicides and the limit of detection was 0.007-0.025 ?g L(-1). The absolute and relative recoveries were 31-83% and 83-107% for white wine, respectively, and 32-85% and 83-108% for red wine, respectively. The intra-day and inter-day precision were 0.5-7.5% and 0.7-6.1%, respectively. Our developed method had good sensitivity and high extraction efficiency. UDSA-DLLME is a desirable method in terms of performance and speed. PMID:25952882

  4. Optimization of a sample preparation method for multiresidue analysis of pesticides in tobacco by single and multi-dimensional gas chromatography-mass spectrometry.

    PubMed

    Khan, Zareen S; Ghosh, Rakesh Kumar; Girame, Rushali; Utture, Sagar C; Gadgil, Manasi; Banerjee, Kaushik; Reddy, D Damodar; Johnson, Nalli

    2014-05-23

    A selective and sensitive multiresidue analysis method, comprising 4 7pesticides, was developed and validated in tobacco matrix. The optimized sample preparation procedure in combination with gas chromatography mass spectrometry in selected-ion-monitoring (GC-MS/SIM) mode offered limits of detection (LOD) and quantification (LOQ) in the range of 3-5 and 7.5-15ng/g, respectively, with recoveries between 70 and 119% at 50-100ng/g fortifications. In comparison to the modified QuEChERS (Quick-Easy-Cheap-Effective-Rugged-Safe method: 2g tobacco+10ml water+10ml acetonitrile, 30min vortexing, followed by dispersive solid phase extraction cleanup), the method performed better in minimizing matrix co-extractives e.g. nicotine and megastigmatrienone. Ambiguity in analysis due to co-elution of target analytes (e.g. transfluthrin-heptachlor) and with matrix co-extractives (e.g. ?-HCH-neophytadiene, 2,4-DDE-linolenic acid) could be resolved by selective multi-dimensional (MD)GC heart-cuts. The method holds promise in routine analysis owing to noticeable efficiency of 27 samples/person/day. PMID:24746872

  5. Sublimation extraction coupled with gas chromatography-mass spectrometry: A new technique for future in situ analyses of purines and pyrimidines on Mars

    NASA Astrophysics Data System (ADS)

    Glavin, D. P.; Cleaves, H. J.; Buch, A.; Schubert, M.; Aubrey, A.; Bada, J. L.; Mahaffy, P. R.

    2006-12-01

    We have developed a sublimation technique coupled with chemical derivatization and gas chromatography mass spectrometry (GC-MS) to detect nucleobases and other volatile organic compounds derived from bacteria in Mars analog materials. To demonstrate this technique, a sample of serpentine inoculated with Escherichia coli ( E. coli) cells was heated to 500 C for several seconds under Martian ambient pressure. The sublimate was collected on a cold finger, then derivatized and analyzed by GC-MS. We found that adenine, cytosine, thymine and uracil were the most abundant molecules detected in the sublimed E. coli extract by GC-MS. In addition, nucleobases were also detected in sublimed extracts of a deep-sea sediment sample, seawater, and soil collected from the Atacama Desert in Chile after heating the samples under the same conditions. Our results indicate that nucleobases can be easily isolated directly from natural samples using sublimation and then detected by GC-MS after chemical derivatization. The sublimation-based extraction technique is one approach that should be considered for use by future in situ instruments designed to detect organic compounds relevant to life in the Martian regolith.

  6. Gas chromatography-mass spectrometry assay for the simultaneous quantification of drugs of abuse in human placenta at 12th week of gestation.

    PubMed

    Joya, Xavier; Pujadas, Mitona; Falcn, Mara; Civit, Ester; Garcia-Algar, Oscar; Vall, Oriol; Pichini, Simona; Luna, Aurelio; de la Torre, Rafael

    2010-03-20

    We describe the development and validation of a method for the quantification of drugs of abuse, using gas chromatography-mass spectrometry (GC/MS), in human placenta. Concentration ranges covered were 5-500 ng/g for amphetamine, methamphetamine, MDMA, methadone, cocaine, benzoylecgonine, cocaethylene, morphine, 11-nor-9-carboxy-delta-9-tetrahydrocannabinol, nicotine, and cotinine. Intra-assay and inter-assay imprecisions were less than 15.7% for lower quality control samples and less than 14.9% for medium and high quality control samples. Recovery range was 36.2-83.7%. Placenta samples were kept at -80 degrees C until analysis; analytes were stable after three freeze-thaw cycles (samples stored at -20 degrees C). This accurate and precise assay has sufficient sensitivity and specificity for the analysis of specimens collected from women who voluntarily terminated their pregnancy at 12th week of gestation. The method has proven to be robust and accurate for the quantification of the principal recreational drugs of abuse in this period of the prenatal life. This is the first report that highlights the presence of drugs of abuse during the first trimester of gestation. PMID:20056364

  7. Headspace solid-phase microextraction gas chromatography-mass spectrometry determination of volatile compounds in different varieties of African star apple fruit (Chrysophillum albidum).

    PubMed

    Lasekan, Ola; Khatib, Alfi; Juhari, Hanisah; Patiram, Parveen; Lasekan, Seye

    2013-12-01

    The volatile compounds in four selected African star apple fruit (Chrysophyllum albidum) varieties were isolated and identified using the headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). A total of 59 compounds were identified. Application of the aroma extract dilution analysis (AEDA) to the aroma distillates from the fruits revealed 45 odour-active compounds in the flavour dilution (FD) factor range of 4-128. Among them, the highest odour activities (FD factors) were determined for methylhexanoate, acetophenone and ethyl dodecanoate. Moreover, aroma lipophilicity appears to reflect molecular conformation. Further analysis of the similarities and differences between the fruit varieties in terms of the key odourants by the application of PLS-DA and PLS-regression coefficient showed strong positive correlation between the very sweet/sweet varieties and 10 key odourants. The odourants included ethyl acetate, acetyl methyl carbinol, methylhexanoate, sabinene, p-cymene, methylbenzoate, ethylbenzoate, geraniol, cis-α-bergomotene, acetophenone, and ethyl dodecanoate. PMID:23870932

  8. The identification of the urinary metabolites of 3-(4-methoxybenzoyl)-1-pentylindole (RCS-4), a novel cannabimimetic, by gas chromatography-mass spectrometry.

    PubMed

    Kavanagh, Pierce; Grigoryev, Andrej; Melnik, Aleksandra; Simonov, Anton

    2012-06-01

    3-(4-Methoxybenzoyl)-1-pentylindole (RCS-4), a synthetic indole-derived cannabimimetic, was first reported to the European Monitoring Centre for Drugs and Drug Addiction via the Early Warning System by Hungarian authorities in 2010 and later identified in head shop test purchases in Ireland. Using gas chromatography-mass spectrometry, we have identified a series of RCS-4 metabolites in urine samples from individuals admitted to hospitals with symptoms of drug intoxication. The metabolites were tentatively identified as products of (i) aromatic monohydroxylation; (ii) dihydroxylation; (iii) aromatic hydroxylation/oxidation of the N-pentyl chain to a ketone; (iv) O-demethylation; (v) O-demethylation/monohydroxylation of N-pentyl chain; (vi) O-demethylation/oxidation of the N-pentyl chain to a ketone; (vii) O-demethylation/aromatic hydroxylation/oxidation of the N-pentyl chain to a ketone; (viii) N-depentylation/aromatic monohydroxylation; and (ix) N and O-dealkylation. The parent compound was not detected. The O-demethylated metabolites were found to be the most useful metabolic markers for the identification of RCS-4 ingestion. PMID:22582265

  9. Rapid determination of polycyclic aromatic hydrocarbons in grilled meat using microwave-assisted extraction and dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Kamankesh, Marzieh; Mohammadi, Abdorreza; Hosseini, Hedayat; Modarres Tehrani, Zohreh

    2015-05-01

    A simple and rapid analytical tech nique for the simultaneous determination of 16 polycyclic aromatic hydrocarbons (PAHs) in grilled meat was developed using microwave-assisted extraction and dispersive liquid-liquid microextraction (MAE-DLLME) followed by gas chromatography-mass spectrometry (GC-MS). The effective parameters in DLLME process were optimized. Good linear relationships were obtained for 16 PAHs in a range of 1-200 ng g(-1), with a correlation coefficient (R(2)) higher than 0.98. Limits of detection and limits of quantification were 0.15-0.3 ng g(-1) and 0.47-1 ng g(-1), respectively. The relative standard deviations (RSD%) for seven analyses were less than 9%. The recoveries of those compounds in grilled meat were obtained from 85% to 104%. Low consumption of the solvent, high recovery, short extraction time, no matrix interference and good merit figures compared to other methods are advantages of the proposed method. The performance of the present method was evaluated for the determination of PAHs in various types of real grilled meat samples, and satisfactory results were obtained. PMID:25618021

  10. Development and validation of an analytical method for total amitraz in fruit and honey with quantification by gas chromatography-mass spectrometry.

    PubMed

    Caldow, Marianne; Fussell, Richard J; Smith, Frankie; Sharman, Matthew

    2007-03-01

    The EU maximum residue limit (MRL) definition for amitraz is 'the sum of amitraz plus all its metabolites containing the 2,4-aniline moiety, expressed as amitraz'. A rapid and sensitive method has been developed and validated in-house for the determination of total amitraz in pears, strawberries, oranges and honey. Samples were hydrolysed (under acidic followed by alkaline conditions) to convert amitraz to 2,4-dimethyaniline, which was then partitioned into 2,2,4-trimethylpentane prior to quantification by gas chromatography-mass spectrometry. The method was validated at 0.02 and 0.1 mg kg(-1) amitraz (well below MRL requirements) with a lowest calibrated level (LCL) for 2,4-dimethylaniline of 0.002 mg kg(-1) (equivalent to 0.0024 mg kg(-1) amitraz). A single partition step yielded recoveries of approximately 60% (with % CV values in the range 3.3-8.2), which is satisfactory for screening purposes. A second partition increased recoveries by 10-20%, making the method suitable for the quantification of residues. PMID:17364930

  11. Application of an automatic thermal desorption-gas chromatography-mass spectrometry system for the analysis of polycyclic aromatic hydrocarbons in airborne particulate matter.

    PubMed

    Gil-Molt, J; Varea, M; Galindo, N; Crespo, J

    2009-02-27

    The application of the thermal desorption (TD) method coupled with gas chromatography-mass spectrometry (GC-MS) to the analysis of aerosol organics has been the focus of many studies in recent years. This technique overcomes the main drawbacks of the solvent extraction approach such as the use of large amounts of toxic organic solvents and long and laborious extraction processes. In this work, the application of an automatic TD-GC-MS instrument for the determination of particle-bound polycyclic aromatic hydrocarbons (PAHs) is evaluated. This device offers the advantage of allowing the analysis of either gaseous or particulate organics without any modification. Once the thermal desorption conditions for PAH extraction were optimised, the method was verified on NIST standard reference material (SRM) 1649a urban dust, showing good linearity, reproducibility and accuracy for all target PAHs. The method has been applied to PM10 and PM2.5 samples collected on quartz fibre filters with low volume samplers, demonstrating its capability to quantify PAHs when only a small amount of sample is available. PMID:19150718

  12. Microwave-assisted headspace solid-phase microextraction for the rapid determination of organophosphate esters in aqueous samples by gas chromatography-mass spectrometry.

    PubMed

    Tsao, Yu-Chi; Wang, Yu-Chen; Wu, Shin-Fang; Ding, Wang-Hsien

    2011-04-15

    The rapid and solvent-free determination of organophosphate esters (OPEs) in aqueous samples via one-step microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS) analysis is described. Tri-n-butyl phosphate (TnBP) and tris-(2-ethylhexyl) phosphate (TEHP) were selected as model compounds for the method of development and validation. The effects of various extraction parameters for the quantitative extraction of these analytes by MA-HS-SPME were systematically investigated and optimized. The analytes, in a 20 mL water sample (in a 40 mL sample bottle containing 2g of NaCl, pH 3.0), were efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the system was microwave irradiated at 140 W for 5 min. The limits of quantification (LOQs) for TnBP and TEHP were 0.5 and 4 ng/L, respectively. Using the standard addition method, MA-HS-SPME coupled with GC-MS was utilized to determine selected OPEs in surface water and wastewater treatment plants (WWTP) influent/effluent samples. Preliminary results show that TnBP was commonly detected OPEs in these aqueous samples, the correlation coefficients (r(2)) of the standard addition curves were greater than 0.9822, indicating that the developed method appears to be a good alternative technique for analyzing OPEs in aqueous samples. PMID:21376965

  13. A simple and sensitive single-step method for gas chromatography-mass spectrometric determination of fipronil and its metabolites in sugarcane juice, jaggery and sugar.

    PubMed

    Ramasubramanian, Thirumalaiandi; Paramasivam, Mariappan; Jayanthi, Ramabhadran; Chandrasekaran, Subramaniam

    2014-05-01

    A simple and sensitive single-step method for gas chromatography-mass spectrometric determination of fipronil and its metabolites viz., fipronil desulfinyl, fipronil sulphide and fipronil sulphone in sugarcane juice, jaggery and sugar has been developed. Acetonitrile was superior to ethyl acetate in terms of selectivity, though they were on par with each other in terms of recoveries. This method does not require any cleanup as the PSA-based cleanup was on par with no-cleanup treatment. Interestingly, the recoveries of fipronil and its metabolites decreased with increased amounts of C18 from 10 to 50mg/g of matrix. Matrix effects were insignificant and the limit of quantification was 0.005μg/g. The recoveries of fipronil and its metabolites varied between 87.5% and 108.5% with the RSD of 0.2-5.3% for all the three matrices studied. This method has also been validated by monitoring fipronil and its metabolites in the retail outlet samples of sugarcane juice, jaggery and sugar. PMID:24360469

  14. Analysis of Essential Oil in Jerusalem Artichoke (Helianthus tuberosus L.) Leaves and Tubers by Gas Chromatography-Mass Spectrometry

    PubMed Central

    Helmi, Zead; Al Azzam, Khaldun Mohammad; Tsymbalista, Yuliya; Ghazleh, Refat Abo; Shaibah, Hassan; Aboul-Enein, Hassan

    2014-01-01

    Purpose: To investigate, for the first time, the chemical composition of essential oil of the tubers and leaves of Jerusalem artichoke (Helianthus tuberosus L.), a species of sunflower native to eastern North America, growing in Ukraine. Methods: A hydrodistillation apparatus was used for the extraction of volatile components and then it was analysed by gas chromatography equipped with a split-splitless injector (split ratio, 1:50) and flame ionization detector (FID). The oil was analyzed under linear temperature programming applied at 4°C/min from 50°C - 340°C. Temperatures of the injector and FID detector were maintained at 280°C and 300°C, respectively. The chemical analysis of the oil was carried out using gas chromatography coupled to mass spectrometry (GC-MS), to determine the chemical composition of the volatile fraction. Results: The essential oils content ranged from 0.00019 to 0.03486 and 0.00011 to 0.00205 (g/100g), in leaves and tubers, respectively. The qualitative and quantitative analysis led to the identification of 17 components in both species samples. The major component found in leaves and tubers was (-)-β-bisabolene with 70.7% and 63.1%, respectively. Conclusion: Essential oil profile of Jerusalem artichoke species showed significant differences between leaves and tubers species. Additionally, the leaves of Jerusalem artichoke are a promising source of natural β-bisabolene. PMID:25671184

  15. Seeking organic compounds on Mars : in situ analysis of organic compounds by Gas Chromatography-Mass Spectrometry on MOMA experiment

    NASA Astrophysics Data System (ADS)

    Buch, A.; Freissinet, C.; Sternberg, R.; Pinnick, V.; Szopa, C.; Coll, P. J.; Rodier, C.; Garnier, C.; Steininger, H.; Moma Team

    2010-12-01

    The search for signs of past or present life is one of the primary goals of future Mars exploratory missions. The Mars Organic Molecule Analyzer (MOMA) experiment of the ExoMars mission (set to launch 2016-2018) is a joint venture by the European Space Agency and NASA to develop a sensitive detector for organics on Mars. MOMA will be one of the main analytical instruments aboard the ExoMars Rover aimed at characterizing possible signs-of-life molecules in the Martian environment such as amino acids, carboxylic acids, nucleobases or polycyclic aromatic hydrocarbons (PAHs). With the aim to separate and detect organic compounds from Martian soil, the French MOMA team has built a gas chromatograph able to work in standalone mode by using a TCD detector. The gas chromatograph can also be coupled with an ion trap mass spectrometer developed by the US MOMA team. Moreover, a GC-MS compatible sample processing system (SPS) allowing the extraction and the chemical transformation of the organic compounds from the soil, that fits within space flight conditions, has also been developed. The sample processing is performed in an oven, dedicated to the MOMA experiment containing the solid sample (50-100mg). The internal temperature of oven can be ranged from 20 to 1000 C which allows for pyrolysis, thermochemolysis or derivatization. The organic extraction step is achieved by using thermodesorption in the range of 100 to 300C for 0.5 to 5 min. Then, the chemical derivatization and/or thermochemolysis of the extracted compounds is performed directly on the soil with a mixture of MTBSTFA-DMF, TMAH or DMF-DMA solution when enantiomeric separation is required. By decreasing the polarity of the target molecules, this step allows for their volatilization at a temperature below 250C without any chemical degradation. Once derivatized, the volatile target molecules are trapped in a cold chemical trap and promptly desorbed into the gas chromatograph coupled to the mass spectrometer. Preliminary tests, performed on several analogue soils such as Atacama soil, with the MOMA SPS-GC/MS experiment demonstrated the capability to detect organic compounds such as amino and carboxylic acids with sensitivities below the ppm level.

  16. Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Bandy, Alan R.; Thornton, Donald C.; Driedger, Arthur R., III

    1993-01-01

    A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

  17. Hydrocarbons identified in extracts from estuarine water accommodated no. 2 fuel oil by gas chromatography-mass spectrometry

    NASA Technical Reports Server (NTRS)

    Lewis, B. W.; Walker, A. L.; Bieri, R. H.

    1974-01-01

    Results are presented on a computerized gas chromatograph-mass spectrometer analysis of methylene chloride and n-heptane extracts of a No. 2 fuel oil accommodated estuarine water sample. The analytical method is briefly described, and the limitations on the identifications are categorized. Some attempt was made to determine major and trace constituents in the water accommodate. Altogether 66 hydrocarbon compounds were identified specifically, and 75 compounds were partially identified. Seven compounds could be recognized as major constituents of the water accommodated oil and ten were present only as traces. The aromatic compounds found were alkyl benzenes, naphthalene, tetralin, indane, biphenyl, fluorene, anthracene, and some of their alkyl substituted isomers in the range of carbon numbers C7 to C15. Four n-alkanes, C10 to C13, were found along with four other assorted hydrocarbons.

  18. Determination of glycerol concentrations and glycerol isotopic enrichments in human plasma by gas chromatography/mass spectrometry.

    PubMed

    Ackermans, M T; Ruiter, A F; Endert, E

    1998-04-10

    An analytical method is presented to determine glycerol concentrations and stable isotope tracer enrichments in human plasma after intravenous tracer infusion in a single analytical run, using gas chromatography coupled to mass spectrometry. The method uses an internal standard, which is also a stable isotope labeled form of glycerol. Three substances were tested as model compounds viz. [2-13C]glycerol, and [1,2,3-13C3]glycerol, and [1,1,2,3, 3-2H5]glycerol. Any combination of two can be used (one as internal standard, one as tracer), even if overlapping of the mass spectra occurs. The method is precise (recovery of spiked glycerol and tracer are, respectively, 99.7 and 99.8%) and reproducible (intraassay variation <1.5%, interassay variation <6%) and needs only a small amount of plasma (100 microl). PMID:9527852

  19. [Analysis of volatile and non-volatile compositions in ginger oleoresin by gas chromatography-mass spectrometry].

    PubMed

    Zhan, Kunyou; Wang, Chao; Xu, Kun; Yin, Hongzong

    2008-11-01

    Ginger oleoresin was extracted from Zingiber officinale Rose. var. Laiwudajiang by the technique of supercritical fluid extraction. Gas chromatography and mass spectrometry technique were employed to analyze the ginger oleoresin. This analysis resulted in the detection of 3 hitherto unknown natural compounds, 24 compounds previously reported as pungent compounds and 50 volatile compounds from ginger. The volatile compounds were mainly alpha-zingiberene (22.29%), beta-sesquiphellandrene (8.58%), alpha-farnesene (3.93%), beta-bisabolene (3.87%), alpha-curcumene (2.63%), which were mostly consisted of sesquiterpene hydrocarbons. The pungent compounds of ginger were mainly 6-gingerol (9.38%), 6-shogaol (7.59%), zingerone (9.24%) produced by the thermal degradation of gingerols or shogaols. The mass spectral fragmentation patterns for the three new compounds (6-isogingerol, (Z)-10-isoshogaol, (E)-10-isoshogaol) are discussed and interpreted. PMID:19253546

  20. Use of an injection port for thermochemolysis-gas chromatography/mass spectrometry: rapid profiling of biomaterials.

    PubMed

    Shadkami, Farzad; Helleur, Robert

    2009-07-31

    A simple and direct approach was developed for thermochemolytic analysis of a wide range of biomolecules present in plant materials using an injection port of a gas chromatograph/mass spectrometer (GC/MS) and a novel solids injector consisting of a coiled stainless steel wire placed inside a modified needle syringe. Optimum thermochemolysis (or Thermally Assisted Hydrolysis/Methylation) was achieved by using a suitable methanolic solution of trimethylsulfonium hydroxide (TMSH) or tetramethylammonium hydroxide (TMAH) with an injection port temperature of 350 degrees C. Intact, methylated flavonoids, saccharides, phenolic and fatty acids, lignin dimers and diterpene resin acids were identified. Samples include tea leaves, hemicelluloses, lignin isolates and herbal medicines. Unexpected chromatographic results using TMAH reagent revealed the presence of intact methylated trisaccharides (658 Da) and structurally informative dimer lignin markers. PMID:19559444

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

    SciTech Connect

    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 {mu}g/mL or higher. This method is ideal for screening samples for quick response situations.

  2. [Simultaneous determination of 25 persistent organic pollutants in rice by gas chromatography-mass spectrometry with selected ion monitoring mode].

    PubMed

    Hou, Shengjun; Chen, Dandan; Li, Xiang; Li, Gang; Yang, Qiang; Min, Shungeng; Zhong, Weike; Chu, Xiaogang; Wang, Daning

    2005-05-01

    A multi-residue analytical method for the simultaneous determination of persistent organic pollutants (POPs) in rice samples was developed. POPs were extracted from rice with ethyl acetate/n-hexane (80:20, v/v) by sonication, and determined by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode. A fused silica capillary column DB-35MS (30 m x 0.25 mm i.d. x 0.25 microm) was employed. Operating conditions were as follows: injector port temperature, 300 degrees C; column temperature, programming; carrier gas, helium; flow rate, 1.0 mL/min; sample size, 1 microL with splitless injection. The mass spectrometric detector (MSD) was operated in electron impact ionization mode with an ionizing energy of 70 eV. Analysis was performed with selected ion monitoring (SIM) using one target and one or two qualifier ion. POPs were confirmed by their retention times, their qualifier and target ions, and their qualifier/target abundance ratios. Recovery studies were performed at 0.05, 0.1, and 0.5 mg/L spiked levels of each POPs, and the recoveries obtained ranged from 81.99% to 100.60% with relative standard deviations between 2.37% and 18.48%. The detection limits of the method ranged from 0.1 to 5 ng/g for the different POPs except endrin, trans-chlordane and cis-chlordane. The results show that the method developed is sensitive and reliable. PMID:16124561

  3. Chemical composition of Titan's aerosols analogues characterized with a systematic pyrolysis-gas chromatography-mass spectrometry characterization

    NASA Astrophysics Data System (ADS)

    Szopa, Cyril; Raulin, Francois; Coll, Patrice; Cabane, Michel; GCMS Team

    2014-05-01

    The in situ chemical characterization of Titan's atmosphere was achieved in 2005 with two instruments present onboard the Huygens atmospheric probe : the Aerosol Collector and Pyrolyzer (ACP) devoted to collect and pyrolyse Titan's aerosols ; the Gas Chromatograph-Mass Spectrometer (GCMS) experiment devoted to analyze gases collected in the atmosphere or coming from the aerosols pyrolysis. The GCMS was developed by Hasso Niemann in the filiation of the quadrupole mass spectrometers he built for several former space missions. The main objectives were to : determine the concentration profile of the most abundant chemical species; seek for minor atmospheric organic species not detected with remote observations ; give a first view of the organic aerosols structure; characterize the condensed volatiles present at the surface (e.g. lakes) in case of survival of the probe to the landing impact. Taking into account for the potential complexity of the gaseous samples to be analyzed, it was decided to couple to the MS analyzer a gas chromatograph capable to separate volatile species from light inorganic molecules and noble gases, to organic compounds including aromatics. This was the first GCMS analyzer that worked in an extraterrestrial environment since the Viking missions on Mars. Even if the GCMS coupling mode did not provide any result of interest, it has been demonstrated to be functional during the Huygens descent. But, the direct MS analysis of the atmosphere, and the pyrolysis-MS analysis of aerosols allowed to make great discoveries which are still of primary importance to describe the Titan's lower atmosphere composition. This contribution aims at presenting this instrument that worked in the Titan's atmosphere, and summarizing the most important discoveries it allowed.

  4. Sample Processing technique onboard ExoMars (MOMA) to analyze organic compounds by Gas Chromatography-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Buch, A.; Freissinet, C.; Sternberg, R.; Szopa, C.; Coll, P. J.; Brault, A.; Pinnick, V.; Siljestrm, S.; Raulin, F.; Steininger, H.; Goesmann, F.; MOMA Team

    2011-12-01

    With the aim of separating and detecting organic compounds from Martian soil onboard the Mars Organic Molecule Analyzer (MOMA) experiment of the ExoMars 2018 upcoming joint ESA/NASA mission, we have developed three different space compatible sample preparation techniques compatible with space missions, able to extract and analyze by GC-MS a wide range of volatile and refractory compounds, including chirality analysis. Then, a sample processing utilizing three derivatization/extraction reactions has been carried out. The first reaction is based on a silyl reagent N-Methyl-N- (Tert-Butyldimethylsilyl)trifluoroacetamide (MTBSTFA) [1], the second one, N,N-Dimethylformamide Dimethylacetal (DMF-DMA) [2,3] is dedicated to the chirality detection and the third one is a thermochemolysis based on the use of tetramethylammoniumhydroxide (TMAH). The sample processing system is performed in an oven, dedicated to the MOMA experiment containing the solid sample (50-100mg). The internal temperature of the oven ranges from 20 to 900 C. The extraction step is achieved by using thermodesorption in the range of 100 to 300C for 5 to 20 min. Then, the chemical derivatization of the extracted compounds is performed directly on the soil sample by using a derivatyization capsule which contains a mixture of MTBSTFA-DMF or DMF-DMA solution when enantiomeric separation is required. By decreasing the polarity of the targeted molecules, this step allows their volatilization at a temperature below 250C without any thermal degradation. Once derivatized, the volatile target molecules are trapped in a chemical trap and promptly desorbed into the gas chromatograph coupled to a mass spectrometer. Thermochemolysis is directly performed in the oven at 400C during 5 min with a 25% (w/w) methanol solution of tetramethylammonium hydroxide (TMAH). Then, pyrolysis in the presence of TMAH allows both an efficient cleavage of polar bonds and the subsequent methylation of COOH, OH and NH2 groups, hence the release of less polar, GC-amenable compounds. By using thermochemolysis several families of biological molecules were detected such as fatty acids, n-alkenes and n-alkanols [4]. [1] A. Buch et al., Development of a gas chromatography compatible Sample Processing System (SPS) for the in-situ analysis of refractory organic matter in martian soil: preliminary result. Advances in Space Research 43, 143-151, 2009. [2] C. Freissinet et al., Journal of Chromatography A.1217 (5), 731-740, 2010. [3] U. Meierhenrich et al., Journal of Analytical and Applied Pyrolysis 60, 13-26, 2001. [4] C. Geffroy-Rodier et al., Journal of Analytical and Applied Pyrolysis, 85, 2009.

  5. Methods of Analysis - Determination of Pyrethroid Insecticides in Water and Sediment Using Gas Chromatography/Mass Spectrometry

    USGS Publications Warehouse

    Hladik, Michelle L.; Smalling, Kelly L.; Kuivila, Kathryn M.

    2009-01-01

    A method for the determination of 14 pyrethroid insecticides in environmental water and sediment samples is described. The method was developed by the U.S. Geological Survey in response to increasing concern over the effects of pyrethroids on aquatic organisms. The pyrethroids included in this method are ones that are applied to many agricultural and urban areas. Filtered water samples are extracted for pyrethroids using solid-phase extraction (SPE) with no additional cleanup steps. Sediment and soil samples are extracted using a microwave-assisted extraction system, and the pyrethroids of interest are separated from co-extracted matrix interferences by passing the extracts through stacked graphitized carbon and alumina SPE cartridges, along with the use of high-performance liquid chromatography and gel-permeation chromatography (HPLC/GPC). Quantification of the pyrethroids from the extracted water and sediment samples is done using gas chromatography with mass spectrometry (GC/MS) or gas chromatography with tandem mass spectrometry (GC/MS/MS). Recoveries in test water samples fortified at 10 ng/L ranged from 83 to 107 percent, and recoveries in test sediment samples fortified at 10 ug/kg ranged from 82 to 101 percent; relative standard deviations ranged from 5 to 9 percent in the water samples and 3 to 9 percent in the sediment samples. Method detection limits (MDLs), calculated using U.S. Environmental Protection Agency procedures (40 CFR 136, Appendix B), in water ranged from 2.0 to 6.0 ng/L using GC/MS and 0.5 to 1.0 ng/L using GC/MS/MS. For sediment, the MDLs ranged from 1.0 to 2.6 ug/kg dry weight using GC/MS and 0.2 to 0.5 ug/kg dry weight using GC/MS/MS. The matrix-spike recoveries for each compound, when averaged for 12 environmental water samples, ranged from 84 to 96 percent, and when averaged for 27 environmental sediment samples, ranged from 88 to 100 percent.

  6. Development and application of compact denuder sampling techniques with in situ derivatization followed by gas chromatography-mass spectrometry for halogen speciation in volcanic plumes

    NASA Astrophysics Data System (ADS)

    Rüdiger, Julian; Bobrowski, Nicole; Hoffmann, Thorsten

    2015-04-01

    Volcanoes are a large source for several reactive atmospheric trace gases including sulphur and halogen containing species. The detailed knowledge of volcanic plume chemistry can give insights into subsurface processes and can be considered as a useful geochemical tool for monitoring of volcanic activity, especially halogen to sulphur ratios (e.g. Bobrowski and Giuffrida, 2012; Donovan et al., 2014). The reactive bromine species bromine monoxide (BrO) is of particular interest, because BrO as well as SO2 are readily measurable by UV spectrometers at a safe distance. Furthermore it is formed in the plume by a multiphase reaction mechanism under depletion of ozone in the plume. The abundance of BrO changes as a function of the reaction time and therefore distance from the vent as well as the spatial position in the plume. Due to the lack of analytical approaches for the accurate speciation of certain halogens (HBr, Br2, Br, BrCl, HOBr etc.) there are still uncertainties about the magnitude of volcanic halogen emissions and in particular their specificationtheir species and therefore also in the understanding of the bromine chemistry in volcanic plumes (Bobrowski et al., 2007). In this study, the first application of a 1,3,5-trimethoxybenzene (1,3,5-TMB)-coated gas diffusion denuder (Huang and Hoffmann, 2008) on volcanic gases proved to be suitable to collect selectively gaseous bromine species with oxidation states of +1 or 0 (Br2 and BrO(H)), while being ignorant to HBr (OS -1). The reaction of 1,3,5-TMB with bromine gives 1-bromo-2,4,6-trimethoxybenzene (1-bromo-2,4,6-TMB) - other halogens give corresponding products. The diffusion denuder technique allows sampling of gaseous compounds exclusively without collecting particulate matter. Choosing a flow rate of 500 mL-min-1 and a denuder length of 0.5 m a nearly quantitative collection efficiency was achieved. Solvent elution of the derivatized analytes and subsequent analysis with gas chromatography-mass spectrometry gives a limit of detection below 1 ng of bromine. The method was applied on volcanic gas plumes at Mt. Etna and Mt. Stromboli in Italy in July 2014 and on fumarolic gas emissions at Mt. Lastarria in Chile in November 2014. The results show significant amounts of the concerning bromine species (lower ppb range). Comprehensive data evaluation and comparison with results of impinger extraction with NaOH solution as well as chamber experiments are still in progress. References Bobrowski, N. and G. Giuffrida: Bromine monoxide / sulphur dioxide ratios in relation to volcanological observations at Mt. Etna 2006-2009. Solid Earth, 3, 433-445, 2012 Bobrowski, N., R. von Glasow, A. Aiuppa, S. Inguaggiato, I. Louban, O. W. Ibrahim and U. Platt: Reactive halogen chemistry in volcanic plumes. J. Geophys. Res., 112, 2007 Donovan A., V. Tsanev, C. Oppenheimer and M. Edmonds: Reactive halogens (BrO and OClO) detected in the plume of Soufrière Hills Volcano during an eruption hiatus. Geochem. Geophys. Geosyst., 15, 3346-3363, 2014 Huang, R.-J. and T. Hoffmann: A denuder-impinger system with in situ derivatization followed by gas chromatography-mass spectrometry for the determination of gaseous iodine-containing halogen species. Journal of Chromatography A, 1210, 135-141, 2008

  7. Microemulsion mediated in situ derivatization-extraction and gas chromatography-mass spectrometric analysis of alkylphosphonic acids.

    PubMed

    Pardasani, Deepak; Palit, Meehir; Gupta, A K; Kanaujia, Pankaj K; Sekhar, K; Dubey, D K

    2006-03-10

    Detection and identification of environmental signatures of chemical warfare agents is an important aspect of verification program of Chemical Weapons Convention (CWC). Alkylphosphonic acids (APAs) are ultimate and persistent degradation products of nerve agents. Their identification in a sample submitted for off-site analysis infers possible indication of contamination with nerve agents. This paper describes the development of a new sample preparation method which involves 'in situ derivatization and extraction' (INDEX) of acids from water. Derivatization is performed by alkylation of APAs with alkylbromides in surfactant less microemulsion (SLME). The derivatized analytes were analyzed by gas chromatography coupled with mass spectrometry. The developed method involves simultaneous derivatization (alkylation) and extraction of acidic analytes mediated by surfactant less microemulsion. Various derivatization-extraction parameters such as solvent, reaction time and temperature, base and alkyl bromides were optimized. Pentyl bromide in the presence of potassium carbonate and diisopropylamine at 100 degrees C derivatized the selected acids efficiently. Kinetic data for alkylation of methylphosphonic acids and some carboxylic acids were obtained to assess their relative susceptibility for alkylation in microemulsion. Methylphosphonic acid and isopropyl methylphosphonic acid took 140-150 min to reach completion while carboxylic acids took 100 min to complete the reaction. INDEX could be successfully performed even in the presence of interfering Ca(2+) and Mg(2+) ions. PMID:16455095

  8. Determination of Tuta absoluta pheromones in water and tomato samples by headspace-gas chromatography-mass spectrometry.

    PubMed

    del Carmen Alcudia-Len, Mara; Lucena, Rafael; Crdenas, Soledad; Valcrcel, Miguel

    2015-01-01

    Tuta absoluta is a tomato pest which is originally from South America. This pest was detected in eastern Spain in 2006 and it rapidly invaded various European countries and spread throughout the Mediterranean basin. The usual detection of this pest is based on the physical evaluation of the crops and in the exhaustive count of potential insects in dedicated traps. The early detection of that pest on the basis of more objective or measurable indicators is desirable. In this case, the combination of headspace and gas chromatography with mass spectrometric detection is proposed for the identification of Tuta absoluta pest using two of its pheromone components as markers. These components, namely: (3E,8Z,11Z)-tetradecatrien-1-yl acetate and (3E,8Z)-tetradecadien-1-yl acetate, are characteristic of Tuta absoluta and they are not present in other insect pheromones. The developed combination allows the determination of both components in water and tomato samples with limits of detection in the range from 25-32 ng/L to 89-111 ng/kg, respectively. The precision, expressed as relative standard deviation, was better than 4.6% for water samples and better than 7.1% when tomato samples were analyzed. The relative recovery values varied in the interval 94-100 and 83-99% for water and tomato samples. PMID:24928116

  9. Gas Chromatography-Mass Spectrometry-Based Metabolite Profiling of Salmonella enterica Serovar Typhimurium Differentiates between Biofilm and Planktonic Phenotypes

    PubMed Central

    Maker, Garth L.; Trengove, Robert D.; O'Handley, Ryan M.

    2015-01-01

    The aim of this study was to utilize gas chromatography coupled with mass spectrometry (GC-MS) to compare and identify patterns of biochemical change between Salmonella cells grown in planktonic and biofilm phases and Salmonella biofilms of different ages. Our results showed a clear separation between planktonic and biofilm modes of growth. The majority of metabolites contributing to variance between planktonic and biofilm supernatants were identified as amino acids, including alanine, glutamic acid, glycine, and ornithine. Metabolites contributing to variance in intracellular profiles were identified as succinic acid, putrescine, pyroglutamic acid, and N-acetylglutamic acid. Principal-component analysis revealed no significant differences between the various ages of intracellular profiles, which would otherwise allow differentiation of biofilm cells on the basis of age. A shifting pattern across the score plot was illustrated when analyzing extracellular metabolites sampled from different days of biofilm growth, and amino acids were again identified as the metabolites contributing most to variance. An understanding of biofilm-specific metabolic responses to perturbations, especially antibiotics, can lead to the identification of novel drug targets and potential therapies for combating biofilm-associated diseases. We concluded that under the conditions of this study, GC-MS can be successfully applied as a high-throughput technique for bottom-up metabolomic biofilm research. PMID:25636852

  10. Determination of emerging halogenated flame retardants and polybrominated diphenyl ethers in serum by gas chromatography mass spectrometry.

    PubMed

    Cequier, Enrique; Marc, Rosa Maria; Becher, Georg; Thomsen, Cathrine

    2013-10-01

    Emerging flame retardants are used in a great variety of household goods and thus have the potential to pollute our indoor environment. Health concerns regarding exposure to these flame retardants demand new methods to survey their occurrence in humans. This work describes development and optimization of an analytical method comprising solid phase extraction and gas chromatography coupled to mass spectrometry for the determination of besides 15 polybrominated diphenyl ethers, 7 emerging halogenated flame retardants in human serum (1,2-bis[2,4,6-tribromophenoxy] ethane, decabromodiphenyl ethane, hexabromobenzene, Dechlorane Plus(), hexachlorocyclopentenyl-dibromocyclooctane, dechlorane 602 and 603). The method was thoroughly validated at three spiking levels obtaining averaged recoveries >80% with a RSD of 5% (n=12). Accuracies ranged from 88 to 125% except for DBDPE, which averaged 66% with overall RSD of 11% (n=12). Method limits of detection (MLD) ranged from 0.3 to 5.4 pg/mL serum, except for decabromodiphenyl ether and decabromodiphenyl ethane for which MLDs were 14 and 20 pg/mL serum, respectively. In human serum samples from Norway, we were able to detect and quantify hexabromobenzene, 1,2-bis[2,4,6-tribromophenoxy] ethane, Dechlorane Plus(), Dechlorane 602 and 603. PMID:23992842

  11. Determination of tricyclic antidepressants in human plasma using pipette tip solid-phase extraction and gas chromatography-mass spectrometry.

    PubMed

    Lee, Xiao-Pen; Hasegawa, Chika; Kumazawa, Takeshi; Shinmen, Natsuko; Shoji, Yukiko; Seno, Hiroshi; Sato, Keizo

    2008-07-01

    A method for the simultaneous extraction of four tricyclic antidepressants from human plasma samples using pipette tip SPE with MonoTip C(18) tips is presented. Human plasma (0.1 mL) containing four tricyclic antidepressants (amitriptyline, amoxapine, imipramine, and trimipramine) and an internal standard (IS), protriptyline, was mixed with 0.4 mL of distilled water and 100 microL 1 M NaOH solution. After centrifugation of the mixture, the supernatant was extracted to the C(18) phase of the tip by 20 repeated aspirating/dispensing cycles using a manual micropipettor. The analytes retained in the tip were eluted with methanol by five repeated aspirating/dispensing cycles. Without evaporation and reconstitution, the eluate was directly injected into a gas chromatograph injector and detected by a mass spectrometer with SIM in the positive-ion electron impact mode. Recovery of the four antidepressants and IS spiked into human plasma was 80.2-92.1%. The regression equations for the four antidepressants showed excellent linearity in the range of 0.2-40 ng/0.1 mL. LODs and LOQs for the four drugs were 0.05-0.2 ng/0.1 mL and 0.2-0.5 ng/0.1 mL, respectively. Intra- and interday CVs for the four drugs in plasma were no greater than 9.5%. PMID:18546392

  12. Multi-Component Profiling of Trace Volatiles in Blood by Gas Chromatography/Mass Spectrometry with Dynamic Headspace Extraction

    PubMed Central

    Kakuta, Shoji; Yamashita, Toshiyuki; Nishiumi, Shin; Yoshida, Masaru; Fukusaki, Eiichiro; Bamba, Takeshi

    2015-01-01

    A dynamic headspace extraction method (DHS) with high-pressure injection is described. This dynamic extraction method has superior sensitivity to solid phase micro extraction, SPME and is capable of extracting the entire gas phase by purging the headspace of a vial. Optimization of the DHS parameters resulted in a highly sensitive volatile profiling system with the ability to detect various volatile components including alcohols at nanogram levels. The average LOD for a standard volatile mixture was 0.50 ng mL−1, and the average LOD for alcohols was 0.66 ng mL−1. This method was used for the analysis of volatile components from biological samples and compared with acute and chronic inflammation models. The method permitted the identification of volatiles with the same profile pattern as in vitro oxidized lipid-derived volatiles. In addition, the concentration of alcohols and aldehydes from the acute inflammation model samples were significantly higher than that for the chronic inflammation model samples. The different profiles between these samples could also be identified by this method. Finally, it was possible to analyze alcohols and low-molecular-weight volatiles that are difficult to analyze by SPME in high sensitivity and to show volatile profiling based on multi-volatile simultaneous analysis. PMID:26819905

  13. Fast determination of paraquat in plasma and urine samples by solid-phase microextraction and gas chromatography-mass spectrometry.

    PubMed

    Gao, Lina; Liu, Junting; Wang, Chunyuan; Liu, Guojie; Niu, Xiaodong; Shu, Cuixia; Zhu, Juan

    2014-01-01

    A simple, sensitive and reliable gas chromatographic-mass spectrometric method (GC-MS) for quantifying paraquat concentration in biological samples has been developed, using ethyl paraquat as an internal standard. The method involved the procedures of sodium borohydride-nickel chloride (NaBH4-NiCl2) reduction and solid-phase microextraction (SPME) of the perhydrogenated products. GC-MS was used to identify and quantify the analytes in selected ion monitoring (SIM) mode. Under the optimal conditions, recoveries in plasma and urine samples were 94.00-99.85% and 95.00-100.34%, respectively. Excellent sample clean-up was observed and good linearities (r=0.9982 for plasma sample and 0.9987 for urine sample) were obtained in the range of 0.1-50?g/mL. The limits of detection (S/N=3) were 0.01?g/mL in plasma and urine samples. The intra-day precision was less than 8.43%, 4.19% (n=3), and inter-day precision was less than 10.90%, 10.49% (n=5) for plasma and urine samples, respectively. This method was successfully applied to the analysis of the biological samples collected from a victim who died as a result of ingestion of paraquat. PMID:24316524

  14. Simultaneous determination of HFBA-derivatized amphetamines and ketamines in urine by gas chromatography-mass spectrometry.

    PubMed

    Lee, Hei Hwa; Lee, Jong Feng; Lin, Sin Yu; Chen, Ping Ho; Chen, Bai Hsiun

    2011-04-01

    To facilitate the analysis of targeted drugs under high sample volume testing environment, an extraction, derivatization and gas chromatographic-mass spectrometric analysis method was developed for simultaneously determination of amphetamine (AMP), methamphetamine (MAMP), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyethylamphetamine (MDEA), ketamine, and norketamine in urine. This method utilized solid-phase extraction in conjunction with derivatization using heptafluorobutyric anhydride (HFBA) as the derivatization reagent. Using a 1-mL sample, the limits of quantitation achieved for the analysis of AMP, MAMP, MDA, MDMA, MDEA, ketamine, and norketamine were 25, 15, 60, 60, 70, 25, and 30 ng/mL, respectively. Upper limits of quantitation were 8000 ng/mL for all amphetamines and 6000 ng/mL for ketamine and norketamine. Except for dehydronorketamine (DHNK), within-day and between-day precisions (as expressed in CV%) for quality control samples were ≤ 3.1% and ≤ 4.95%, respectively. Except DHNK, the within-day accuracy ranged between 96.0% and 110.7% and the between-day accuracy ranged between 96.9% and 108.7%. A group of 107 urine samples previously determined to contain the target analytes were analyzed by this new approach. Quantitative data produced by both methods agreed well. With this new approach, we were able to use a single analytical protocol to conduct the confirmation test for samples that preliminarily tested positive (by immunoassay) for amphetamines, ketamine, or both. PMID:21439152

  15. Detection of high molecular weight organic tracers in vegetation smoke samples by high-temperature gas chromatography-mass spectrometry

    SciTech Connect

    Elias, V.O.; Simoneit, B.R.T. ); Pereira, A.S.; Cardoso, J.N. ); Cabral, J.A. )

    1999-07-15

    High-temperature high-resolution gas chromatography (HTGC) is an established technique for the separation of complex mixtures of high molecular weight (HMW) compounds which do not elute when analyzed on conventional GC columns. The combination of this technique with mass spectrometry is not so common and application to aerosols is novel. The HTGC and HTGC-MS analyses of smoke samples taken by particle filtration from combustion of different species of plants provided the characterization of various classes of HMW compounds reported to occur for the first time in emissions from biomass burning. Among these components are a series of wax esters with up to 58 carbon numbers, aliphatic hydrocarbons, triglycerides, long chain methyl ketones, alkanols and a series of triterpenyl fatty acid esters which have been characterized as novel natural products. Long chain fatty acids with more than 32 carbon numbers are not present in the smoke samples analyzed. The HMW compounds in smoke samples from the burning of plants from Amazonia indicate the input of directly volatilized natural products in the original plants during their combustion. However, the major organic compounds extracted from smoke consist of a series of lower molecular weight polar components, which are not natural products but the result of the thermal breakdown of cellulose and lignin. In contrast, the HMW natural products may be suitable tracers for specific sources of vegetation combustion because they are emitted as particles without thermal alternation in the smoke and can thus be related directly to the original plant material.

  16. Meningococcal endotoxin in lethal septic shock plasma studied by gas chromatography, mass-spectrometry, ultracentrifugation, and electron microscopy.

    PubMed Central

    Brandtzaeg, P; Bryn, K; Kierulf, P; Ovsteb, R; Namork, E; Aase, B; Jantzen, E

    1992-01-01

    We have compared gas chromatography and mass spectrometry (GC-MS) analysis with the Limulus amebocyte lysate (LAL) assay to quantify native meningococcal lipopolysaccharides (LPS) in five patient plasmas containing greater than 5 micrograms/liter by LAL. 3-Hydroxy lauric acid (3-OH-12:0) was used as a specific lipid A marker of neisserial LPS. The quantitative LAL results were confirmed by GC-MS (r = 0.98, P = 0.006). Seven patient plasmas were centrifuged at 103,000 g and the sedimentation behavior of native LPS compared with reference plasma proteins and with apo A1 and apo B100 representing high and low density lipoproteins. After 15 min of centrifugation, 84 +/- 2% (mean +/- SE) of the recovered LPS were found in the lower one-third of the centrifuged volume, whereas 6 +/- 1% remained in the upper one-third volume, indicating that meningococcal endotoxin circulates as complexes with high sedimentation coefficients. Bacterial outer membrane fragments were detected in the bottom fractions of three patient plasmas examined by means of electron microscopy. In three patient plasmas ultracentrifuged for 60 min at 103,000 g, the levels of apo A1 and apo B100 revealed minor changes, whereas only 1 +/- 1% of the recovered LPS remained in the upper one-third and 91 +/- 2% were found in the lower one-third volume. Few bioreactive LPS appear to be complexed with high and low density lipoproteins in meningococcal septic shock plasma. Images PMID:1541674

  17. Evaluation of trace analyte identification in complex matrices by low-resolution gas chromatography - Mass spectrometry through signal simulation.

    PubMed

    Bettencourt da Silva, Ricardo J N

    2016-04-01

    The identification of trace levels of compounds in complex matrices by conventional low-resolution gas chromatography hyphenated with mass spectrometry is based in the comparison of retention times and abundance ratios of characteristic mass spectrum fragments of analyte peaks from calibrators with sample peaks. Statistically sound criteria for the comparison of these parameters were developed based on the normal distribution of retention times and the simulation of possible non-normal distribution of correlated abundances ratios. The confidence level used to set the statistical maximum and minimum limits of parameters defines the true positive rates of identifications. The false positive rate of identification was estimated from worst-case signal noise models. The estimated true and false positive identifications rate from one retention time and two correlated ratios of three fragments abundances were combined using simple Bayes' statistics to estimate the probability of compound identification being correct designated examination uncertainty. Models of the variation of examination uncertainty with analyte quantity allowed the estimation of the Limit of Examination as the lowest quantity that produced "Extremely strong" evidences of compound presence. User friendly MS-Excel files are made available to allow the easy application of developed approach in routine and research laboratories. The developed approach was successfully applied to the identification of chlorpyrifos-methyl and malathion in QuEChERS method extracts of vegetables with high water content for which the estimated Limit of Examination is 0.14mgkg(-1) and 0.23mgkg(-1) respectively. PMID:26838443

  18. Chemical characterisation of two Australian-grown strawberry varieties by using comprehensive two-dimensional gas chromatography-mass spectrometry.

    PubMed

    Samykanno, Kavitha; Pang, Edwin; Marriott, Philip J

    2013-12-01

    The volatile compositions of two strawberry varieties ('Albion' and 'Juliette') grown in Australia were analysed with comprehensive two-dimensional gas chromatography (GCGC) combined with time-of-flight mass spectrometry (ToFMS). A suitable data processing method was created that should be sufficiently robust to compare sample chromatograms within a harvest season as well as between seasons with relative ease. Ninety-four compounds were tentatively or positively identified between the two varieties of which 20 have apparently not been previously reported to be components of strawberry volatiles. It was determined that Albion and Juliette have comparable total soluble solids content close to 11Brix. However, since Juliette exhibited a lower titratable acidity content than Albion, it consequently has a slightly larger sugar/acid ratio. The presence of 2,5-dimethyl-4-hydroxy-(2H)-furan-3-one (furaneol) was detected only in Juliette and this variety also had a higher area percentage of 2,5-dimethyl-4-methoxy-(2H)-furan-3-one (mesifuran), according to the sampling protocol. These experimental results offer possible explanations as to why Juliette is perceived to have a sweeter flavour than Albion. PMID:23870920

  19. Determination of 17 pyrethroid residues in troublesome matrices by gas chromatography/mass spectrometry with negative chemical ionization.

    PubMed

    Shen, Chong-yu; Cao, Xiao-wen; Shen, Wei-jian; Jiang, Yuan; Zhao, Zeng-yun; Wu, Bin; Yu, Ke-yao; Liu, Han; Lian, Hong-zhen

    2011-03-15

    An analytical method with the technique of QuEChERS (quick, easy, cheap, effective, rugged and safe) and gas chromatography (GC)/mass spectrometry (MS) in negative chemical ionization (NCI) has been developed for the determination of 17 pyrethroid pesticide residues in troublesome matrices, including garlic, onion, spring onion and chili. Pyrethroid residues were extracted with acidified acetonitrile saturated by hexane. After a modified QuEChERS clean-up step, the extract was analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode. An isotope internal standard of trans-cypermethrin-D(6) was employed for quantitation. Chromatograms of pyrethroids obtained in all these matrices were relatively clean and without obvious interference. The limits of detection (LODs) ranged from 0.02 to 6 ?g kg(-1) and recovery yields were from 54.0% to 129.8% at three spiked levels (20, 40 and 60 ?g kg(-1) for chili, and 10, 20 and 30 ?g kg(-1) for others) in four different matrices depending on the compounds determined. The relative standard deviations (RSDs) were all below 14%. Isomerization enhancement of pyrethroids in chili extract was observed and preliminarily explained, especially for acrinathrin and deltamethrin. PMID:21315911

  20. The Global Volatile Signature of Veal via Solid-phase Microextraction and Gas Chromatography-mass Spectrometry

    PubMed Central

    2014-01-01

    The volatile composition of veal has yet to be reported and is one of the important factors determining meat character and quality. To identify the most important aroma compounds in veal from Holstein bull calves fed one of three diets, samples were subjected to solid-phase microextraction (SPME) combined with gas chromatography-quadrupole mass spectrometry (GC-MS). Most of the important odorants were aldehydes and alcohols. For group A (veal calves fed entirely on milk for 90 d before slaughter), the most abundant compound class was the aldehydes (52.231%), while that was alcohols (26.260%) in group C (veal calves fed starter diet for at least 60 d before slaughter). In both classes the absolute percentages of the volatile compounds in veal were different indicating that the veal diet significantly (p<0.05) affected headspace volatile composition in veal as determined by principal component analysis (PCA). Twenty three volatile compounds showed significance by using a partial least-squared discriminate analysis (PLS-DA) (VIP>1). The establishment of the global volatile signature of veal may be a useful tool to define the beef diet that improves the organoleptic characteristics of the meat and consequently impacts both its taste and economic value. PMID:26761505

  1. Laboratory Activity for the Determination of Nicotine in Electronic Cigarette Liquids using Gas Chromatography-Mass Spectrometry

    PubMed Central

    Pagano, Todd; Bida, Morgan R.; Robinson, Risa J.

    2015-01-01

    In recent years the prevalence and popularity of electronic cigarettes (ECs) has increased noticeably and a large market for their refillable nicotine solutions (e-liquids) has also rapidly increased. These e-liquids contain nicotine, an addictive and potentially dangerous stimulant, but often the actual nicotine content differs significantly from manufacturers labelling, due in part to lack of regulation for these products. A laboratory activity for undergraduate students was developed to directly test e-liquids for nicotine content using gas chromatography combined with mass spectrometry (GC-MS) as a means for teaching the instrumentation to undergraduate students using an authentic, real-world example. The activity introduces and/or re-emphasizes the theory and operation of GC-MS, standard/sample preparation, calibration curves, internal standards, selected ion monitoring mode of MS operation, and method validation. The laboratory experiment is designed for students enrolled in Quantitative Analysis courses (like Analytical Chemistry or Instrumental Analysis), but portions are also suitable for lower level chemistry courses or even those designed for allied health professionals or non-chemistry majors. Given the current popularity of ECs, this activity can provide the chemistry curriculum with a timely, real-world, and contemporary application in which crucial course content is taught. Students can also benefit from the inherent discussion of ECs, regulations, and related social aspects of smoking and EC vaping which can serve as a secondary learning outcome. PMID:26478904

  2. Magnetic solid phase extraction and static headspace gas chromatography-mass spectrometry method for the analysis of polycyclic aromatic hydrocarbons.

    PubMed

    Cai, Ying; Yan, Zhihong; Wang, Lijia; NguyenVan, Manh; Cai, Qingyun

    2016-01-15

    A magnetic solid phase extraction (MSPE) protocol combining a static headspace gas chromatography coupled to mass spectrometry (HS-GC-MS) method has been developed for extraction, and determination of 16 polycyclic aromatic hydrocarbons (PAHs) in drinking water samples. Magnetic nanoparticles (MNPs) were coated with 3-aminopropyltriethoxysilane and modified by cholesterol chloroformate. Transmission electron microscope, vibrating sample magnetometer, Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy were used to characterize the cholesterol-functionalized sorbents, and the main parameters affecting the extraction as well as HS sampling, such as sorbent amount, extraction time, oven temperature and equilibration time have been investigated and established. Combination with HS sampling, the MSPE procedure was simple, fast and environmentally friendly, without need of any organic solvent. Method validation proved the feasibility of the developed sorbents for the quantitation of the investigated analytes at trace levels obtaining the limit of detection (S/N=3) ranging from 0.20 to 7.8ng/L. Good values for intra and inter-day precision were obtained (RSDs≤9.9%). The proposed method was successfully applied to drinking water samples. PMID:26724892

  3. Nitrogen incorporation in Titan's tholins inferred by high resolution orbitrap mass spectrometry and gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Gautier, Thomas; Carrasco, Nathalie; Schmitz-Afonso, Isabelle; Touboul, David; Szopa, Cyril; Buch, Arnaud; Pernot, Pascal

    2014-10-01

    Influx of solar photons and heavy charged particles from Saturn's magnetosphere on Titan's atmosphere - mainly comprised of methane and nitrogen - induce an intense organic photochemistry which leads to the formation of a large amount of aerosols in suspension in the atmosphere. In order to infer the role of nitrogen in aerosol formation processes we produced laboratory analogs of Titan's aerosols. In this work, we compare the composition of different analogs by using high resolution mass spectrometry and propose an additional study using gas-chromatography coupled to mass-spectrometry for a new kind of analog produced by polymerization of cryogenically trapped gaseous neutral species. The comparison of these materials emphasizes the importance of ion chemistry processes for the inclusion of nitrogen in molecules constituting Titan's tholins. A statistical approach is also used for the treatment of high resolution mass spectra of these highly complex organic materials. This method allows distinguishing molecular families that can be reconstructed by an ideal copolymer. We investigate several copolymer reconstructions, and we suggest that an HCN (or CH3CN)/C2H4 based copolymer agrees well with the polymeric structure of tholins produced with 5% of methane in nitrogen.

  4. Multi-Component Profiling of Trace Volatiles in Blood by Gas Chromatography/Mass Spectrometry with Dynamic Headspace Extraction.

    PubMed

    Kakuta, Shoji; Yamashita, Toshiyuki; Nishiumi, Shin; Yoshida, Masaru; Fukusaki, Eiichiro; Bamba, Takeshi

    2015-01-01

    A dynamic headspace extraction method (DHS) with high-pressure injection is described. This dynamic extraction method has superior sensitivity to solid phase micro extraction, SPME and is capable of extracting the entire gas phase by purging the headspace of a vial. Optimization of the DHS parameters resulted in a highly sensitive volatile profiling system with the ability to detect various volatile components including alcohols at nanogram levels. The average LOD for a standard volatile mixture was 0.50 ng mL(-1), and the average LOD for alcohols was 0.66 ng mL(-1). This method was used for the analysis of volatile components from biological samples and compared with acute and chronic inflammation models. The method permitted the identification of volatiles with the same profile pattern as in vitro oxidized lipid-derived volatiles. In addition, the concentration of alcohols and aldehydes from the acute inflammation model samples were significantly higher than that for the chronic inflammation model samples. The different profiles between these samples could also be identified by this method. Finally, it was possible to analyze alcohols and low-molecular-weight volatiles that are difficult to analyze by SPME in high sensitivity and to show volatile profiling based on multi-volatile simultaneous analysis. PMID:26819905

  5. Application of gas chromatography-mass spectrometry metabolite profiling techniques to the analysis of heathland plant diets of sheep.

    PubMed

    Parveen, Ifat; Moorby, Jon M; Fraser, Mariecia D; Allison, Gordon G; Kopka, Joachim

    2007-02-21

    Little is known about how plant biochemistry influences the grazing behavior of animals consuming heterogeneous plant communities. The biochemical profiles of grassland species are mostly restricted to major nutritional characteristics, although recent developments in analytical techniques and data analysis have made possible the detailed analysis of minor components that may influence animal feeding preferences, performance, and health. In the present study, gas chromatography coupled with time-of-flight mass spectrometry (GC-TOF/MS) was used to profile the abundances of metabolites in nine specific heathland plant groups and in three mixed forage diets containing 10, 20, or 30% heather (Calluna vulgaris) and also in plasma and feces from sheep offered one of the three diets. Statistical and chemometric approaches, that is, principal component analysis (PCA) and hierarchical cluster analysis (HCA), were used to discriminate between these diets and between individual animals maintained on these diets. It is shown that GC-TOF/MS analysis of sheep plasma allowed distinction between the very similar diets by PCA and HCA, and, moreover, the plant metabolites responsible for the differences observed have been identified. Furthermore, metabolite markers of herbage mixtures and individual plant groups have been identified, and markers have been detected in sheep plasma and feces. PMID:17249687

  6. Measurement of boar taint in porcine fat using a high-throughput gas chromatography-mass spectrometry protocol.

    PubMed

    Sørensen, Klavs M; Engelsen, Søren Balling

    2014-10-01

    This work outlines an optimized gas chromatrography-mass spectrometry (GC-MS) based protocol for screening of the presence of the three boar-taint-producing compounds indole, skatole (3-methylindole), and androstenone (5α-androst-16-en-3-one) in porcine fat. The study shows that an accuracy suitable for sample screening can be achieved even when speed and ease of sample handling is prioritized and without the use of internal standards. The method provides levels of detection of 82 ng/g for indole, 97 ng/g for skatole, and 623 ng/g for androstenone (in a 2 g natural backfat matrix). A least-squares approach of predicting the sample analyte mass from instrument response is shown to have prediction errors (root-mean-square error) of 96 ng/g for indole, 94 ng/g for skatole, and 331.3 ng/g for androstenone. The method is intended for discrimination of samples in risk groups, and a scheme is proposed to turn the GC-MS response of the boar-taint analytes into risk classes. PMID:25230360

  7. Identification of volatile lung cancer markers by gas chromatography-mass spectrometry: comparison with discrimination by canines.

    PubMed

    Buszewski, Bogus?aw; Ligor, Tomasz; Jezierski, Tadeusz; Wenda-Piesik, Anna; Walczak, Marta; Rudnicka, Joanna

    2012-07-01

    In this work, a chromatographic method for identification of volatile organic compounds was compared with canine recognition. Gas chromatography and mass spectrometry (GC-TOF MS) were used for determination of concentrations of trace gases present in human breath. The technique enables rapid determination of compounds in human breath, at the parts per billion level. Linear correlations were from 0.83-234.05 ppb, the limit of detection was the range 0.31-0.75 ppb, and precision, expressed as relative standard deviation (RSD), was less than 10.00 %. Moreover, trained dogs are able to discriminate breath samples of patients with diagnosed cancer. We found a positive correlation between dog indications and the ethyl acetate and 2-pentanone content of breath (r = 0.85 and r = 0.97, respectively). The methods presented for detection of lung cancer markers in exhaled air could be used as a potential non-invasive tool for screening. In addition, the canine method is relatively simple and inexpensive in comparison with chromatography. PMID:22660158

  8. Novel multiresidue method for determination of pesticides in red wine using gas chromatography-mass spectrometry and solid phase extraction.

    PubMed

    Pelajić, Maja; Peček, Gorana; Mutavdžić Pavlović, Dragana; Vitali Čepo, Dubravka

    2016-06-01

    A new multiresidue method was developed for determination of 25 pesticide residues in red wine by gas chromatography coupled to mass spectrometry with a single run of 23.63min. Samples were extracted from wine with solid phase extraction using Oasis HLB. Mixture of methanol and water was used for rinsing, while acetonitrile and n-hexane were used as elution solvents. Method was validated according to SANCO/12571/2013 criteria in wide linearity range (limit of quantification - 400μgL(-1)). Limits of quantification (LOQ) were well below 10μgL(-1) for most pesticides and recoveries at 2×LOQ and 10×LOQ concentration levels were in range 70-120%. Precision, expressed as a relative standard deviation, was always under 14%. The method was applied to 32 red wine samples from Croatia. Pesticides were detected in 30 samples with a total of 15 pesticides found, 7 of which were at a high concentration. PMID:26830566

  9. Determination of dextromethorphan in human plasma using pipette tip solid-phase extraction and gas chromatography-mass spectrometry.

    PubMed

    Hasegawa, Chika; Kumazawa, Takeshi; Uchigasaki, Seisaku; Lee, Xiao-Pen; Sato, Keizo; Terada, Masaru; Kurosaki, Kunihiko

    2011-10-01

    Dextromethorphan was extracted from human plasma samples (100 ?L) using MonoTip C(18) tips, which are packed with C(18)-bonded monolithic silica gel that is attached to the inside of the tip. The samples, which contained dextromethorphan and trimeprazine as an internal standard (IS), were mixed with 200 ?L of distilled water and 50 ?L of 1 mol/L glycine-sodium hydroxide buffer (pH 10). The mixture was extracted to the C(18) phase of the tip by 20 sequential aspirating/dispensing cycles using a manual micropipettor. The analytes retained on the C(18) phase were then eluted with methanol by five sequential aspirating/dispensing cycles. The eluate was injected directly into a gas chromatograph and detected by a mass spectrometer with selected ion monitoring in positive electron ionization mode. An Equity-5 fused silica capillary column (30 m 0.32 mm i.d., film thickness 0.5 ?m) gave adequate separation of the dextromethorphan, IS, and impurities. The recoveries of dextromethorphan and the IS spiked into plasma were >87.4%. The regression equation for dextromethorphan showed excellent linearity from 2.5 to 320 ng/mL of plasma, and the limit of detection was 1.25 ng/mL of plasma. The intraday and interday coefficients of variation were less than 10.5% and 14.7%, respectively. The accuracy ranged from 91.9% to 107%. The validated method was successfully used to quantify the plasma concentration of dextromethorphan in a human subject after oral administration of the drug. PMID:21874269

  10. Pipette tip solid-phase extraction and gas chromatography-mass spectrometry for the determination of mequitazine in human plasma.

    PubMed

    Kumazawa, Takeshi; Hasegawa, Chika; Lee, Xiao-Pen; Marumo, Akemi; Shimmen, Natsuko; Ishii, Akira; Seno, Hiroshi; Sato, Keizo

    2006-09-15

    Mequitazine has been found to be extractable from human plasma samples using MonoTip C(18) tips, inside which C(18)-bonded monolithic silica gel was fixed. Human plasma (0.1mL) containing mequitazine and cyproheptadine as an internal standard (IS) was mixed with 0.4mL of distilled water and 25muL of 1M potassium phosphate buffer (pH 8.0). After centrifugation of the mixture, the supernatant fraction was extracted to the C(18) phase of the tip by 25 repeated aspirating/dispensing cycles using a manual micropipettor. The analytes retained on the C(18) phase were then eluted with methanol by five repeated aspirating/dispensing cycles. Without evaporation and reconstitution, the eluate was injected into a gas chromatograph injector and detected by a mass spectrometer with selected ion monitoring in the positive-ion electron impact mode. The separation of mequitazine and the IS from each other and from impurities was generally satisfactory using a DB-1MS capillary column (30mx0.32mm i.d., film thickness 0.25mum). The recoveries of mequitazine and the IS spiked into plasma were more than 90.0%. The regression equation for mequitazine showed excellent linearity in the range of 0.2-200ng0.1mL(-1), and the detection limit was 0.05ng0.1mL(-1)of plasma. The intra-day and inter-day coefficients of variation for mequitazine in human plasma were not greater than 8.16 and 9.24%, respectively. Accuracy for the drug was in the range of 90.0-97.4%. The data obtained from determination of mequitazine in human plasma after oral administration of the drug are also presented. PMID:18970795

  11. Studies on anabolic steroids. III. Detection and characterization of stanozolol urinary metabolites in humans by gas chromatography-mass spectrometry.

    PubMed

    Mass, R; Ayotte, C; Bi, H G; Dugal, R

    1989-12-29

    The metabolism of stanozolol (17 beta-hydroxy-17 alpha-methyl-5 alpha-androstano[3,2-c]pyrazole), an androgenic-anabolic steroid widely used in sport for the purpose of enhancing performance, was investigated in humans. The analysis method was based on the use of solid-phase extraction on the Sep-Pak C18 cartridge, enzymic hydrolysis of steroid conjugates and high-resolution gas chromatograph-mass spectrometric (GC-MS) analysis of trimethylsilylated steroid extracts. After administration of a single 20-mg oral dose, twelve metabolites including unchanged stanozolol were recovered predominantly from the conjugated steroid fraction and characterized by GC-MS. In the unconjugated fraction, 16 alpha-hydroxystanozolol, 17-epistanozolol, stanozolol and 3'-hydroxy-17-epistanozolol were the most abundant metabolites. In the aglycone fraction, 16 alpha- and 16 beta-hydroxystanozolol, stanozolol and 3'-hydroxystanozolol were the most abundant metabolites. Other metabolites resulted from regioselective hydroxylation of stanozolol at C-4, whereas other were 17-epimers of 3'- and 16 alpha-hydroxystanozolol. Further hydroxylation leading to the formation of four isomeric dihydroxylated metabolites was also observed. They were tentatively assigned the structures of 3',16 alpha-, 4 beta,16 alpha-, 3',16 beta- and 4 beta,16 beta-dihydroxystanozolol. The mass spectral features of their bis-N,O-trimethylsilyl derivatives obtained under electron-impact ionization are presented. The effect of pH on the relative recovery of some of these metabolites is also presented. The usefulness of this analytical methodology for the detection and identification of stanozolol urinary metabolites in doping-control situations is demonstrated. The metabolism of stanozolol is also discussed, and metabolic pathways accounting for the formation of its biotransformation products are proposed. PMID:2625454

  12. Hyphenation of supercritical fluid chromatography and two-dimensional gas chromatography-mass spectrometry for group type separations.

    PubMed

    Potgieter, H; van der Westhuizen, R; Rohwer, E; Malan, D

    2013-06-14

    The Fischer-Tropsch (FT) process produces a variety of compounds over a wide carbon number range and the synthetic crude oil produced by this process is rich in highly valuable olefins and oxygenates, which crude oil only contains at trace levels. The characterization of these products is very challenging even when using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCGC-TOF-MS). The separation between cyclic paraffins and olefins is especially difficult since they elute in similar positions on the GCGC chromatogram and since they have identical molecular masses with indistinguishable fragmentation patterns. Previously, a high performance liquid chromatography (HPLC) fractionation procedure was used prior to GCGC-TOF-MS analysis to distinguish between alkenes and alkanes, both cyclic and non-cyclic, however, there was co-elution of the solvents used in the HPLC fractionation procedure, and the volatile components in the gasoline sample and the dilution introduced by the off-line fractionation procedure made it very difficult to investigate components present at very low concentrations. The hyphenation of supercritical fluid chromatography (SFC) to GCGC is less complicated and the removal of the supercritical CO2 can be easily achieved without any loss of the volatile sample components, eliminating the introduction of co-eluting solvents as well as the dilution effect. This paper describes the on-line hyphenation of SFC to a GCGC system in order to comprehensively characterize the chemical groups (saturates, unsaturates, oxygenates and aromatics) in an FT sample. PMID:23647609

  13. Seized cannabis seeds cultivated in greenhouse: A chemical study by gas chromatography-mass spectrometry and chemometric analysis.

    PubMed

    Mariotti, Kristiane de Cássia; Marcelo, Marcelo Caetano Alexandre; Ortiz, Rafael S; Borille, Bruna Tassi; Dos Reis, Monique; Fett, Mauro Sander; Ferrão, Marco Flôres; Limberger, Renata Pereira

    2016-01-01

    Cannabis sativa L. is cultivated in most regions of the world. In 2013, the Brazilian Federal Police (BFP) reported 220tons of marijuana seized and about 800,000 cannabis plants eradicated. Efforts to eradicate cannabis production may have contributed to the development of a new form of international drug trafficking in Brazil: the sending of cannabis seeds in small amounts to urban centers by logistics postal. This new and increasing panorama of cannabis trafficking in Brazil, encouraged the chemical study of cannabis seeds cultivated in greenhouses by gas-chromatography coupled with mass spectrometry (GC-MS) associated with exploratory and discriminant analysis. Fifty cannabis seeds of different varieties and brands, seized by the BFP were cultivated under predefined conditions for a period of 4.5weeks, 5.5weeks, 7.5weeks, 10weeks and 12weeks. Aerial parts were analyzed and cannabigerol, cannabinol, cannabidiol, cannabichromene Δ9-tetrahydrocannabinol (THC) and other terpenoids were detected. The chromatographic chemical profiles of the samples were significantly different, probably due to different variety, light exposition and age. THC content increased with the age of the plant, however, for other cannabinoids, this correlation was not observed. The chromatograms were plotted in a matrix with 50 rows (samples) and 3886 columns (abundance in a retention time) and submitted to PCA, HCA and PLS-DA after pretreatment (normalization, first derivative and autoscale). The PCA and HCA showed age separation between samples however it was not possible to verify the separation by varieties and brands. The PLS-DA classification provides a satisfactory prediction of plant age. PMID:26746824

  14. Method development for the determination of wood preservatives in commercially treated wood using gas chromatography-mass spectrometry.

    PubMed

    ?vov, Jana; Sedgeman, Carl A; Smith, Zachary T; Frink, Lillian A; Hart, Jessica A; Niri, Vadoud H; Kubtov, Alena

    2011-09-30

    Fungicides and insecticides are commonly used preservatives to protect wood products against microbiological degradations. Currently, there is a lack of analytical methods addressing the quantitative determination of a wide range of wood preserving species in wood matrices. In this study, a reliable method was developed for the determination of a mixture of wood preserving agents with differing chemical structures (i.e., properties), including tebuconazole (TAZ), propiconazole (PAZ), 3-iodo-2-propynyl butylcarbamate (IPBC), and permethrin (PER), in pine wood. The analyte recoveries obtained by Soxhlet and multiple-stage sonication extractions were compared. While both extraction methods yielded similar results (80-100%), Soxhlet extraction was found to be less labor-intensive and thus preferred providing also lower RSDs of 1-6%. In comparison to methanol, commonly used as an extraction solvent for triazoles, acetone yielded similar extraction efficiencies for all analytes while reducing the time of sample concentration. The solid phase extraction method for triazoles was adapted to allow for a separation of IPBC and PER from the wood matrix. As opposed to previous studies, three recovery standards were employed, which enabled the correction of individual analyte losses during the sample preparation. The matrix-affected limits of detection (LODs) using gas chromatography with mass spectrometric detection were nearly the same for triazoles 0.07 and 0.21 ng g(-1) for PAZ and TAZ in sapwood and 0.18 and 0.21 ng g(-1) in heartwood, respectively. Higher LODs were observed for IPBC and PER: 3.9 and 1.7 ng g(-1) in sapwood, and 2.0 and 6.0 ng g(-1) in heartwood, respectively. The recoveries in the wood submitted to commercial sample treatment showed gradient distribution of analytes depending on the penetration of the treatment. PMID:21839199

  15. [Simultaneous determination of phthalates and parabens in cosmetic products by gas chromatog