WorldWideScience

Sample records for headspace analysis

  1. Headspace Analysis of Ammonium Nitrate

    Science.gov (United States)

    2017-01-25

    explosive ammonium nitrate produces ammonia and nitric acid in the gaseous headspace above bulk solids, but the concentrations of the products have been...and NO2-, a product of nitrate fragmentation (Figure 7). Brief spikes in the background and dips in oxalic acid signal were observed at the time of...either filtered air or experimental nitric acid vapor sources so that analyte signal could be measured directly opposite background. With oxalic

  2. Headspace analysis of foams and fixatives

    Energy Technology Data Exchange (ETDEWEB)

    Harper, Kyle [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Truong, Thanh-Tam [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Magwood, Leroy [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Peters, Brent [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Nicholson, James [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Washington, II, Aaron L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-07-27

    In the process of decontaminating and decommissioning (D&D) older nuclear facilities, special precautions must be taken with removable or airborne contamination. One possible strategy utilizes foams and fixatives to affix these loose contaminants. Many foams and fixatives are already commercially available, either generically or sold specifically for D&D. However, due to a lack of revelant testing in a radioactive environment, additional verification is needed to confirm that these products not only affix contamination to their surfaces, but also will function in a D&D environment. Several significant safety factors, including flammability and worker safety, can be analyzed through the process of headspace analysis, a technique that analyzes the off gas formed before or during the curing process of the foam/fixative, usually using gas chromatography-mass spectrometry (GC-MS). This process focuses on the volatile components of a chemical, which move freely between the solid/liquid form within the sample and the gaseous form in the area above the sample (the headspace). Between possibly hot conditions in a D&D situation and heat created in a foaming reaction, the volatility of many chemicals can change, and thus different gasses can be released at different times throughout the reaction. This project focused on analysis of volatile chemicals involved in the process of using foams and fixatives to identify any potential hazardous or flammable compounds.

  3. Performance Demonstration Program Plan for Analysis of Simulated Headspace Gases

    International Nuclear Information System (INIS)

    2006-01-01

    The Performance Demonstration Program (PDP) for headspace gases distributes sample gases of volatile organic compounds (VOCs) for analysis. Participating measurement facilities (i.e., fixed laboratories, mobile analysis systems, and on-line analytical systems) are located across the United States. Each sample distribution is termed a PDP cycle. These evaluation cycles provide an objective measure of the reliability of measurements performed for transuranic (TRU) waste characterization. The primary documents governing the conduct of the PDP are the Quality Assurance Program Document (QAPD) (DOE/CBFO-94-1012) and the Waste Isolation Pilot Plant (WIPP) Waste Analysis Plan (WAP) contained in the Hazardous Waste Facility Permit (NM4890139088-TSDF) issued by the New Mexico Environment Department (NMED). The WAP requires participation in the PDP; the PDP must comply with the QAPD and the WAP. This plan implements the general requirements of the QAPD and the applicable requirements of the WAP for the Headspace Gas (HSG) PDP. Participating measurement facilities analyze blind audit samples of simulated TRU waste package headspace gases according to the criteria set by this PDP Plan. Blind audit samples (hereafter referred to as PDP samples) are used as an independent means to assess each measurement facility's compliance with the WAP quality assurance objectives (QAOs). To the extent possible, the concentrations of VOC analytes in the PDP samples encompass the range of concentrations anticipated in actual TRU waste package headspace gas samples. Analyses of headspace gases are required by the WIPP to demonstrate compliance with regulatory requirements. These analyses must be performed by measurement facilities that have demonstrated acceptable performance in this PDP. These analyses are referred to as WIPP analyses and the TRU waste package headspace gas samples on which they are performed are referred to as WIPP samples in this document. Participating measurement

  4. Performance Demonstration Program Plan for Analysis of Simulated Headspace Gases

    International Nuclear Information System (INIS)

    2007-01-01

    The Performance Demonstration Program (PDP) for headspace gases distributes blind audit samples in a gas matrix for analysis of volatile organic compounds (VOCs). Participating measurement facilities (i.e., fixed laboratories, mobile analysis systems, and on-line analytical systems) are located across the United States. Each sample distribution is termed a PDP cycle. These evaluation cycles provide an objective measure of the reliability of measurements performed for transuranic (TRU) waste characterization. The primary documents governing the conduct of the PDP are the Quality Assurance Program Document (QAPD) (DOE/CBFO-94-1012) and the Waste Isolation Pilot Plant (WIPP) Waste Analysis Plan (WAP) contained in the Hazardous Waste Facility Permit (NM4890139088-TSDF) issued by the New Mexico Environment Department (NMED). The WAP requires participation in the PDP; the PDP must comply with the QAPD and the WAP. This plan implements the general requirements of the QAPD and the applicable requirements of the WAP for the Headspace Gas (HSG) PDP. Participating measurement facilities analyze blind audit samples of simulated TRU waste package headspace gases according to the criteria set by this PDP Plan. Blind audit samples (hereafter referred to as PDP samples) are used as an independent means to assess each measurement facility's compliance with the WAP quality assurance objectives (QAOs). To the extent possible, the concentrations of VOC analytes in the PDP samples encompass the range of concentrations anticipated in actual TRU waste package headspace gas samples. Analyses of headspace gases are required by the WIPP to demonstrate compliance with regulatory requirements. These analyses must be performed by measurement facilities that have demonstrated acceptable performance in this PDP. These analyses are referred to as WIPP analyses and the TRU waste package headspace gas samples on which they are performed are referred to as WIPP samples in this document

  5. Quality control of raw cows' milk by headspace analysis

    NARCIS (Netherlands)

    Hettinga, K.A.; Valenberg, van H.J.F.; Hooijdonk, van A.C.M.

    2008-01-01

    This study investigated whether headspace analysis of volatile components can be used for monitoring the quality of raw cows¿ milk. The detection of different quality defects caused by cows¿ feed, microbiological and chemical contamination, as well as enzymatic deterioration was studied. Fresh raw

  6. Organic analysis of the headspace in Hanford waste tanks

    International Nuclear Information System (INIS)

    Lucke, R.B.; McVeety, B.D.; Clauss, T.W.; Fruchter, J.S.; Goheen, S.C.

    1994-01-01

    Before radioactive mixed waste in Hanford waste tanks can be isolated and permanently stored, several safety issues need to be addressed. The headspace vapors in Hanford Tank 103-C raise two issues: (1) the potential flammability of the vapor and aerosol, and (2) the potential worker health and safety hazards associated with the toxicity of the constituents. As a result, the authors have implemented organic analysis methods to characterize the headspace vapors in Hanford waste tanks. To address the flammability issue, they have used OSHA versatile sampling (OVS) tubes as the sampling method followed by solvent extraction and GC/MS analysis. For analyzing volatile organics and organic air toxins, they have implemented SUMMA trademark canisters as the collection device followed by cryogenic trapping and GC/MS analysis. Strategies for modifying existing NIOSH and EPA methods to make them applicable to vapors in Hanford waste tanks are discussed. Identification and quantification results of volatile and semivolatile organics are presented

  7. Performance demonstration program plan for analysis of simulated headspace gases

    International Nuclear Information System (INIS)

    1995-06-01

    The Performance Demonstration Program (PDP) for analysis of headspace gases will consist of regular distribution and analyses of test standards to evaluate the capability for analyzing VOCs, hydrogen, and methane in the headspace of transuranic (TRU) waste throughout the Department of Energy (DOE) complex. Each distribution is termed a PDP cycle. These evaluation cycles will provide an objective measure of the reliability of measurements performed for TRU waste characterization. Laboratory performance will be demonstrated by the successful analysis of blind audit samples of simulated TRU waste drum headspace gases according to the criteria set within the text of this Program Plan. Blind audit samples (hereinafter referred to as PDP samples) will be used as an independent means to assess laboratory performance regarding compliance with the QAPP QAOs. The concentration of analytes in the PDP samples will encompass the range of concentrations anticipated in actual waste characterization gas samples. Analyses which are required by the WIPP to demonstrate compliance with various regulatory requirements and which are included in the PDP must be performed by laboratories which have demonstrated acceptable performance in the PDP

  8. Analysis of Cyanide in Blood by Headspace-Isotope-Dilution-GC-MS

    DEFF Research Database (Denmark)

    Løbger, Lise Lotte; Petersen, Henning Willads; Andersen, Jens Enevold Thaulov

    2008-01-01

    An uncomplicated, rapid, automated procedure for the analysis of low cyanide concentrations in whole blood is reported. The analysis was performed by headspace gas chromatography and mass spectrometry in the (1H12C14N) and m/z 29 (1H13C15N). Carryover from cyanide adsorption onto the surface...

  9. Optimizing headspace sampling temperature and time for analysis of volatile oxidation products in fish oil

    DEFF Research Database (Denmark)

    Rørbæk, Karen; Jensen, Benny

    1997-01-01

    Headspace-gas chromatography (HS-GC), based on adsorption to Tenax GR(R), thermal desorption and GC, has been used for analysis of volatiles in fish oil. To optimize sam sampling conditions, the effect of heating the fish oil at various temperatures and times was evaluated from anisidine values (AV...

  10. Gram-negative and -positive bacteria differentiation in blood culture samples by headspace volatile compound analysis.

    Science.gov (United States)

    Dolch, Michael E; Janitza, Silke; Boulesteix, Anne-Laure; Graßmann-Lichtenauer, Carola; Praun, Siegfried; Denzer, Wolfgang; Schelling, Gustav; Schubert, Sören

    2016-12-01

    Identification of microorganisms in positive blood cultures still relies on standard techniques such as Gram staining followed by culturing with definite microorganism identification. Alternatively, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry or the analysis of headspace volatile compound (VC) composition produced by cultures can help to differentiate between microorganisms under experimental conditions. This study assessed the efficacy of volatile compound based microorganism differentiation into Gram-negatives and -positives in unselected positive blood culture samples from patients. Headspace gas samples of positive blood culture samples were transferred to sterilized, sealed, and evacuated 20 ml glass vials and stored at -30 °C until batch analysis. Headspace gas VC content analysis was carried out via an auto sampler connected to an ion-molecule reaction mass spectrometer (IMR-MS). Measurements covered a mass range from 16 to 135 u including CO2, H2, N2, and O2. Prediction rules for microorganism identification based on VC composition were derived using a training data set and evaluated using a validation data set within a random split validation procedure. One-hundred-fifty-two aerobic samples growing 27 Gram-negatives, 106 Gram-positives, and 19 fungi and 130 anaerobic samples growing 37 Gram-negatives, 91 Gram-positives, and two fungi were analysed. In anaerobic samples, ten discriminators were identified by the random forest method allowing for bacteria differentiation into Gram-negative and -positive (error rate: 16.7 % in validation data set). For aerobic samples the error rate was not better than random. In anaerobic blood culture samples of patients IMR-MS based headspace VC composition analysis facilitates bacteria differentiation into Gram-negative and -positive.

  11. Dynamic Headspace Sampling as an Initial Step for Sample Preparation in Chromatographic Analysis.

    Science.gov (United States)

    Wojnowski, Wojciech; Majchrzak, Tomasz; Dymerski, Tomasz; Gębicki, Jacek; Namieśnik, Jacek

    2017-11-01

    This work represents a brief summary of the use of dynamic headspace (DHS) as a technique for sample preparation in chromatographic analysis. Despite numerous developments in the area of analyte isolation and enrichment, DHS remains one of the fundamental methods used with GC. In our opinion, interest in this technique will not diminish significantly because it conforms to stipulations of green analytical chemistry. Moreover, DHS fulfills the need for methods that facilitate detection and determination of analytes present at ultratrace levels in complex matrixes. The main focus of this work was placed on the theoretical fundamentals of this method. Also described herein were DHS development, the advantages and disadvantages of this technique compared with other headspace sampling techniques, and selected examples of its applications in food and environmental analyses.

  12. Organic analysis of the headspace of Hanford waste Tank 241-C-103

    International Nuclear Information System (INIS)

    Goheen, S.C.; McVeety, B.D.; Clauss, T.W.; Lucke, R.B.; Ligotke, M.W.; Edwards, J.A.; Fruchter, J.S.

    1996-01-01

    Organic species from the headspace of one Hanford radioactive waste tank are described. Samples were collected either using a sorbent trap or a SUMMA TM canister and were analyzed by gas chromatography and mass spectrometry. The headspace contained several organic components, including alkanes, alkanes, ketones, aldehydes, organic nitriles, and chlorinated hydrocarbons. Sorbent trap samples were designed to collect only normal paraffin hydrocarbons (NPHs). A comparison of NPH data from sorbent traps and SUMMA TM cans revealed results of 693 and 1320 mg/m 3 , NPH respectively. Significant differences were observed in NPH values when samples were collected at different times, or at different locations in the tank. These data suggest either the time of collection, or the position of the sampling device are important variables in the analysis of organic species from Hanford tanks. (author). 16 refs., 3 figs., 2 tabs

  13. Quantitative analysis of perfumes in talcum powder by using headspace sorptive extraction.

    Science.gov (United States)

    Ng, Khim Hui; Heng, Audrey; Osborne, Murray

    2012-03-01

    Quantitative analysis of perfume dosage in talcum powder has been a challenge due to interference of the matrix and has so far not been widely reported. In this study, headspace sorptive extraction (HSSE) was validated as a solventless sample preparation method for the extraction and enrichment of perfume raw materials from talcum powder. Sample enrichment is performed on a thick film of poly(dimethylsiloxane) (PDMS) coated onto a magnetic stir bar incorporated in a glass jacket. Sampling is done by placing the PDMS stir bar in the headspace vial by using a holder. The stir bar is then thermally desorbed online with capillary gas chromatography-mass spectrometry. The HSSE method is based on the same principles as headspace solid-phase microextraction (HS-SPME). Nevertheless, a relatively larger amount of extracting phase is coated on the stir bar as compared to SPME. Sample amount and extraction time were optimized in this study. The method has shown good repeatability (with relative standard deviation no higher than 12.5%) and excellent linearity with correlation coefficients above 0.99 for all analytes. The method was also successfully applied in the quantitative analysis of talcum powder spiked with perfume at different dosages. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Analysis of hydrogen and methane in seawater by "Headspace" method: Determination at trace level with an automatic headspace sampler.

    Science.gov (United States)

    Donval, J P; Guyader, V

    2017-01-01

    "Headspace" technique is one of the methods for the onboard measurement of hydrogen (H 2 ) and methane (CH 4 ) in deep seawater. Based on the principle of an automatic headspace commercial sampler, a specific device has been developed to automatically inject gas samples from 300ml syringes (gas phase in equilibrium with seawater). As valves, micro pump, oven and detector are independent, a gas chromatograph is not necessary allowing a reduction of the weight and dimensions of the analytical system. The different steps from seawater sampling to gas injection are described. Accuracy of the method is checked by a comparison with the "purge and trap" technique. The detection limit is estimated to 0.3nM for hydrogen and 0.1nM for methane which is close to the background value in deep seawater. It is also shown that this system can be used to analyze other gases such as Nitrogen (N 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ) and light hydrocarbons. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Time since discharge of 9mm cartridges by headspace analysis, part 1: Comprehensive optimisation and validation of a headspace sorptive extraction (HSSE) method.

    Science.gov (United States)

    Gallidabino, M; Romolo, F S; Weyermann, C

    2017-03-01

    Estimating the time since discharge of spent cartridges can be a valuable tool in the forensic investigation of firearm-related crimes. To reach this aim, it was previously proposed that the decrease of volatile organic compounds released during discharge is monitored over time using non-destructive headspace extraction techniques. While promising results were obtained for large-calibre cartridges (e.g., shotgun shells), handgun calibres yielded unsatisfying results. In addition to the natural complexity of the specimen itself, these can also be attributed to some selective choices in the methods development. Thus, the present series of paper aimed to more systematically evaluate the potential of headspace analysis to estimate the time since discharge of cartridges through the use of more comprehensive analytical and interpretative techniques. Specifically, in this first part, a method based on headspace sorptive extraction (HSSE) was comprehensively optimised and validated, as the latter recently proved to be a more efficient alternative than previous approaches. For this purpose, 29 volatile organic compounds were preliminary selected on the basis of previous works. A multivariate statistical approach based on design of experiments (DOE) was used to optimise variables potentially involved in interaction effects. Introduction of deuterated analogues in sampling vials was also investigated as strategy to account for analytical variations. Analysis was carried out by selected ion mode, gas chromatography coupled to mass spectrometry (GC-MS). Results showed good chromatographic resolution as well as detection limits and peak area repeatability. Application to 9mm spent cartridges confirmed that the use of co-extracted internal standards allowed for improved reproducibility of the measured signals. The validated method will be applied in the second part of this work to estimate the time since discharge of 9mm spent cartridges using multivariate models. Copyright

  16. Analysis of pollutants in air and water using gas chromatography and headspace gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Stenner, H.

    1980-01-01

    The combination 'personal sampling' with headspace gas chromatography to determine traces of formaldehyde, phenol and benzene in air is investigated in this work, with the aim of developing maximum workplace concentration values (MWL values). Further possible applications of gas chromatography in trace analysis in the environmentally protected area. The analysis of chromium in waste waters (Cr III as acetyl acetonate complex) is investigated as further possible application, whereby optimum conditions are obtained. A modified flame ionization detector was used to increase the detection sensitivity.

  17. Headspace Analysis of Volatile Compounds Coupled to Chemometrics in Leaves from the Magnoliaceae Family

    Directory of Open Access Journals (Sweden)

    Mohamed A. Farag

    2015-01-01

    Full Text Available Headspace volatile analysis has been used for volatiles profiling in leaves of 4 Magnolia species with a total of 75 compounds were identified. Monterpene hydrocarbons dominated the volatile blend of M. calophylla (86%, M. acuminata (78%, M. virginiana (70% and M. grandiflora (47% with b -pinene and b -ocimene occurring in the largest amounts, whereas sesquiterpenes were the most abundant compounds in M. grandiflora (39%. High levels of oxygenated compounds were only found in M. virginiana volatile blend (11.4% with 2-phenylethyl alcohol as major component. Hierarchical cluster analysis performed on volatiles content revealed the close relationship between M. acuminata and M. calophylla.

  18. Analysis of Furaneol in tomato using dynamic headspace sampling with sodium sulfate.

    Science.gov (United States)

    Buttery, R G; Takeoka, G R; Naim, M; Rabinowitch, H; Nam, Y

    2001-09-01

    High-flow dynamic headspace sampling with excess anhydrous sodium sulfate was found to be an effective method of isolating Furaneol from fresh tomatoes. Quantitative analysis was carried out by gas chromatography using maltol as internal standard. Furaneol was found in the highest concentrations (660-1100 ppb) in the summer crop of home-grown tomatoes and in some of the greenhouse hydroponically grown tomatoes, which are ripened on the plant before being transported to the supermarkets. Furaneol was found in the lowest concentrations (38-180 ppb) in the common ethylene-ripened, field-grown, supermarket tomatoes.

  19. Headspace analysis gas-phase infrared spectroscopy: a study of xanthate decomposition on mineral surfaces

    Science.gov (United States)

    Vreugdenhil, Andrew J.; Brienne, Stephane H. R.; Markwell, Ross D.; Butler, Ian S.; Finch, James A.

    1997-03-01

    The O-ethyldithiocarbonate (ethyl xanthate, CH 3CH 2OCS -2) anion is a widely used reagent in mineral processing for the separation of sulphide minerals by froth flotation. Ethyl xanthate interacts with mineral powders to produce a hydrophobic layer on the mineral surface. A novel infrared technique, headspace analysis gas-phase infrared spectroscopy (HAGIS) has been used to study the in situ thermal decomposition products of ethyl xanthate on mineral surfaces. These products include CS 2, COS, CO 2, CH 4, SO 2, and higher molecular weight alkyl-containing species. Decomposition pathways have been proposed with some information determined from 2H- and 13C-isotope labelling experiments.

  20. Grains colonised by moulds: fungal identification and headspace analysis of produced volatile metabolites

    Directory of Open Access Journals (Sweden)

    Maria Paola Tampieri

    2010-01-01

    Full Text Available The aim of this work was to verify if the headspace analysis of fungal volatile compounds produced by some species of Fusarium can be used as a marker of mould presence on maize. Eight samples of maize (four yellow maize from North Italy and four white maize from Hungary, naturally contaminated by Fusarium and positive for the presence of fumonisins, were analyzed to detect moisture content, Aw, volatile metabolites and an enumeration of viable moulds was performed by means of a colony count technique. Headspace samples were analysed using a gas-chromatograph equipped with a capillary column TR-WAX to detect volatile metabolites of moulds. Furthermore macro and microscopic examination of the colonies was performed in order to distinguish, according to their morphology, the genera of the prevalent present moulds. Prevalent mould of eight samples was Fusarium, but other fungi, like Aspergillus, Penicillum and Mucoraceae, were observed. The metabolites produced by F.graminearum and F. moniliforme were Isobutyl-acetate, 3-Methyl-1-butanol and, only at 8 days, 3-Octanone. The incubation time can affect off flavour production in consequence of the presence of other moulds. Further studies on maize samples under different conditions are needed in order to establish the presence of moulds using the count technique and through the identification of volatile compounds.

  1. Analysis of residual toluene in food packaging via headspace extraction method using gas chromatography

    International Nuclear Information System (INIS)

    Lim, Ying Chin; Mohd Marsin Sanagi

    2008-01-01

    Polymeric materials are used in many food contact applications as packaging material. The presence of residual toluene in this food packaging material can migrate into food and thus affect the quality of food. In this study, a manual headspace analysis was successfully designed and developed. The determination of residual toluene was carried out with standard addition method and multiple headspace extraction, MHE) method using gas chromatography-flame ionization detector, GC-FID). Identification of toluene was performed by comparison of its retention time with standard toluene and GC-MS. It was found that the suitable heating temperature was 180 degree Celsius with an optimum heating time of 10 minutes. The study also found that the concentration of residual toluene in multicolored sample was higher compared to mono colored sample whereas residual toluene in sample analyzed using standard addition method was higher compared to MHE method. However, comparison with the results obtained from De Paris laboratory, France found that MHE method gave higher accuracy for sample with low analyte concentration. On the other hand, lower accuracy was obtained for sample with high concentration of residual toluene due to systematic errors. Comparison between determination methods showed that MHE method is more precise compared to standard addition method. (author)

  2. Quantitative Analysis of Bioactive Compounds from Aromatic Plants by Means of Dynamic Headspace Extraction and Multiple Headspace Extraction-Gas Chromatography-Mass Spectrometry

    NARCIS (Netherlands)

    Omar, Jone; Olivares, Maitane; Alonso, Ibone; Vallejo, Asier; Aizpurua-Olaizola, Oier; Etxebarria, Nestor

    2016-01-01

    Seven monoterpenes in 4 aromatic plants (sage, cardamom, lavender, and rosemary) were quantified in liquid extracts and directly in solid samples by means of dynamic headspace-gas chromatography-mass spectrometry (DHS-GC-MS) and multiple headspace extraction-gas chromatography-mass spectrometry

  3. Uncertainty of Blood Alcohol Concentration (BAC Results as Related to Instrumental Conditions: Optimization and Robustness of BAC Analysis Headspace Parameters

    Directory of Open Access Journals (Sweden)

    Haleigh A. Boswell

    2015-12-01

    Full Text Available Analysis of blood alcohol concentration is a routine analysis performed in many forensic laboratories. This analysis commonly utilizes static headspace sampling, followed by gas chromatography combined with flame ionization detection (GC-FID. Studies have shown several “optimal” methods for instrumental operating conditions, which are intended to yield accurate and precise data. Given that different instruments, sampling methods, application specific columns and parameters are often utilized, it is much less common to find information on the robustness of these reported conditions. A major problem can arise when these “optimal” conditions may not also be robust, thus producing data with higher than desired uncertainty or potentially inaccurate results. The goal of this research was to incorporate the principles of quality by design (QBD in the adjustment and determination of BAC (blood alcohol concentration instrumental headspace parameters, thereby ensuring that minor instrumental variations, which occur as a matter of normal work, do not appreciably affect the final results of this analysis. This study discusses both the QBD principles as well as the results of the experiments, which allow for determination of more favorable instrumental headspace conditions. Additionally, method detection limits will also be reported in order to determine a reporting threshold and the degree of uncertainty at the common threshold value of 0.08 g/dL. Furthermore, the comparison of two internal standards, n-propanol and t-butanol, will be investigated. The study showed that an altered parameter of 85 °C headspace oven temperature and 15 psi headspace vial pressurization produces the lowest percent relative standard deviation of 1.3% when t-butanol is implemented as an internal standard, at least for one very common platform. The study also showed that an altered parameter of 100 °C headspace oven temperature and 15-psi headspace vial pressurization

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

    Science.gov (United States)

    Mills, G A; Walker, V

    2000-12-01

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

  5. Analysis of Volatile Compounds from Solanumbetaceum Cav. Fruits from Panama by Head-Space Micro Extraction

    Directory of Open Access Journals (Sweden)

    Armando A. Durant

    2013-01-01

    Full Text Available The characterization of the volatile compounds of two varieties of Solanum betaceum Cav. by means of headspace solid-phase microextraction (HS-SPME coupled with gas chromatography-mass spectrometry ( GC-MS i s presented. The HS-SPME method for extraction of the volatiles compounds was optimized by using a 2 3 central composite design. Maximum extraction of volatile compounds was achieved by using a divinylbenzene-carboxen-polydimethylsiloxane (DVB/CAR/PDMS fiber, extraction temperature 76° C, incubation time 44 min, and extraction time of 46 min. The main types of compounds detected in both varieties are terpenoids, followed by aromatics, esters, and aldehydes. Golden-yellow cultivars contained higher levels of esters and terpenes, while the reddish-purple variety contained a significant amount of aromatic compounds. The data structure of the chemical information obtained as well as the relationship between variables was evaluated by means of principal component analysis and cluster analysis.

  6. Bromination of Aromatic Compounds by Residual Bromide in Sodium Chloride Matrix Modifier Salt During Heated Headspace GC/MS Analysis

    Science.gov (United States)

    Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation rea...

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

    DEFF Research Database (Denmark)

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

    1996-01-01

    Head-space solid-phase microextraction (HS-SPME) has been used to collect volatile organic compounds (VOCs) emitted from fungi of the genus Penicillium. Gas chromatography combined with mass spectrometry (GC-MS) was employed for the analysis of the profiles of volatile metabolites characteristic...

  8. Dynamic collection and analysis of volatile organic compounds from the headspace of cell cultures.

    Science.gov (United States)

    Baranska, A; Smolinska, A; Boots, A W; Dallinga, J W; van Schooten, F J

    2015-10-15

    interactions. Measurements were performed with gas chromatography time-of-flight mass spectrometry. Multivariate data analysis allowed detection of significant altered compounds in the compared groups. We found a significant change (p  ⩽  0.001) of the composition of VOCs due to the stressing of the Caco-2 cells by H2O2. A total of ten VOCs showed either increased or decreased abundance in the headspace of the cell cultures due to the presence of the H2O2 stressor.

  9. Determination of dissolved methane in natural waters using headspace analysis with cavity ring-down spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, Hannah M.; Shiller, Alan M., E-mail: alan.shiller@usm.edu

    2015-01-26

    Highlights: • A method for determining low nanomolar dissolved CH{sub 4} was developed. • The methane detection utilizes cavity ring-down spectroscopy (CRDS). • Use of CRDS requires less time, materials and labor than typical of GC analysis. • Relative standard deviations of ∼4% were achieved at low nM CH{sub 4}. • Applications to seawater and river water are presented. - Abstract: Methane (CH{sub 4}) is the third most abundant greenhouse gas (GHG) but is vastly understudied in comparison to carbon dioxide. Sources and sinks to the atmosphere vary considerably in estimation, including sources such as fresh and marine water systems. A new method to determine dissolved methane concentrations in discrete water samples has been evaluated. By analyzing an equilibrated headspace using laser cavity ring-down spectroscopy (CRDS), low nanomolar dissolved methane concentrations can be determined with high reproducibility (i.e., 0.13 nM detection limit and typical 4% RSD). While CRDS instruments cost roughly twice that of gas chromatographs (GC) usually used for methane determination, the process presented herein is substantially simpler, faster, and requires fewer materials than GC methods. Typically, 70-mL water samples are equilibrated with an equivalent amount of zero air in plastic syringes. The equilibrated headspace is transferred to a clean, dry syringe and then drawn into a Picarro G2301 CRDS analyzer via the instrument’s pump. We demonstrate that this instrument holds a linear calibration into the sub-ppmv methane concentration range and holds a stable calibration for at least two years. Application of the method to shipboard dissolved methane determination in the northern Gulf of Mexico as well as river water is shown. Concentrations spanning nearly six orders of magnitude have been determined with this method.

  10. Comparative analysis of the vapor headspace of military-grade TNT versus NESTT TNT under dynamic and static conditions

    Science.gov (United States)

    Edge, Cindy C.; Gibb, Julie; Wasserzug, Louis S.

    1998-09-01

    The Institute for Biological Detection Systems (IBDS) has developed a quantitative vapor delivery system that can aid in characterizing dog's sensitivity and ability to recognize odor signatures for explosives and contraband substances. Determining of the dog's odor signature for detection of explosives is important because it may aid in eliminating the risk of handling explosives and reducing cross-contamination. Progress is being made in the development of training aids that represent the headspace of the explosives. NESTTTM TNT materials have been proposed as an approach to developing training aid simulates. In order for such aids to be effective they must mimic the headspace of the target material. This study evaluates the NESTTTM TNT product with regard to this criterion. NESTTTM TNT vapor was generated by the IBDS vapor delivery system, which incorporates a vapor generation cell that enables the user to control the conditions under which a substance is tested. The NESTTTM TNT vapor was compared to the headspace of military-grade TNT. The findings identify and quantify major vapor constituents of military-grade TNT and NESTTTM TNT. A comparative analysis evaluated the degree to which the NESTTTM TNT mimics the headspace of an actual TNT sample.

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

    Science.gov (United States)

    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.

  12. Analysis of volatile headspace gases sampled by cryogenic traps from Westinghouse Hanford Company Tank 242-C-112 March 1992

    International Nuclear Information System (INIS)

    Lucke, R.B.; Clauss, S.A.

    1993-10-01

    Results are given from gas chromatography/mass spectrometry (GC/MS) analyses of the headspace samples obtained by using cryogenic traps from Westinghouse Hanford Company (WHC) Tank 112-C during the month of March, 1992. Samples were analyzed as received with no sample preparation. Analyses included direct GC/MS for volatile/semivolatile components, and direct GC/MS for ammonia. Purge and trap GC/MS analysis was not done. In addition, aliquots were sent to Karl Pool, Pacific Northwest Laboratory, for hydrogen cyanide analysis by ion chromatography, the results are reported here. All concentrations are reported for the methanol extract solutions. To calculate concentrations in the headspace, the cryo-sampling air volume and the methanol rinse volume must be obtained from cryo-sampling personnel at WHC. Triplicate analyses were done on all samples, and average concentrations and standard deviations are reported. One significant result was that no ammonia was detected

  13. Field portable low temperature porous layer open tubular cryoadsorption headspace sampling and analysis part I: Instrumentation.

    Science.gov (United States)

    Bruno, Thomas J

    2016-01-15

    Building on the successful application in the laboratory of PLOT-cryoadsorption as a means of collecting vapor (or headspace) samples for chromatographic analysis, in this paper a field portable apparatus is introduced. This device fits inside of a briefcase (aluminum tool carrier), and can be easily transported by vehicle or by air. The portable apparatus functions entirely on compressed air, making it suitable for use in locations lacking electrical power, and for use in flammable and explosive environments. The apparatus consists of four aspects: a field capable PLOT-capillary platform, the supporting equipment platform, the service interface between the PLOT-capillary and the supporting equipment, and the necessary peripherals. Vapor sampling can be done with either a hand piece (containing the PLOT capillary) or with a custom fabricated standoff module. Both the hand piece and the standoff module can be heated and cooled to facilitate vapor collection and subsequent vapor sample removal. The service interface between the support platform and the sampling units makes use of a unique counter current approach that minimizes loss of cooling and heating due to heat transfer with the surroundings (recuperative thermostatting). Several types of PLOT-capillary elements and sampling probes are described in this report. Applications to a variety of samples relevant to forensic and environmental analysis are discussed in a companion paper. Published by Elsevier B.V.

  14. Headspace Solid Phase Microextraction in Pesticide Residues Analysis:1. Optimisation of Extraction Conditions

    Directory of Open Access Journals (Sweden)

    Rada Đurović

    2007-01-01

    Full Text Available The method of headspace solid phase microextraction (HS/SPME was successfully used in a simultaneous multicomponent analysis of hexachlorobenzene (HCB, tefluthrin, heptachlor, aldrin, chlorpyrifos, fenthion and bifenthrin in aqueous medium. Measurementswere performed using a nonpolar polydimethyl siloxane (PDMS fiber. Detection and quantification were done by gas chromatography/mass spectrometry (GC/MS.Optimal conditions for HS/SPME were determined both by performing extraction at different temperatures and examining extraction time profiles at constant temperature. Optimal extraction temperature for each pesticide studied was determined as follows: 60°C for HCB and for heptachlor, 80°C for aldrin and for chlorpyrifos, fenthion and tefluthrin, and temperature exceeding 80°C for bifenthrin. For the pesticide mixture studied, 60°C was identified as the optimum extraction temperature.Based on the time profiles obtained, it was confirmed that satisfactory extraction sensitivity can be obtained even for extraction times shorter than the time required to reach a sorption equilibrium. This conclusion was confirmed by linear concentration profiles obtained for the following ranges: 0.05-10 ng/ml (HCB, 0.05-25 ng/ml (tefluthrin, 0.05-40 ng/ml (heptachlor, 0.05-40 ng/ml (aldrin, 0.05-25 ng/ml (chlorpyrifos, 0.05-25 ng/ml (fenthionand 0.05-25 ng/ml (bifenthrin.Relative standard deviation (RSD values for triplicate measurements did not exceed 15%.

  15. Headspace Solid Phase Microextraction in Pesticide Residues Analysis: 2. Apple Samples

    Directory of Open Access Journals (Sweden)

    Jelena Milinović

    2007-01-01

    Full Text Available Headspace solid phase microextraction method (HS/SPME, optimised previously for pesticide water solutions, was applied to trace residues of the pesticides chlorpyrifos, fenthion and bifenthrin in apple samples. One-hour extraction procedure was performed at 60oC extraction temperature. Nonpolar polydimethyl siloxane (PDMS fiber was used. Detection and quantification were carried out by gas chromatography/mass spectrometry (GC/MS. A non-pesticide treated apple sample was fortified with the pesticides over a 0.025-1.25 mg/kg concentration range in order to determine analytical parameters of the method applied. Linearity with regression coefficient (R values higher than 0.99 were obtained over the whole concentration range investigated for chlorpyrifos and fenthion, while linear dependence was observed in the 0.1-1.25 mg/kg range for bifenthrin. Relative recovery values for samples fortified at different levels were in the 56.68-82.91% range. Limit of detection (LOD values were determined as follows: 0.014 mg/kg for chlorpyrifos, 0.021 mg/kg for fenthion and 0.053 mg/kg for bifenthrin. Relative standard deviation (RSD values obtained for multiple analysis of the sample fortified at 0.6 mg/kg level were not higher than 20%.

  16. Method detection limit determination and application of a convenient headspace analysis method for methyl tert-butyl ether in water.

    Science.gov (United States)

    O'Neill, Dennis T; Rochette, Elizabeth A; Ramsey, Philip J

    2002-11-15

    Methyl tert-butyl ether (MTBE) is a common groundwater contaminant, introduced to the environment by leaking petroleum storage tanks, urban runoff, and motorized watercraft. In this study. a simplified (static) headspace analysis method was adapted for determination of MTBE in water samples and soil water extracts. The MDL of the headspace method was calculated to be 2.0 microg L(-1) by the EPA single-concentration design method(1) and 1.2 microg L(-1) by a calibration method developed by Hubaux and Vos (Hubaux, A.; Vos, G. Anal. Chem. 1970,42, 849-855). The MDL calculated with the Hubaux and Vos method was favored because it considers both a true positive and a false positive. The static headspace method was applied to analysis of a tap water sample and a monitoring well sample from a gasoline service station, a river sample, and aqueous extracts from soil excavated during removal of a leaking underground storage tank (LUST). The water samples examined in this study had MTTBE concentrations ranging from 6 to 19 microg L(-1). Aqueous extracts of a soil sample taken from the LUST site had 8 microg L(-1) MTBE.

  17. Analysis of benzene, toluene, ethylbenzene and xylenes in soils by headspace and gas chromatography/flame ionization detector

    Directory of Open Access Journals (Sweden)

    Jurandir Pereira Pinto

    2006-02-01

    Full Text Available The constituents of gasoline: benzene, toluene, ethylbenzene and xylenes (BTEX are frequently found in soils due to leaks in fuel storage tanks and they present chronic toxicity. In this work it was developed and validated a methodology of BTEX analysis in soil by gas chromatography/ flame ionization detector and static headspace. The recovery of BTEX in soil samples was evaluated using soils with different textures (sandy and loamy. The analysis method showed good resolution, in a low time of analysis (less than 30 minutes. Limits of quantification of 0.05 mg Kg¯¹ soil for benzene, toluene, ethylbenzene and xylenes are below the guiding values that range from 0.15 to 95 mg Kg¯¹ soil, established to determine soil quality. It was verified that the methodology enables the use of this method for BTEX analysis of soil samples for passive environmental identification of gas stations.

  18. Determination of Porosity in Shale by Double Headspace Extraction GC Analysis.

    Science.gov (United States)

    Zhang, Chun-Yun; Li, Teng-Fei; Chai, Xin-Sheng; Xiao, Xian-Ming; Barnes, Donald

    2015-11-03

    This paper reports on a novel method for the rapid determination of the shale porosity by double headspace extraction gas chromatography (DHE-GC). Ground core samples of shale were placed into headspace vials and DHE-GC measurements of released methane gas were performed at a given time interval. A linear correlation between shale porosity and the ratio of consecutive GC signals was established both theoretically and experimentally by comparing with the results from the standard helium pycnometry method. The results showed that (a) the porosity of ground core samples of shale can be measured within 30 min; (b) the new method is not significantly affected by particle size of the sample; (c) the uncertainties of measured porosities of nine shale samples by the present method range from 0.31 to 0.46 p.u.; and (d) the results obtained by the DHE-GC method are in a good agreement with those from the standard helium pycnometry method. In short, the new DHE-GC method is simple, rapid, and accurate, making it a valuable tool for shale gas-related research and applications.

  19. Quantitative analysis of total starch content in wheat flour by reaction headspace gas chromatography.

    Science.gov (United States)

    Xie, Wei-Qi; Gong, Yi-Xian; Yu, Kong-Xian

    2017-09-01

    This paper proposed a new reaction headspace gas chromatographic (HS-GC) method for efficiently quantifying the total starch content in wheat flours. A certain weight of wheat flour was oxidized by potassium dichromate in an acidic condition in a sealed headspace vial. The results show that the starch in wheat flour can be completely transferred to carbon dioxide at the given conditions (at 100 °C for 40 min) and the total starch content in wheat flour sample can be indirectly quantified by detecting the CO 2 formed from the oxidation reaction. The data showed that the relative standard deviation of the reaction HS-GC method in the precision test was less than 3.06%, and the relative differences between the new method and the reference method (titration method) were no more than 8.90%. The new reaction HS-GC method is automated, accurate, and can be a reliable tool for determining the total starch content in wheat flours in both laboratory and industrial applications. Graphical abstract The total starch content in wheat flour can be indirectly quantified by the GC detection of the CO 2 formed from the oxidation reaction between wheat flour and potassium dichromate in an acidic condition.

  20. Ethanol analysis by headspace gas chromatography with simultaneous flame-ionization and mass spectrometry detection.

    Science.gov (United States)

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

    2011-09-01

    Ethanol is the most frequently identified compound in forensic toxicology. Although confirmation involving mass spectrometry is desirable, relatively few methods have been published to date. A novel technique utilizing a Dean's Switch to simultaneously quantitate and confirm ethyl alcohol by flame-ionization (FID) and mass spectrometric (MS) detection after headspace sampling and gas chromatographic separation is presented. Using 100 μL of sample, the limits of detection and quantitation were 0.005 and 0.010 g/dL, respectively. The zero-order linear range (r(2) > 0.990) was determined to span the concentrations of 0.010 to 1.000 g/dL. The coefficient of variation of replicate analyses was less than 3.1%. Quantitative accuracy was within ±8%, ±6%, ±3%, and ±1.5% at concentrations of 0.010, 0.025, 0.080, and 0.300 g/dL, respectively. In addition, 1,1-difluoroethane was validated for qualitative identification by this method. The validated FID-MS method provides a procedure for the quantitation of ethyl alcohol in blood by FID with simultaneous confirmation by MS and can also be utilized as an identification method for inhalants such as 1,1-difluoroethane.

  1. Quantitative analysis of aldehydes in canned vegetables using static headspace-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Serrano, María; Gallego, Mercedes; Silva, Manuel

    2017-11-17

    Volatile aldehydes appear in canned vegetables as constituents and some of them can also be present as disinfection by-products (DBPs) because of the contact between vegetables and treated water. This paper describes two static headspace-gas chromatography-mass spectrometry (SHS-GC-MS) methods to determine 15 aldehydes in both the solid and the liquid phases of canned vegetables. The treatment for both phases of samples was carried out simultaneously into an SHS unit, including the leaching of the aldehydes (from the vegetable), their derivatization and volatilization of the oximes formed. Detection limits were obtained within the range of 15-400μg/kg and 3-40μg/L for aldehydes in the solid and the liquid phases of the food, respectively. The relative standard deviation was lower than 7% -for the whole array of the target analytes-, the trueness evaluated by recovery experiments provided %recoveries between 89 and 99% and short- and long-term stability studies indicated there was no significant variation in relative peak areas of all aldehydes in both phases of canned vegetables after their storing at 4°C for two weeks. The study of the origin of the 15 aldehydes detected between both phases of canned vegetables showed that: i) the presence of 13 aldehydes -at average concentrations of 2.2-39μg/kg and 0.25-71μg/L for the solid and the liquid phases, respectively- is because they are natural constituents of vegetables; and ii) the presence of glyoxal and methylglyoxal -which are mainly found in the liquid phase (average values, 1.4-4.1μg/L)- is ascribed to the use of treated water, thereby being DBPs. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Development of a Direct Headspace Collection Method from Arabidopsis Seedlings Using HS-SPME-GC-TOF-MS Analysis

    Directory of Open Access Journals (Sweden)

    Kazuki Saito

    2013-04-01

    Full Text Available Plants produce various volatile organic compounds (VOCs, which are thought to be a crucial factor in their interactions with harmful insects, plants and animals. Composition of VOCs may differ when plants are grown under different nutrient conditions, i.e., macronutrient-deficient conditions. However, in plants, relationships between macronutrient assimilation and VOC composition remain unclear. In order to identify the kinds of VOCs that can be emitted when plants are grown under various environmental conditions, we established a conventional method for VOC profiling in Arabidopsis thaliana (Arabidopsis involving headspace-solid-phase microextraction-gas chromatography-time-of-flight-mass spectrometry (HS-SPME-GC-TOF-MS. We grew Arabidopsis seedlings in an HS vial to directly perform HS analysis. To maximize the analytical performance of VOCs, we optimized the extraction method and the analytical conditions of HP-SPME-GC-TOF-MS. Using the optimized method, we conducted VOC profiling of Arabidopsis seedlings, which were grown under two different nutrition conditions, nutrition-rich and nutrition-deficient conditions. The VOC profiles clearly showed a distinct pattern with respect to each condition. This study suggests that HS-SPME-GC-TOF-MS analysis has immense potential to detect changes in the levels of VOCs in not only Arabidopsis, but other plants grown under various environmental conditions.

  3. Multi-volatile method for aroma analysis using sequential dynamic headspace sampling with an application to brewed coffee.

    Science.gov (United States)

    Ochiai, Nobuo; Tsunokawa, Jun; Sasamoto, Kikuo; Hoffmann, Andreas

    2014-12-05

    A novel multi-volatile method (MVM) using sequential dynamic headspace (DHS) sampling for analysis of aroma compounds in aqueous sample was developed. The MVM consists of three different DHS method parameters sets including choice of the replaceable adsorbent trap. The first DHS sampling at 25 °C using a carbon-based adsorbent trap targets very volatile solutes with high vapor pressure (>20 kPa). The second DHS sampling at 25 °C using the same type of carbon-based adsorbent trap targets volatile solutes with moderate vapor pressure (1-20 kPa). The third DHS sampling using a Tenax TA trap at 80 °C targets solutes with low vapor pressure (0.9910) and high sensitivity (limit of detection: 1.0-7.5 ng mL(-1)) even with MS scan mode. The feasibility and benefit of the method was demonstrated with analysis of a wide variety of aroma compounds in brewed coffee. Ten potent aroma compounds from top-note to base-note (acetaldehyde, 2,3-butanedione, 4-ethyl guaiacol, furaneol, guaiacol, 3-methyl butanal, 2,3-pentanedione, 2,3,5-trimethyl pyrazine, vanillin, and 4-vinyl guaiacol) could be identified together with an additional 72 aroma compounds. Thirty compounds including 9 potent aroma compounds were quantified in the range of 74-4300 ng mL(-1) (RSD<10%, n=5). Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

  4. Solid phase microextraction headspace sampling of chemical warfare agent contaminated samples : method development for GC-MS analysis

    Energy Technology Data Exchange (ETDEWEB)

    Jackson Lepage, C.R.; Hancock, J.R. [Defence Research and Development Canada, Medicine Hat, AB (Canada); Wyatt, H.D.M. [Regina Univ., SK (Canada)

    2004-07-01

    Defence R and D Canada-Suffield (DRDC-Suffield) is responsible for analyzing samples that are suspected to contain chemical warfare agents, either collected by the Canadian Forces or by first-responders in the event of a terrorist attack in Canada. The analytical techniques used to identify the composition of the samples include gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), Fourier-transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy. GC-MS and LC-MS generally require solvent extraction and reconcentration, thereby increasing sample handling. The authors examined analytical techniques which reduce or eliminate sample manipulation. In particular, this paper presented a screening method based on solid phase microextraction (SPME) headspace sampling and GC-MS analysis for chemical warfare agents such as mustard, sarin, soman, and cyclohexyl methylphosphonofluoridate in contaminated soil samples. SPME is a method which uses small adsorbent polymer coated silica fibers that trap vaporous or liquid analytes for GC or LC analysis. Collection efficiency can be increased by adjusting sampling time and temperature. This method was tested on two real-world samples, one from excavated chemical munitions and the second from a caustic decontamination mixture. 7 refs., 2 tabs., 3 figs.

  5. Multivariate analysis of the volatile components in tobacco based on infrared-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Yang, Yanqin; Pan, Yuanjiang; Zhou, Guojun; Chu, Guohai; Jiang, Jian; Yuan, Kailong; Xia, Qian; Cheng, Changhe

    2016-11-01

    A novel infrared-assisted extraction coupled to headspace solid-phase microextraction followed by gas chromatography with mass spectrometry method has been developed for the rapid determination of the volatile components in tobacco. The optimal extraction conditions for maximizing the extraction efficiency were as follows: 65 μm polydimethylsiloxane-divinylbenzene fiber, extraction time of 20 min, infrared power of 175 W, and distance between the infrared lamp and the headspace vial of 2 cm. Under the optimum conditions, 50 components were found to exist in all ten tobacco samples from different geographical origins. Compared with conventional water-bath heating and nonheating extraction methods, the extraction efficiency of infrared-assisted extraction was greatly improved. Furthermore, multivariate analysis including principal component analysis, hierarchical cluster analysis, and similarity analysis were performed to evaluate the chemical information of these samples and divided them into three classifications, including rich, moderate, and fresh flavors. The above-mentioned classification results were consistent with the sensory evaluation, which was pivotal and meaningful for tobacco discrimination. As a simple, fast, cost-effective, and highly efficient method, the infrared-assisted extraction coupled to headspace solid-phase microextraction technique is powerful and promising for distinguishing the geographical origins of the tobacco samples coupled to suitable chemometrics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Zhi Zeng

    2013-01-01

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

  7. Rapid analysis of dissolved methane, ethylene, acetylene and ethane using partition coefficients and headspace-gas chromatography.

    Science.gov (United States)

    Lomond, Jasmine S; Tong, Anthony Z

    2011-01-01

    Analysis of dissolved methane, ethylene, acetylene, and ethane in water is crucial in evaluating anaerobic activity and investigating the sources of hydrocarbon contamination in aquatic environments. A rapid chromatographic method based on phase equilibrium between water and its headspace is developed for these analytes. The new method requires minimal sample preparation and no special apparatus except those associated with gas chromatography. Instead of Henry's Law used in similar previous studies, partition coefficients are used for the first time to calculate concentrations of dissolved hydrocarbon gases, which considerably simplifies the calculation involved. Partition coefficients are determined to be 128, 27.9, 1.28, and 96.3 at 30°C for methane, ethylene, acetylene, and ethane, respectively. It was discovered that the volume ratio of gas-to-liquid phase is critical to the accuracy of the measurements. The method performance can be readily improved by reducing the volume ratio of the two phases. Method validation shows less than 6% variation in accuracy and precision except at low levels of methane where interferences occur in ambient air. Method detection limits are determined to be in the low ng/L range for all analytes. The performance of the method is further tested using environmental samples collected from various sites in Nova Scotia.

  8. Headspace Hanging Drop Liquid Phase Microextraction and Gas Chromatography-Mass Spectrometry for the Analysis of Flavors from Clove Buds

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Mi Jin; Shin, Yeon Jae; Oh, Se Yeon; Kim, Nam Sun; Kim, Kun; Lee, Dong Sun [Seoul Women' s University, Seoul (Korea, Republic of)

    2006-02-15

    A novel sample pretreatment technique, headspace hanging drop liquid phase microextraction (HS-LPME) was studied and applied to the determination of flavors from solid clove buds by gas chromatography-mass spectrometry (GC-MS). Several parameters affecting on HS-LPME such as organic solvent drop volume, extraction time, extraction temperature and phase ratio were investigated. 1-Octanol was selected as the extracting solvent, drop size was fixed to 0.6 μL. 60 min extraction time at 25 .deg. C was chosen. HS-LPME has the good efficiency demonstrated by the higher partition equilibrium constant (K{sub lh}) values and concentration factor (CF) values. The limits of detection (LOD) were 1.5-3.2 ng. The amounts of eugenol, β-caryophyllene and eugenol acetate from the clove bud sample were 1.90 mg/g, 1.47 mg/g and 7.0 mg/g, respectively. This hanging drop based method is a simple, fast and easy sample enrichment technique using minimal solvent. HSLPME is an alternative sample preparation method for the analysis of volatile aroma compounds by GC-MS.

  9. Direct analysis of volatile organic compounds in foods by headspace extraction atmospheric pressure chemical ionisation mass spectrometry.

    Science.gov (United States)

    Perez-Hurtado, P; Palmer, E; Owen, T; Aldcroft, C; Allen, M H; Jones, J; Creaser, C S; Lindley, M R; Turner, M A; Reynolds, J C

    2017-11-30

    The rapid screening of volatile organic compounds (VOCs) by direct analysis has potential applications in the areas of food and flavour science. Currently, the technique of choice for VOC analysis is gas chromatography/mass spectrometry (GC/MS). However, the long chromatographic run times and elaborate sample preparation associated with this technique have led a movement towards direct analysis techniques, such as selected ion flow tube mass spectrometry (SIFT-MS), proton transfer reaction mass spectrometry (PTR-MS) and electronic noses. The work presented here describes the design and construction of a Venturi jet-pump-based modification for a compact mass spectrometer which enables the direct introduction of volatiles for qualitative and quantitative analysis. Volatile organic compounds were extracted from the headspace of heated vials into the atmospheric pressure chemical ionization source of a quadrupole mass spectrometer using a Venturi pump. Samples were analysed directly with no prior sample preparation. Principal component analysis (PCA) was used to differentiate between different classes of samples. The interface is shown to be able to routinely detect problem analytes such as fatty acids and biogenic amines without the requirement of a derivatisation step, and is shown to be able to discriminate between four different varieties of cheese with good intra and inter-day reproducibility using an unsupervised PCA model. Quantitative analysis is demonstrated using indole standards with limits of detection and quantification of 0.395 μg/mL and 1.316 μg/mL, respectively. The described methodology can routinely detect highly reactive analytes such as volatile fatty acids and diamines without the need for a derivatisation step or lengthy chromatographic separations. The capability of the system was demonstrated by discriminating between different varieties of cheese and monitoring the spoilage of meats. © 2017 The Authors. Rapid Communications in Mass

  10. Zero-Headspace Coal-Core Gas Desorption Canister, Revised Desorption Data Analysis Spreadsheets and a Dry Canister Heating System

    Science.gov (United States)

    Barker, Charles E.; Dallegge, Todd A.

    2005-01-01

    Coal desorption techniques typically use the U.S. Bureau of Mines (USBM) canister-desorption method as described by Diamond and Levine (1981), Close and Erwin (1989), Ryan and Dawson (1993), McLennan and others (1994), Mavor and Nelson (1997) and Diamond and Schatzel (1998). However, the coal desorption canister designs historically used with this method have an inherent flaw that allows a significant gas-filled headspace bubble to remain in the canister that later has to be compensated for by correcting the measured desorbed gas volume with a mathematical headspace volume correction (McLennan and others, 1994; Mavor and Nelson, 1997).

  11. Headspace needle-trap analysis of priority volatile organic compounds from aqueous samples: application to the analysis of natural and waste waters.

    Science.gov (United States)

    Alonso, Monica; Cerdan, Laura; Godayol, Anna; Anticó, Enriqueta; Sanchez, Juan M

    2011-11-11

    Combining headspace (HS) sampling with a needle-trap device (NTD) to determine priority volatile organic compounds (VOCs) in water samples results in improved sensitivity and efficiency when compared to conventional static HS sampling. A 22 gauge stainless steel, 51-mm needle packed with Tenax TA and Carboxen 1000 particles is used as the NTD. Three different HS-NTD sampling methodologies are evaluated and all give limits of detection for the target VOCs in the ng L⁻¹ range. Active (purge-and-trap) HS-NTD sampling is found to give the best sensitivity but requires exhaustive control of the sampling conditions. The use of the NTD to collect the headspace gas sample results in a combined adsorption/desorption mechanism. The testing of different temperatures for the HS thermostating reveals a greater desorption effect when the sample is allowed to diffuse, whether passively or actively, through the sorbent particles. The limits of detection obtained in the simplest sampling methodology, static HS-NTD (5 mL aqueous sample in 20 mL HS vials, thermostating at 50 °C for 30 min with agitation), are sufficiently low as to permit its application to the analysis of 18 priority VOCs in natural and waste waters. In all cases compounds were detected below regulated levels. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Dynamic headspace-gas-chromatography-olfactometry analysis of different anatomical parts of lovage (Levisticum officinale Koch.) at eight growing stages

    NARCIS (Netherlands)

    Bylaite, E.; Roozen, J.P.; Legger, A.; Venskutonis, R.P.; Posthumus, M.A.

    2000-01-01

    Volatiles of five different parts of lovage (leaves, stems, flowers, seeds, and roots) were isolated by dynamic headspace (DHS) method and analyzed by GC-FID and GC-olfactometry (GC-O) techniques. In total, 98 compounds were identified in the samples, of which 41 are reported as lovage volatiles for

  13. Analysis of aroma compounds of Roselle by Dynamic Headspace Sampling using different preparation methods

    DEFF Research Database (Denmark)

    Juhari, Nurul Hanisah Binti; Varming, Camilla; Petersen, Mikael Agerlin

    2015-01-01

    The influence of different methods of sample preparation on the aroma profiles of dried Roselle (Hibiscus sabdariffa) was studied. Least amounts of aroma compounds were recovered by analysis of whole dry calyxes (WD) followed by ground dry (GD), blended together with water (BTW), and ground...

  14. Detection of Pseudomonas aeruginosa in sputum headspace through volatile organic compound analysis

    Directory of Open Access Journals (Sweden)

    Goeminne Pieter C

    2012-10-01

    Full Text Available Abstract Introduction Chronic pulmonary infection is the hallmark of Cystic Fibrosis lung disease. Searching for faster and easier screening may lead to faster diagnosis and treatment of Pseudomonas aeruginosa (P. aeruginosa. Our aim was to analyze and build a model to predict the presence of P. aeruginosa in sputa. Methods Sputa from 28 bronchiectatic patients were used for bacterial culturing and analysis of volatile compounds by gas chromatography–mass spectrometry. Data analysis and model building were done by Partial Least Squares Regression Discriminant analysis (PLS-DA. Two analysis were performed: one comparing P. aeruginosa positive with negative cultures at study visit (PA model and one comparing chronic colonization according to the Leeds criteria with P. aeruginosa negative patients (PACC model. Results The PA model prediction of P. aeruginosa presence was rather poor, with a high number of false positives and false negatives. On the other hand, the PACC model was stable and explained chronic P. aeruginosa presence for 95% with 4 PLS-DA factors, with a sensitivity of 100%, a positive predictive value of 86% and a negative predictive value of 100%. Conclusion Our study shows the potential for building a prediction model for the presence of chronic P. aeruginosa based on volatiles from sputum.

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

    Directory of Open Access Journals (Sweden)

    Chih-Hsin Yeh

    2014-09-01

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

  16. Evaluation and application of static headspace-multicapillary column-gas chromatography-ion mobility spectrometry for complex sample analysis.

    Science.gov (United States)

    Denawaka, Chamila J; Fowlis, Ian A; Dean, John R

    2014-04-18

    An evaluation of static headspace-multicapillary column-gas chromatography-ion mobility spectrometry (SHS-MCC-GC-IMS) has been undertaken to assess its applicability for the determination of 32 volatile compounds (VCs). The key experimental variables of sample incubation time and temperature have been evaluated alongside the MCC-GC variables of column polarity, syringe temperature, injection temperature, injection volume, column temperature and carrier gas flow rate coupled with the IMS variables of temperature and drift gas flow rate. This evaluation resulted in six sets of experimental variables being required to separate the 32 VCs. The optimum experimental variables for SHS-MCC-GC-IMS, the retention time and drift time operating parameters were determined; to normalise the operating parameters, the relative drift time and normalised reduced ion mobility for each VC were determined. In addition, a full theoretical explanation is provided on the formation of the monomer, dimer and trimer of a VC. The optimum operating condition for each VC calibration data was obtained alongside limit of detection (LOD) and limit of quantitation (LOQ) values. Typical detection limits ranged from 0.1ng bis(methylthio)methane, ethylbutanoate and (E)-2-nonenal to 472ng isovaleric acid with correlation coefficient (R(2)) data ranging from 0.9793 (for the dimer of octanal) through to 0.9990 (for isobutyric acid). Finally, the developed protocols were applied to the analysis of malodour in sock samples. Initial work involved spiking an inert matrix and sock samples with appropriate concentrations of eight VCs. The average recovery from the inert matrix was 101±18% (n=8), while recoveries from the sock samples were lower, that is, 54±30% (n=8) for sock type 1 and 78±24% (n=6) for sock type 2. Finally, SHS-MCC-GC-IMS was applied to sock malodour in a field trial based on 11 volunteers (mixed gender) over a 3-week period. By applying the SHS-MCC-GC-IMS database, four VCs were

  17. Analysis of volatile organic compounds in pleural effusions by headspace solid-phase microextraction coupled with cryotrap gas chromatography and mass spectrometry.

    Science.gov (United States)

    Huang, Zhongping; Zhang, Jie; Zhang, Peipei; Wang, Hong; Pan, Zaifa; Wang, Lili

    2016-07-01

    Headspace solid-phase microextraction coupled with cryotrap gas chromatography and mass spectrometry was applied to the analysis of volatile organic compounds in pleural effusions. The highly volatile organic compounds were separated successfully with high sensitivity by the employment of a cryotrap device, with the construction of a cold column head by freezing a segment of metal capillary with liquid nitrogen. A total of 76 volatile organic compounds were identified in 50 pleural effusion samples (20 malignant effusions and 30 benign effusions). Among them, 34 more volatile organic compounds were detected with the retention time less than 8 min, by comparing with the normal headspace solid-phase microextraction coupled with gas chromatography and mass spectrometry method. Furthermore, 24 volatile organic compounds with high occurrence frequency in pleural effusion samples, 18 of which with the retention time less than 8 min, were selected for the comparative analysis. The results of average peak area comparison and box-plot analysis showed that except for cyclohexanone, 2-ethyl-1-hexanol, and tetramethylbenzene, which have been reported as potential cancer biomarkers, cyclohexanol, dichloromethane, ethyl acetate, n-heptane, ethylbenzene, and xylene also had differential expression between malignant and benign effusions. Therefore, the proposed approach was valuable for the comprehensive characterization of volatile organic compounds in pleural effusions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    1999-03-01

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

  19. Headspace techniques in foods, fragrances and flavors: an overview.

    Science.gov (United States)

    Rouseff, R; Cadwallader, K

    2001-01-01

    Headspace techniques have traditionally involved the collection of volatiles in the vapor state under either dynamic or static conditions as a means of determining concentrations in the product of interest. A brief overview of contemporary headspace applications and recent innovations are presented from the literature and Chapters in this book. New approaches used to concentrate volatiles under static conditions such as solid phase micro extraction, SPME, are examined. Advances in purge and trap applications and automation are also presented. Innovative methods of evaluating headspace volatiles using solid state sensor arrays (electronic noses) or mass spectrometers without prior separation are referenced. Numerous food and beverage headspace techniques are also reviewed. Advantages, limitations and alternatives to headspace analysis are presented.

  20. [Analysis of the components of floral scent in Glochidion puberum using gas chromatography-mass spectrometry with dynamic headspace adsorption].

    Science.gov (United States)

    Huang, Daihong; Zhang, Zhenguo; Chen, Guoping; Li, Houhun; Shi, Fuchen

    2015-03-01

    The floral scent plays the important key role in maintaining the obligate pollination mutualism between Glochidion plants and Epicephala moths. In the study, the dynamic headspace adsorption technique was employed to collect the floral scent emitted by Glochidion puberum, gas chromatography coupled with mass spectrometry (GC-MS) was used for the detection and identification of volatile chemical components in headspace samples of flowers from G. puberum. The peak area normalization was used to determine the relative contents of each odour component. The results showed that 45 compounds mainly consisting of monoterpenes and sesquiterpenes were isolated from the floral scent produced by G. puberum. Especially, both linalool (38.06%) and β-elemene (23.84%) were considered as the major scent components of G. puberum. It was speculated that linalool and β-elemene may be the two potential compounds attracting female Epicephala moths. The study provided the basic data for further electroantennographic detection and bioassays to identify the compounds having the actual physiological activity to female Epicephala moths.

  1. Optimization of headspace experimental factors to determine chlorophenols in water by means of headspace solid-phase microextraction and gas chromatography coupled with mass spectrometry and parallel factor analysis.

    Science.gov (United States)

    Morales, Rocío; Cruz Ortiz, M; Sarabia, Luis A

    2012-11-19

    In this work an analytical procedure based on headspace solid-phase microextraction and gas chromatography coupled with mass spectrometry (HS-SPME-GC/MS) is proposed to determine chlorophenols with prior derivatization step to improve analyte volatility and therefore the decision limit (CCα). After optimization, the analytical procedure was applied to analyze river water samples. The following analytes are studied: 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TrCP), 2,3,4,6-tetrachlorophenol (2,4,6-TeCP) and pentachlorophenol (PCP). A D-optimal design is used to study the parameters affecting the HS-SPME process and the derivatization step. Four experimental factors at two levels and one factor at three levels were considered: (i) equilibrium/extraction temperature, (ii) extraction time, (iii) sample volume, (iv) agitation time and (v) equilibrium time. In addition two interactions between four of them were considered. The D-optimal design enables the reduction of the number of experiments from 48 to 18 while maintaining enough precision in the estimation of the effects. As every analysis took 1h, the design is blocked in 2 days. The second-order property of the PARAFAC (parallel factor analysis) decomposition avoids the need of fitting a new calibration model each time that the experimental conditions change. In consequence, the standardized loadings in the sample mode estimated by a PARAFAC decomposition are the response used in the design because they are proportional to the amount of analyte extracted. It has been found that block effect is significant and that 60°C equilibrium temperature together with 25min extraction time are necessary to achieve the best extraction for the chlorophenols analyzed. The other factors and interactions were not significant. After that, a calibration based in a PARAFAC2 decomposition provided the following values of CCα: 120, 208, 86, 39ngL(-1) for 2,4-DCP, 2,4,6-TrCP, 2,3,4,5-TeCP and PCP respectively for a

  2. Analysis of volatiles in silver carp by headspace solid phase micro-extraction coupled with GC-MS

    International Nuclear Information System (INIS)

    Yang Yuping; Xiong Guangquan; Cheng Wei; Liao Tao; Lin Ruotai; Geng Shengrong; Li Xin; Li Xiaoding; Wu Wenjin

    2010-01-01

    In this paper, a method for the determination of volatiles using headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) was presented. The extraction conditions were optimized with reference to these volatiles as hexanal, heptanal, benzaldehyde, 1-Octen-3-ol, octanal, nonanal, decenal, 2,4-heptadienal and 2,4-decadienal. The extraction of fish muscle followed by incubation on a StableFlex divinyl benzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber during 50 in at 60 obtained the most effective extraction of the analytes. The methods by HS-SPME and GC-MS were effective in detecting volatiles in the gills, scales, viscera and fish muscles. The types of volatiles in the gill were more than other organs and the number of odors compounds was 63, and the number of volatiles in scales, viscera and fish muscles was 48, 44 and 42 respectively. (authors)

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

    Science.gov (United States)

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

    2002-05-25

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

  4. Liquid paraffin as new dilution medium for the analysis of high boiling point residual solvents with static headspace-gas chromatography.

    Science.gov (United States)

    D'Autry, Ward; Zheng, Chao; Bugalama, John; Wolfs, Kris; Hoogmartens, Jos; Adams, Erwin; Wang, Bochu; Van Schepdael, Ann

    2011-07-15

    Residual solvents are volatile organic compounds which can be present in pharmaceutical substances. A generic static headspace-gas chromatography analysis method for the identification and control of residual solvents is described in the European Pharmacopoeia. Although this method is proved to be suitable for the majority of samples and residual solvents, the method may lack sensitivity for high boiling point residual solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and benzyl alcohol. In this study, liquid paraffin was investigated as new dilution medium for the analysis of these residual solvents. The headspace-gas chromatography method was developed and optimized taking the official Pharmacopoeia method as a starting point. The optimized method was validated according to ICH criteria. It was found that the detection limits were below 1μg/vial for each compound, indicating a drastically increased sensitivity compared to the Pharmacopoeia method, which failed to detect the compounds at their respective limit concentrations. Linearity was evaluated based on the R(2) values, which were above 0.997 for all compounds, and inspection of residual plots. Instrument and method precision were examined by calculating the relative standard deviations (RSD) of repeated analyses within the linearity and accuracy experiments, respectively. It was found that all RSD values were below 10%. Accuracy was checked by a recovery experiment at three different levels. Mean recovery values were all in the range 95-105%. Finally, the optimized method was applied to residual DMSO analysis in four different Kollicoat(®) sample batches. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. A headspace solid-phase microextraction procedure coupled with gas chromatography-mass spectrometry for the analysis of volatile polycyclic aromatic hydrocarbons in milk samples

    Energy Technology Data Exchange (ETDEWEB)

    Aguinaga, N.; Campillo, N.; Vinas, P.; Hernandez-Cordoba, M. [University of Murcia, Department of Analytical Chemistry, Faculty of Chemistry, Murcia (Spain)

    2008-06-15

    A sensitive and solvent-free method for the determination of ten polycyclic aromatic hydrocarbons, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene and chrysene, with up to four aromatic rings, in milk samples using headspace solid-phase microextraction and gas chromatography-mass spectrometry detection has been developed. A polydimethylsiloxane-divinylbenzene fiber was chosen and used at 75 C for 60 min. Detection limits ranging from 0.2 to 5 ng L{sup -1} were attained at a signal-to-noise ratio of 3, depending on the compound and the milk sample under analysis. The proposed method was applied to ten different milk samples and the presence of six of the analytes studied in a skimmed milk with vegetal fiber sample was confirmed. The reliability of the procedure was verified by analyzing two different certified reference materials and by recovery studies. (orig.)

  6. Direct thermal desorption in the analysis of cheese volatiles by gas chromatography and gas chromatography-mass spectrometry: comparison with simultaneous distillation-extraction and dynamic headspace.

    Science.gov (United States)

    Valero, E; Sanz, J; Martínez-Castro, I

    2001-06-01

    Direct thermal desorption (DTD) has been used as a technique for extracting volatile components of cheese as a preliminary step to their gas chromatographic (GC) analysis. In this study, it is applied to different cheese varieties: Camembert, blue, Chaumes, and La Serena. Volatiles are also extracted using other techniques such as simultaneous distillation-extraction and dynamic headspace. Separation and identification of the cheese components are carried out by GC-mass spectrometry. Approximately 100 compounds are detected in the examined cheeses. The described results show that DTD is fast, simple, and easy to automate; requires only a small amount of sample (approximately 50 mg); and affords quantitative information about the main groups of compounds present in cheeses.

  7. Headspace solid-phase microextraction coupled to gas chromatography for the analysis of aldehydes in edible oils.

    Science.gov (United States)

    Ma, Chunhua; Ji, Jiaojiao; Tan, Connieal; Chen, Dongmei; Luo, Feng; Wang, Yiru; Chen, Xi

    2014-03-01

    Oxidation has important effects on the quality of edible oils. In particular, the generation of aldehydes produced by the oxidation of oils is one of the deteriorative factors to their quality. The aim of this study was to develop a method to determine the aldehydes as lipid oxidation markers in edible oils. Seven aldehydes generated from lipid oxidation were studied using headspace solid-phase microextraction coupled to gas chromatography with a flame ionization detector. The extraction efficiency of five commercial fibers was investigated and the influence of extraction temperature, extraction time, desorption temperature, and desorption time were optimized. The best result was obtained with 85 μm carboxen/polydimethylsiloxane, extraction at 50 °C for 15 min and desorption in the gas chromatography injector at 250 °C for 2 min. Under the optimized conditions, the content of hexanal was the highest of the seven aldehydes in all edible oils. The limits of detection for hexanal in the three oils were found to range from 4.6 to 10.2 ng L(-1). The reproducibility of the method was evaluated and the relative standard deviations were less than 8.9%. This developed approach was successfully applied to analyze hexanal in peanut oil, soy oil, and olive oil samples, and these results were compared with those obtained using the thiobarbituric acid-reactive substances (TBARs) method. © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

  8. Magnetic solid phase extraction and static headspace gas chromatography-mass spectrometry method for the analysis of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    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 7.8 ng/L. Good values for intra and inter-day precision were obtained (RSDs ≤ 9.9%). The proposed method was successfully applied to drinking water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. GC-MS analysis of headspace and liquid extracts for metabolomic differentiation of citrus Huanglongbing and zinc deficiency in leaves of 'Valencia' sweet orange from commercial groves.

    Science.gov (United States)

    Cevallos-Cevallos, Juan Manuel; García-Torres, Rosalía; Etxeberria, Edgardo; Reyes-De-Corcuera, José Ignacio

    2011-01-01

    Citrus Huanglongbing (HLB) is considered the most destructive citrus disease worldwide. Symptoms-based detection of HLB is difficult due to similarities with zinc deficiency. To find metabolic differences between leaves from HLB-infected, zinc-deficient, and healthy 'Valencia' orange trees by using GC-MS based metabolomics. Analysis based on GC-MS methods for untargeted metabolite analysis of citrus leaves was developed and optimized. Sample extracts from healthy, zinc deficient, or HLB-infected sweet orange leaves were submitted to headspace solid phase micro-extraction (SPME) and derivatization treatments prior to GC-MS analysis. Principal components analysis achieved correct classification of all the derivatized liquid extracts. Analysis of variance revealed 6 possible biomarkers for HLB, of which 5 were identified as proline, β-elemene, (-)trans- caryophyllene, and α-humulene. Significant (P < 0.05) differences in oxo-butanedioic acid, arabitol, and neo-inositol were exclusively detected in samples from plants with zinc deficiency. Levels of isocaryophyllen, α-selinene, β-selinene, and fructose were significantly (P < 0.05) different in healthy leaves only. Results suggest the potential of using identified HLB biomarkers for rapid differentiation of HLB from zinc deficiency. Copyright © 2010 John Wiley & Sons, Ltd.

  10. Multivariate analysis of volatile compounds detected by headspace solid-phase microextraction/gas chromatography: A tool for sensory classification of cork stoppers.

    Science.gov (United States)

    Prat, Chantal; Besalú, Emili; Bañeras, Lluís; Anticó, Enriqueta

    2011-06-15

    The volatile fraction of aqueous cork macerates of tainted and non-tainted agglomerate cork stoppers was analysed by headspace solid-phase microextraction (HS-SPME)/gas chromatography. Twenty compounds containing terpenoids, aliphatic alcohols, lignin-related compounds and others were selected and analysed in individual corks. Cork stoppers were previously classified in six different classes according to sensory descriptions including, 2,4,6-trichloroanisole taint and other frequent, non-characteristic odours found in cork. A multivariate analysis of the chromatographic data of 20 selected chemical compounds using linear discriminant analysis models helped in the differentiation of the a priori made groups. The discriminant model selected five compounds as the best combination. Selected compounds appear in the model in the following order; 2,4,6 TCA, fenchyl alcohol, 1-octen-3-ol, benzyl alcohol and benzothiazole. Unfortunately, not all six a priori differentiated sensory classes were clearly discriminated in the model, probably indicating that no measurable differences exist in the chromatographic data for some categories. The predictive analyses of a refined model in which two sensory classes were fused together resulted in a good classification. Prediction rates of control (non-tainted), TCA, musty-earthy-vegetative, vegetative and chemical descriptions were 100%, 100%, 85%, 67.3% and 100%, respectively, when the modified model was used. The multivariate analysis of chromatographic data will help in the classification of stoppers and provide a perfect complement to sensory analyses. Copyright © 2010 Elsevier Ltd. All rights reserved.

  11. Analysis of the Volatile Profile of Core Chinese Mango Germplasm by Headspace Solid-Phase Microextraction Coupled with Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Xiao-Wei Ma

    2018-06-01

    Full Text Available Despite abundant published research on the volatile characterization of mango germplasm, the aroma differentiation of Chinese cultivars remains unclear. Using headspace solid phase microextraction (HS-SPME coupled with gas chromatography–mass spectrometry (GC-MS, the composition and relative content of volatiles in 37 cultivars representing the diversity of Chinese mango germplasm were investigated. Results indicated that there are distinct differences in the components and content of volatile compounds among and within cultivars. In total, 114 volatile compounds, including 23 monoterpenes, 16 sesquiterpenes, 29 non-terpene hydrocarbons, 25 esters, 11 aldehydes, five alcohols and five ketones, were identified. The total volatile content among cultivars ranged from 211 to 26,022 μg/kg fresh weight (FW, with 123-fold variation. Terpene compounds were the basic background volatiles, and 34 cultivars exhibited abundant monoterpenes. On the basis of hierarchical cluster analysis (HCA and principal component analysis (PCA, terpinolene and α-pinene were important components constituting the aroma of Chinese mango cultivars. Most obviously, a number of mango cultivars with high content of various aroma components were observed, and they can serve as potential germplasms for both breeding and direct use.

  12. Speciation analysis of organotin compounds in human urine by headspace solid-phase micro-extraction and gas chromatography with pulsed flame photometric detection.

    Science.gov (United States)

    Valenzuela, Aníbal; Lespes, Gaëtane; Quiroz, Waldo; Aguilar, Luis F; Bravo, Manuel A

    2014-07-01

    A new headspace solid-phase micro-extraction (HS-SPME) method followed by gas chromatography with pulsed flame photometric detection (GC-PFPD) analysis has been developed for the simultaneous determination of 11 organotin compounds, including methyl-, butyl-, phenyl- and octyltin derivates, in human urine. The methodology has been validated by the analysis of urine samples fortified with all analytes at different concentration levels, and recovery rates above 87% and relative precisions between 2% and 7% were obtained. Additionally, an experimental-design approach has been used to model the storage stability of organotin compounds in human urine, demonstrating that organotins are highly degraded in this medium, although their stability is satisfactory during the first 4 days of storage at 4 °C and pH=4. Finally, this methodology was applied to urine samples collected from harbor workers exposed to antifouling paints; methyl- and butyltins were detected, confirming human exposure in this type of work environment. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Application of headspace and direct immersion solid-phase microextraction in the analysis of organothiophosphates related to the Chemical Weapons Convention from water and complex matrices.

    Science.gov (United States)

    Althoff, Marc André; Bertsch, Andreas; Metzulat, Manfred; Klapötke, Thomas M; Karaghiosoff, Konstantin L

    2017-11-01

    The successful application of headspace (HS) and direct immersion (DI) solid phase microextraction (SPME) for the unambiguous identification and characterization of a series of toxic thiophosphate esters, such as Amiton (I), from aqueous phases and complex matrices (e.g. grass and foliage) has been demonstrated. A Thermo Scientific gas chromatograph (GC) - tandem mass spectrometer (MS/MS) system with a TriPlus RSH® autosampler and a SPME tool was used to investigate the effect of different parameters that influence the extraction efficiency: e.g. pH of the sample matrix and extraction temperature. The developed methods were employed for the detection of several Amiton derivatives (Schedule II of the CWC) that are structurally closely related to each other; some of which are new and have not been reported in literature previously. In addition, a novel DI SPME method from complex matrices for the analysis of organophosphates related to the CWC was developed. The studies clearly show that DI SPME for complex matrices is superior to HS extraction and can potentially be applied to other related compounds controlled under the CWC. Copyright © 2017. Published by Elsevier B.V.

  14. Possibilities and limitations of dynamic headspace sampling as a pre-concentration technique for trace analysis of organics by capillary gas chromatography

    NARCIS (Netherlands)

    Curvers, J.M.P.M.; Noij, T.H.M.; Cramers, C.A.M.G.; Rijks, J.A.

    1984-01-01

    The possibilities, the limitations and the quantitative performance of dynamic headspace sampling, in particular closed-loop stripping, were investigated for various classes of organic substances in aqueous samples with concentrations down to the parts per 1012 (ppt) level. The effects of variations

  15. Rapid analysis of Fructus forsythiae essential oil by ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction followed by gas chromatography–mass spectrometry

    International Nuclear Information System (INIS)

    Jiao, Jiao; Ma, Dan-Hui; Gai, Qing-Yan; Wang, Wei; Luo, Meng; Fu, Yu-Jie; Ma, Wei

    2013-01-01

    Graphical abstract: -- Highlights: •A new ILAMD-HS-SDME method is developed for the microextraction of essential oil. •ILs used as destruction agent of plant cell walls and microwave absorption medium. •Parameters affecting the extraction efficiency are optimized by Box–Behnken design. •Procedure benefits: similar constituents, shorter duration and smaller sample amount. •ILAMD-HS-SDME followed by GC–MS is a promising technique in analytical fields. -- Abstract: A rapid, green and effective miniaturized sample preparation and analytical technique, i.e. ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction (ILAMD-HS-SDME) followed by gas chromatography–mass spectrometry (GC–MS) was developed for the analysis of essential oil (EO) in Fructus forsythiae. In this work, ionic liquids (ILs) were not only used as the absorption medium of microwave irradiation but also as the destruction agent of plant cell walls. 1-Ethyl-3-methylimidazolium acetate ([C 2 mim]OAc) was chosen as the optimal ILs. Moreover, n-heptadecane (2.0 μL) was selected as the appropriate suspended solvent for the extraction and concentration of EO. Extraction conditions of the proposed method were optimized using the relative peak area of EO constituents as the index, and the optimal operational parameters were obtained as follows: irradiation power (300 W), sample mass (0.7 g), mass ratio of ILs to sample (2.4), temperature (78 °C) and time (3.4 min). In comparison to previous reports, the proposed method was faster and required smaller sample amount but could equally monitor all EO constituents with no significant differences

  16. Rapid analysis of Fructus forsythiae essential oil by ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction followed by gas chromatography–mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jiao, Jiao [State Key Laboratory of Tree Genetics and Breeding, Northeast Forestry University, Harbin 150040 (China); Ma, Dan-Hui [College of Life Sciences, Northeast Forestry University, Harbin 150040 (China); Gai, Qing-Yan; Wang, Wei; Luo, Meng [State Engineering Laboratory of Bio-Resource Eco-Utilization, Northeast Forestry University, Harbin 150040 (China); Fu, Yu-Jie, E-mail: yujie_fu2002@yahoo.com [State Engineering Laboratory of Bio-Resource Eco-Utilization, Northeast Forestry University, Harbin 150040 (China); Ma, Wei, E-mail: mawei@hljucm.net [State Key Laboratory of Tree Genetics and Breeding, Northeast Forestry University, Harbin 150040 (China); School of Pharmaceutical, Heilongjiang University of Chinese Medicine, Harbin 150040 (China)

    2013-12-04

    Graphical abstract: -- Highlights: •A new ILAMD-HS-SDME method is developed for the microextraction of essential oil. •ILs used as destruction agent of plant cell walls and microwave absorption medium. •Parameters affecting the extraction efficiency are optimized by Box–Behnken design. •Procedure benefits: similar constituents, shorter duration and smaller sample amount. •ILAMD-HS-SDME followed by GC–MS is a promising technique in analytical fields. -- Abstract: A rapid, green and effective miniaturized sample preparation and analytical technique, i.e. ionic liquids-assisted microwave distillation coupled with headspace single-drop microextraction (ILAMD-HS-SDME) followed by gas chromatography–mass spectrometry (GC–MS) was developed for the analysis of essential oil (EO) in Fructus forsythiae. In this work, ionic liquids (ILs) were not only used as the absorption medium of microwave irradiation but also as the destruction agent of plant cell walls. 1-Ethyl-3-methylimidazolium acetate ([C{sub 2}mim]OAc) was chosen as the optimal ILs. Moreover, n-heptadecane (2.0 μL) was selected as the appropriate suspended solvent for the extraction and concentration of EO. Extraction conditions of the proposed method were optimized using the relative peak area of EO constituents as the index, and the optimal operational parameters were obtained as follows: irradiation power (300 W), sample mass (0.7 g), mass ratio of ILs to sample (2.4), temperature (78 °C) and time (3.4 min). In comparison to previous reports, the proposed method was faster and required smaller sample amount but could equally monitor all EO constituents with no significant differences.

  17. Headspace-SPME-GC/MS as a simple cleanup tool for sensitive 2,6-diisopropylphenol analysis from lipid emulsions and adaptable to other matrices.

    Science.gov (United States)

    Pickl, Karin E; Adamek, Viktor; Gorges, Roland; Sinner, Frank M

    2011-07-15

    Due to increased regulatory requirements, the interaction of active pharmaceutical ingredients with various surfaces and solutions during production and storage is gaining interest in the pharmaceutical research field, in particular with respect to development of new formulations, new packaging material and the evaluation of cleaning processes. Experimental adsorption/absorption studies as well as the study of cleaning processes require sophisticated analytical methods with high sensitivity for the drug of interest. In the case of 2,6-diisopropylphenol - a small lipophilic drug which is typically formulated as lipid emulsion for intravenous injection - a highly sensitive method in the concentration range of μg/l suitable to be applied to a variety of different sample matrices including lipid emulsions is needed. We hereby present a headspace-solid phase microextraction (HS-SPME) approach as a simple cleanup procedure for sensitive 2,6-diisopropylphenol quantification from diverse matrices choosing a lipid emulsion as the most challenging matrix with regard to complexity. By combining the simple and straight forward HS-SPME sample pretreatment with an optimized GC-MS quantification method a robust and sensitive method for 2,6-diisopropylphenol was developed. This method shows excellent sensitivity in the low μg/l concentration range (5-200μg/l), good accuracy (94.8-98.8%) and precision (intraday-precision 0.1-9.2%, inter-day precision 2.0-7.7%). The method can be easily adapted to other, less complex, matrices such as water or swab extracts. Hence, the presented method holds the potential to serve as a single and simple analytical procedure for 2,6-diisopropylphenol analysis in various types of samples such as required in, e.g. adsorption/absorption studies which typically deal with a variety of different surfaces (steel, plastic, glass, etc.) and solutions/matrices including lipid emulsions. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. Use of headspace SPME-GC-MS for the analysis of the volatiles produced by indoor molds grown on different substrates.

    Science.gov (United States)

    Van Lancker, Fien; Adams, An; Delmulle, Barbara; De Saeger, Sarah; Moretti, Antonio; Van Peteghem, Carlos; De Kimpe, Norbert

    2008-10-01

    An automated headspace solid phase microextraction method followed by GC-MS analysis was used to evaluate and compare the in vitro production of microbial volatile organic compounds (MVOCs) on malt extract agar, plasterboard and wallpaper. Five fungal strains were isolated from the walls of water-damaged houses and identified. In addition, four other common molds were studied. In general, MVOC production was the highest on malt extract agar. On this synthetic medium, molds typically produced 2-methylpropanol, 2-methylbutanol and 3-methylbutanol. On wallpaper, mainly 2-ethylhexanol, methyl 2-ethylhexanoate and compounds of the C8-complex such as 1-octene-3-ol, 3-octanone, 3-octanol and 1,3-octadiene were detected. The detection of 2-ethylhexanol and methyl 2-ethylhexanoate indicates an enhanced degradation of the substrate by most fungi. For growth on plasterboard, no typical metabolites were detected. Despite these metabolite differences on malt extract agar, wallpaper and plasterboard, some molds also produced specific compounds independently of the used substrate, such as trichodiene from Fusarium sporotrichioides and aristolochene from Penicillium roqueforti. Therefore, these metabolites can be used as markers for the identification and maybe also mycotoxin production of these molds. All five investigated Penicillium spp. in this study were able to produce two specific diterpenes, which were not produced by the other species studied. These two compounds, which remain unidentified until now, therefore seem specific for Penicillium spp. and are potentially interesting for the monitoring of this fungal genus. Further experiments will be performed with other Penicillium spp. to study the possibility that these two compounds are specific for this group of molds.

  19. Characterization of the major odor-active compounds in Thai durian ( Durio zibethinus L. 'Monthong') by aroma extract dilution analysis and headspace gas chromatography-olfactometry.

    Science.gov (United States)

    Li, Jia-Xiao; Schieberle, Peter; Steinhaus, Martin

    2012-11-14

    An aroma extract dilution analysis applied on the volatile fraction isolated from Thai durian by solvent extraction and solvent-assisted flavor evaporation resulted in 44 odor-active compounds in the flavor dilution (FD) factor range of 1-16384, 41 of which could be identified and 24 that had not been reported in durian before. High FD factors were found for ethyl (2S)-2-methylbutanoate (fruity; FD 16384), ethyl cinnamate (honey; FD 4096), and 1-(ethylsulfanyl)ethanethiol (roasted onion; FD 1024), followed by 1-(ethyldisulfanyl)-1-(ethylsulfanyl)ethane (sulfury, onion), 2(5)-ethyl-4-hydroxy-5(2)-methylfuran-3(2H)-one (caramel), 3-hydroxy-4,5-dimethylfuran-2(5H)-one (soup seasoning), ethyl 2-methylpropanoate (fruity), ethyl butanoate (fruity), 3-methylbut-2-ene-1-thiol (skunky), ethane-1,1-dithiol (sulfury, durian), 1-(methylsulfanyl)ethanethiol (roasted onion), 1-(ethylsulfanyl)propane-1-thiol (roasted onion), and 4-hydroxy-2,5-dimethylfuran-3(2H)-one (caramel). Among the highly volatile compounds screened by static headspace gas chromatography-olfactometry, hydrogen sulfide (rotten egg), acetaldehyde (fresh, fruity), methanethiol (rotten, cabbage), ethanethiol (rotten, onion), and propane-1-thiol (rotten, durian) were found as additional potent odor-active compounds. Fourteen of the 41 characterized durian odorants showed an alkane-1,1-dithiol, 1-(alkylsulfanyl)alkane-1-thiol, or 1,1-bis(alkylsulfanyl)alkane structure derived from acetaldehyde, propanal, hydrogen sulfide, and alkane-1-thiols. Among these, 1-(propylsulfanyl)ethanethiol, 1-{[1-(methylsulfanyl)ethyl]sulfanyl}ethanethiol, and 1-{[1-(ethylsulfanyl)ethyl]sulfanyl}ethanethiol were reported for the first time in a natural product.

  20. TBA PRODUCTION BY ACID HYDROLYSIS OF MTBE DURING HEATED HEADSPACE ANALYSIS & EVALUATION OF A BASE AS A PRESERVATIVE

    Science.gov (United States)

    At room temperature (20°±3°C), purge and trap samplers provide poor sensitivity for analysis of the fuel oxygenates that are alcohols, such as tertiary butyl alcohol (TBA). Because alcohols are miscible or highly soluble in water, they are not efficiently transferred to a gas chr...

  1. Analysis of the volatiles in the headspace above the plasmodium and sporangia of the slime mould (Physarum polycephalum) by SPME-GCMS

    OpenAIRE

    Kateb, Huda al; Costello, Ben de Lacy

    2013-01-01

    Solid phase micro-extraction (SPME) coupled with Gas Chromatography Mass Spectrometry (GC-MS) was used to extract and analyse the volatiles in the headspace above the plasmodial and sporulating stages of the slime mould Physarum Polycephalum. In total 115 compounds were identified from across a broad range of chemical classes. Although more (87) volatile organic compounds (VOCs) were identified when using a higher incubation temperature of 75oC, a large number of compounds (79) were still ide...

  2. Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis

    International Nuclear Information System (INIS)

    Zaitseva, Ksenia V.; Varfolomeev, Mikhail A.; Solomonov, Boris N.

    2012-01-01

    Highlights: ► Solution enthalpies and activity coefficients of amines in methanol were measured. ► Thermodynamic functions of H-bonding of amines with methanol were determined. ► Specific interaction entropy of amines in methanol can be about zero or positive. ► Cooperativity of H-bonds in methanol media is smaller than in water solutions. ► A new view on analysis of specific interaction of solute with methanol is presented. - Abstract: Reactivity and equilibrium properties of organic molecules in self-associated liquids greatly depend on the hydrogen bonding with solvent. This work contains comprehensive thermodynamic analysis of hydrogen bonding of aliphatic and aromatic amines in self-associated solvent methanol. Enthalpies of solution at infinite dilution and limiting activity coefficients for the studied systems were measured experimentally. Enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol were determined. These values were found to be decreased compared with hydrogen bond energy in equimolar complexes “methanol–amine” determined in inert solvent or base media. A linear dependence between enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol was observed. It was firstly revealed that the entropy of specific interactions of amines with neat methanol can be about zero or positive. Disruption of solvent–solvent hydrogen bonds can be regarded as the most important step during dissolution of amine in methanol. It was found that the cooperative effect influences on the Gibbs energies of hydrogen bonding of amines in methanol, but in a lesser extent than in aqueous solutions. The new results show that the hydrogen bonding process in the self-associated solvents differs significantly from equimolar complexation in aprotic media.

  3. Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zaitseva, Ksenia V., E-mail: zaitseva.ksenia@gmail.com [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Varfolomeev, Mikhail A., E-mail: vma.ksu@gmail.com [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Solomonov, Boris N., E-mail: boris.solomonov@ksu.ru [Chemical Institute, Kazan (Volga Region) Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation)

    2012-05-10

    Highlights: Black-Right-Pointing-Pointer Solution enthalpies and activity coefficients of amines in methanol were measured. Black-Right-Pointing-Pointer Thermodynamic functions of H-bonding of amines with methanol were determined. Black-Right-Pointing-Pointer Specific interaction entropy of amines in methanol can be about zero or positive. Black-Right-Pointing-Pointer Cooperativity of H-bonds in methanol media is smaller than in water solutions. Black-Right-Pointing-Pointer A new view on analysis of specific interaction of solute with methanol is presented. - Abstract: Reactivity and equilibrium properties of organic molecules in self-associated liquids greatly depend on the hydrogen bonding with solvent. This work contains comprehensive thermodynamic analysis of hydrogen bonding of aliphatic and aromatic amines in self-associated solvent methanol. Enthalpies of solution at infinite dilution and limiting activity coefficients for the studied systems were measured experimentally. Enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol were determined. These values were found to be decreased compared with hydrogen bond energy in equimolar complexes 'methanol-amine' determined in inert solvent or base media. A linear dependence between enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol was observed. It was firstly revealed that the entropy of specific interactions of amines with neat methanol can be about zero or positive. Disruption of solvent-solvent hydrogen bonds can be regarded as the most important step during dissolution of amine in methanol. It was found that the cooperative effect influences on the Gibbs energies of hydrogen bonding of amines in methanol, but in a lesser extent than in aqueous solutions. The new results show that the hydrogen bonding process in the self-associated solvents differs significantly from equimolar complexation in aprotic media.

  4. Parameters optimization using experimental design for headspace solid phase micro-extraction analysis of short-chain chlorinated paraffins in waters under the European water framework directive.

    Science.gov (United States)

    Gandolfi, F; Malleret, L; Sergent, M; Doumenq, P

    2015-08-07

    The water framework directives (WFD 2000/60/EC and 2013/39/EU) force European countries to monitor the quality of their aquatic environment. Among the priority hazardous substances targeted by the WFD, short chain chlorinated paraffins C10-C13 (SCCPs), still represent an analytical challenge, because few laboratories are nowadays able to analyze them. Moreover, an annual average quality standards as low as 0.4μgL(-1) was set for SCCPs in surface water. Therefore, to test for compliance, the implementation of sensitive and reliable analysis method of SCCPs in water are required. The aim of this work was to address this issue by evaluating automated solid phase micro-extraction (SPME) combined on line with gas chromatography-electron capture negative ionization mass spectrometry (GC/ECNI-MS). Fiber polymer, extraction mode, ionic strength, extraction temperature and time were the most significant thermodynamic and kinetic parameters studied. To determine the suitable factors working ranges, the study of the extraction conditions was first carried out by using a classical one factor-at-a-time approach. Then a mixed level factorial 3×2(3) design was performed, in order to give rise to the most influent parameters and to estimate potential interactions effects between them. The most influent factors, i.e. extraction temperature and duration, were optimized by using a second experimental design, in order to maximize the chromatographic response. At the close of the study, a method involving headspace SPME (HS-SPME) coupled to GC/ECNI-MS is proposed. The optimum extraction conditions were sample temperature 90°C, extraction time 80min, with the PDMS 100μm fiber and desorption at 250°C during 2min. Linear response from 0.2ngmL(-1) to 10ngmL(-1) with r(2)=0.99 and limits of detection and quantification, respectively of 4pgmL(-1) and 120pgmL(-1) in MilliQ water, were achieved. The method proved to be applicable in different types of waters and show key advantages, such

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

    African Journals Online (AJOL)

    A headspace solid-phase microextraction (HS-SPME) method was developed as a preliminary investigation using univariate approach for the analysis of 14 multiclass pesticide residues in fruits and vegetable samples. The gas chromatography mass spectrometry parameters (desorption temperature and time, column flow ...

  6. In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

    Energy Technology Data Exchange (ETDEWEB)

    Neitzel, P.L.; Walther, W. [Dresden University of Technology, Institute for Groundwater Managemant, Dresden (Germany); Nestler, W. [Institute for Technology and Economics, Department of Civil Engineering and Architecture, Dresden (Germany)

    1998-06-01

    Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 {mu}g/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 {mu}g/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles. (orig.) With 3 figs., 2 tabs., 29 refs.

  7. Monitoring gas-phase CO2 in the headspace of champagne glasses through combined diode laser spectrometry and micro-gas chromatography analysis.

    Science.gov (United States)

    Moriaux, Anne-Laure; Vallon, Raphaël; Parvitte, Bertrand; Zeninari, Virginie; Liger-Belair, Gérard; Cilindre, Clara

    2018-10-30

    During Champagne or sparkling wine tasting, gas-phase CO 2 and volatile organic compounds invade the headspace above glasses, thus progressively modifying the chemical space perceived by the consumer. Gas-phase CO 2 in excess can even cause a very unpleasant tingling sensation perturbing both ortho- and retronasal olfactory perception. Monitoring as accurately as possible the level of gas-phase CO 2 above glasses is therefore a challenge of importance aimed at better understanding the close relationship between the release of CO 2 and a collection of various tasting parameters. Here, the concentration of CO 2 found in the headspace of champagne glasses served under multivariate conditions was accurately monitored, all along the 10 min following pouring, through a new combined approach by a CO 2 -Diode Laser Sensor and micro-gas chromatography. Our results show the strong impact of various tasting conditions (volume dispensed, intensity of effervescence, and glass shape) on the release of gas-phase CO 2 above the champagne surface. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Gas flow headspace liquid phase microextraction.

    Science.gov (United States)

    Yang, Cui; Qiu, Jinxue; Ren, Chunyan; Piao, Xiangfan; Li, Xifeng; Wu, Xue; Li, Donghao

    2009-11-06

    There is a trend towards the use of enrichment techniques such as microextraction in the analysis of trace chemicals. Based on the theory of ideal gases, theory of gas chromatography and the original headspace liquid phase microextraction (HS-LPME) technique, a simple gas flow headspace liquid phase microextraction (GF-HS-LPME) technique has been developed, where the extracting gas phase volume is increased using a gas flow. The system is an open system, where an inert gas containing the target compounds flows continuously through a special gas outlet channel (D=1.8mm), and the target compounds are trapped on a solvent microdrop (2.4 microL) hanging on the microsyringe tip, as a result, a high enrichment factor is obtained. The parameters affecting the enrichment factor, such as the gas flow rate, the position of the microdrop, the diameter of the gas outlet channel, the temperatures of the extracting solvent and of the sample, and the extraction time, were systematically optimized for four types of polycyclic aromatic hydrocarbons. The results were compared with results obtained from HS-LPME. Under the optimized conditions (where the extraction time and the volume of the extracting sample vial were fixed at 20min and 10mL, respectively), detection limits (S/N=3) were approximately a factor of 4 lower than those for the original HS-LPME technique. The method was validated by comparison of the GF-HS-LPME and HS-LPME techniques using data for PAHs from environmental sediment samples.

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

    Science.gov (United States)

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

    2017-05-01

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

  10. Tank 241-C-103 headspace flammability

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1994-01-01

    Information regarding flammable vapors, gases, and aerosols is presented for the purpose of resolving the tank 241-C-103 headspace flammability issue. Analyses of recent vapor and liquid samples, as well as visual inspections of the tank headspace, are discussed in the context of tank dynamics. This document is restricted to issues regarding the flammability of gases, vapors, and an aerosol that may exist in the headspace of tank 241-C-103. While discussing certain information about the organic liquid present in tank 241-C-103, this document addresses neither the potential for, nor consequences of, a pool fire involving this organic liquid; they will be discussed in a separate report

  11. Tank 241-C-103 headspace flammability

    Energy Technology Data Exchange (ETDEWEB)

    Huckaby, J.L.

    1994-01-01

    Information regarding flammable vapors, gases, and aerosols is presented for the purpose of resolving the tank 241-C-103 headspace flammability issue. Analyses of recent vapor and liquid samples, as well as visual inspections of the tank headspace, are discussed in the context of tank dynamics. This document is restricted to issues regarding the flammability of gases, vapors, and an aerosol that may exist in the headspace of tank 241-C-103. While discussing certain information about the organic liquid present in tank 241-C-103, this document addresses neither the potential for, nor consequences of, a pool fire involving this organic liquid; they will be discussed in a separate report.

  12. Automated headspace solid-phase dynamic extraction to analyse the volatile fraction of food matrices.

    Science.gov (United States)

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

    2004-01-23

    High concentration capacity headspace techniques (headspace solid-phase microextraction (HS-SPME) and headspace sorptive extraction (HSSE)) are a bridge between static and dynamic headspace, since they give high concentration factors as does dynamic headspace (D-HS), and are as easy to apply and as reproducible as static headspace (S-HS). In 2000, Chromtech (Idstein, Germany) introduced an inside-needle technique for vapour and liquid sampling, solid-phase dynamic extraction (SPDE), also known as "the magic needle". In SPDE, analytes are concentrated on a 50 microm film of polydimethylsiloxane (PDMS) and activated carbon (10%) coated onto the inside wall of the stainless steel needle (5 cm) of a 2.5 ml gas tight syringe. When SPDE is used for headspace sampling (HS-SPDE), a fixed volume of the headspace of the sample under investigation is sucked up an appropriate number of times with the gas tight syringe and an analyte amount suitable for a reliable GC or GC-MS analysis accumulates in the polymer coating the needle wall. This article describes the preliminary results of both a study on the optimisation of sampling parameters conditioning HS-SPDE recovery, through the analysis of a standard mixture of highly volatile compounds (beta-pinene, isoamyl acetate and linalool) and of the HS-SPDE-GC-MS analyses of aromatic plants and food matrices. This study shows that HS-SPDE is a successful technique for HS-sampling with high concentration capability, good repeatability and intermediate precision, also when it is compared to HS-SPME.

  13. Analysis of neutral volatile aroma components in Tilsit cheese using a combination of dynamic headspace technique, capillary gas chromatography and mass spectrometry

    International Nuclear Information System (INIS)

    Dillinger, K.H.

    2000-03-01

    Tilsit cheese is made by the influence of lab ferment and starter cultures on milk. The ripening is done by repeated inoculation of the surface of the Tilsit cheese with yeasts and read smear cultures. This surface flora forms the typical aroma of the Tilsit cheese during the ripening process. The aim of the work was to receive general knowledge about the kind and amount of the neutral volatile aroma components of Tilsit cheese. Beyond this the ability of forming aroma components by read smear cultures and the dispersion of these components in cheese was to be examined. The results were intended to evaluate the formation of aroma components in Tilsit cheese. The semi-quantitative analyses of the aroma components of all samples were done by combining dynamic headspace extraction, gas chromatography and mass spectrometry. In this process the neutral volatile aroma components were extracted by dynamic headspace technique, adsorbed on a trap, thermally desorbed, separated by gas chromatography, detected and identified by mass spectrometry. 63 components belonging to the chemical classes of esters, ketones, aldehydes, alcohols and sulfur containing substances as well as aromatic hydrocarbons, chlorinated hydrocarbons and hydrocarbons were found in the analysed cheese samples of different Austrian Tilsit manufacturing plants. All cheese samples showed a qualitative equal but quantitative varied spectrum of aroma components. The cultivation of pure cultures on a cheese agar medium showed all analysed aroma components to be involved in the biochemical metabolism of these cultures. The ability to produce aroma components greatly differed between the strains and it was not possible to correlate this ability with the taxonomic classification of the strains. The majority of the components had a non-homogeneous concentration profile in the cheese body. This was explained by effects of diffusion and temporal and spatial different forming of components by the metabolism of the

  14. Comparison of different types of coatings in headspace solid phase micro extraction for the analysis of pesticide residues in vegetables and fruits

    International Nuclear Information System (INIS)

    Chai, Mee Kin; Tan, Guan Huat

    2008-01-01

    Despite the continuing development of solid-phase micro extraction (SPME) fiber coatings, their selection presents some difficulties for analytes in choosing the appropriate fiber for a particular application. There are many types of SPME coatings available commercially. The most widely used for determination of pesticide residues in vegetable and fruits are polydimethylsiloxane (PDMS) and polyacrylate (PA). A headspace solid phase micro extraction (HS-SPME) procedure using these two commercialized fibers (PDMS and PA) is presented for the determination of selected groups of organo chlorine and organophosphorus pesticides. The extraction performances of these compounds were compared using these two fibers. The optimal experimental procedures for the adsorption and desorption of pesticides were determined. An explanation for the extraction differences is suggested based on the different thickness, polarity of the polymeric film of fibers and the different extracting matrices. In addition, the higher detector response of the pesticides after addition of aliquots of water and an organic solvent to the vegetable and fruit samples are also discussed. The SPME fibers were reusable until a maximum of 120 extractions. Finally, the optimized procedures were applied successfully for the determination of these compounds in vegetable and fruits samples. Mean recoveries for all pesticides were between 75.0-97 % with RSD below 7 %. (author)

  15. The application of headspace gas chromatography coupled to tandem quadrupole mass spectrometry for the analysis of furan in baby food samples.

    Science.gov (United States)

    Pugajeva, Iveta; Rozentale, Irina; Viksna, Arturs; Bartkiene, Elena; Bartkevics, Vadims

    2016-12-01

    Selective methodology employing a tandem quadrupole mass spectrometer coupled to a gas chromatograph with headspace autosampler (HS-GC-MS/MS) was elaborated in this study. Application of the elaborated procedure resulted in a limit of detection of 0.021μgkg(-1) and a limit of quantification of 0.071μgkg(-1). The mean recoveries during in-house validation ranged from 89% to 109%, and coefficients of variation for repeatability ranged from 4% to 11%. The proposed analytical method was applied for monitoring the furan content of 30 commercial baby food samples available on the Latvian retail market. The level of furan found in these samples varied from 0.45 to 81.9μgkg(-1), indicating that infants whose sole diet comprises baby food sold in jars and cans are exposed constantly to furan. Samples containing vegetables and meat had higher levels of furan than those containing only fruits. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Quantitative analysis of 2-furfural and 5-methylfurfural in different Italian vinegars by headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry using isotope dilution.

    Science.gov (United States)

    Giordano, Lucia; Calabrese, Roberto; Davoli, Enrico; Rotilio, Domenico

    2003-10-31

    A new method was developed for the determination of 2-furfural (2-F) and 5-methylfurfural (5-MF), two products of Maillard reaction in vinegar, with head-space solid-phase microextraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS). A divinylbenzene (DVB)/carboxen (CAR)/polydimethylsiloxane (PDMS) fibre was used and SPME conditions were optimised, studying ionic strength effect, temperature effect and adsorption time. Both analytes were determined by calibration established on 2-furfural-d4 (2-F-d4). The method showed good linearity in the range studied (from 16 to 0.12 mg/l), with a regression coefficient r2 of 0.9999. Inter-batch precision and accuracy were found between 14.9 and 6.0% and between -11.7 and 0.2%, respectively. Detection limit was 15 microg/l. The method is simple and accurate and it has been applied to a series of balsamic and non-balsamic vinegars.

  17. Tequila authenticity assessment by headspace SPME-HRGC-IRMS analysis of 13C/12C and 18O/16O ratios of ethanol.

    Science.gov (United States)

    Aguilar-Cisneros, Blanca O; López, Mercedes G; Richling, Elke; Heckel, Frank; Schreier, Peter

    2002-12-18

    By use of headspace SPME sampling and a PLOT column, on-line capillary gas chromatography-isotope ratio mass spectrometry was employed in the combustion (C) and the pyrolysis (P) modes (HRGC-C/P-IRMS) to determine the delta(13)C(VPDB) and delta(18)O(VSMOW) values of ethanol in authentic (n = 14) and commercial tequila samples (n = 15) as well as a number of other spirits (n = 23). Whereas with delta(13)C(VPDB) values ranging from -12.1 to -13.2 per thousand and from -12.5 to -14.8 per thousand similar variations were found for 100% agave and mixed tequilas, respectively, the delta(18)O(VSMOW) data differed slightly within these categories: ranges from +22.1 to +22.8 per thousand and +20.8 to +21.7 per thousand were determined for both the authentic 100% agave and mixed products, respectively. The data recorded for commercial tequilas were less homogeneous; delta(13)C(VPDB) data from -10.6 to -13.9 per thousand and delta(18)O(VSMOW) values from +15.5 to +22.7 per thousand were determined in tequilas of both categories. Owing to overlapping data, attempts to differentiate between white, rested, and aged tequilas within each of the two categories failed. In addition, discrimination of tequila samples from other spirits by means of delta(13)C(VPDB) and delta(18)O(VSMOW) data of ethanol was restricted to the products originating from C(3) as well as C(4)/CAM raw materials.

  18. Herbs and spices: characterization and quantitation of biologically-active markers for routine quality control by multiple headspace solid-phase microextraction combined with separative or non-separative analysis.

    Science.gov (United States)

    Sgorbini, Barbara; Bicchi, Carlo; Cagliero, Cecilia; Cordero, Chiara; Liberto, Erica; Rubiolo, Patrizia

    2015-01-09

    Herbs and spices are used worldwide as food flavoring, thus determination of their identity, origin, and quality is mandatory for safe human consumption. An analysis strategy based on separative (HS-SPME-GC-MS) and non-separative (HS-SPME-MS) approaches is proposed for the volatile fraction of herbs and spices, for quality control and to quantify the aromatic markers with a single analysis directly on the plant material as such. Eight-to-ten lots of each of the following herbs/spices were considered: cloves (Syzygium aromaticum (L.) Merr. & Perry), American peppertree (Schinus molle L.), black pepper and white pepper (Piper nigrum L.), rosemary (Rosmarinus officinalis L.), sage (Salvia officinalis L.) and thyme (Thymus vulgaris L.). Homogeneity, origin, and chemotypes of the investigated lots of each herb/spice were defined by fingerprinting, through statistical elaboration with principal component analysis (PCA). Characterizing aromatic markers were directly quantified on the solid matrix through multiple headspace extraction-HS-SPME (MHS-SPME). Reliable results were obtained with both separative and non-separative methods (where the latter were applicable); the two were in full agreement, RSD% ranging from 1.8 to 7.7% for eugenol in cloves, 2.2-18.4% for carvacrol+thymol in thyme, and 3.1-16.8% for thujones in sage. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Analysis of carbonyl compounds via headspace solid-phase microextraction with on-fiber derivatization and gas chromatographic-ion trap tandem mass spectrometric determination of their O-(2,3,4,5,6-pentafluorobenzyl)oxime derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Schmarr, Hans-Georg [Dienstleistungszentrum Laendlicher Raum (DLR) Rheinpfalz, Breitenweg 71, D-67435 Neustadt an der Weinstrasse (Germany)], E-mail: hans-georg.schmarr@dlr.rlp.de; Potouridis, Theodoros; Ganss, Sebastian; Sang, Wei; Koepp, Benedikt; Bokuz, Ursula; Fischer, Ulrich [Dienstleistungszentrum Laendlicher Raum (DLR) Rheinpfalz, Breitenweg 71, D-67435 Neustadt an der Weinstrasse (Germany)

    2008-06-09

    An improved method for the analysis of carbonyls is described utilizing a headspace solid-phase microextraction (HS-SPME) step and on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) hydrochloride. Thermal desorption of the oxime derivatives formed on the fiber is followed by gas chromatographic separation coupled to an ion trap tandem mass spectrometer (GC-ITMS). Selecting specific fragment ions within the electron ionization (EI{sup +}) mass spectra of these oxime derivatives as precursor ions for MS-MS fragmentation provides a suitable method for the target analysis of individual carbonyl classes, such as alkanals, (E)-2-alkenals, (E,E)-2,4-alkadienals, and others. Retention indices on polar as well as on apolar stationary phases along with EI{sup +} mass spectra patterns are presented for a large set of oxime derivatives, giving valuable information needed for unambiguous assignment of substances in complex sample matrices. The fast sample preparation and derivatization step via HS-SPME can be automated and is applicable to a variety of biological samples and foodstuffs, allowing rapid and sensitive screening analyses of important aldehydic biomarkers and aroma active compounds.

  20. Vanguard/rearguard strategy for the evaluation of the degradation of yoghurt samples based on the direct analysis of the volatiles profile through headspace-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Carrillo-Carrión, C; Cárdenas, S; Valcárcel, M

    2007-02-02

    A vanguard/rearguard analytical strategy for the monitoring of the degradation of yoghurt samples is proposed. The method is based on the headspace-gas chromatography-mass spectrometry (HS-GC-MS) instrumental coupling. In this combination, the chromatographic column is firstly used as an interface between the HS and the MS (vanguard mode) avoiding separation of the volatile components by maintaining the chromatographic oven at high, constant temperature. By changing the thermal conditions of the oven, the aldehydes can be properly separated for individual identification/quantification (rearguard mode). In the vanguard method, the quantification of the volatile aldehydes was calculated through partial least square and given as a total index. The rearguard method permits the detection of the aldehydes at concentrations between 12 and 35 ng/g. Both methods were applied to the study of the environmental factors favouring the presence of the volatile aldehydes (C(5)-C(9)) in the yoghurt samples. Principal component analysis of the total concentration of aldehydes with the time (from 0 to 30 days) demonstrates the capability of the HS-MS coupling for the estimation of the quality losses of the samples. The results were corroborated by the HS-GC-MS which also indicates that pentanal was present in the yoghurt from the beginning of the study and the combination of light/oxygen was the most negative influence for sample conservation.

  1. Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography.

    Science.gov (United States)

    Zhang, Cheng; Cagliero, Cecilia; Pierson, Stephen A; Anderson, Jared L

    2017-01-20

    A simple and rapid ionic liquid (IL)-based in situ dispersive liquid-liquid microextraction (DLLME) method was developed and coupled to headspace gas chromatography (HS-GC) employing electron capture (ECD) and mass spectrometry (MS) detection for the analysis of polychlorinated biphenyls (PCBs) and acrylamide at trace levels from milk and coffee samples. The chemical structures of the halide-based ILs were tailored by introducing various functional groups to the cations to evaluate the effect of different structural features on the extraction efficiency of the target analytes. Extraction parameters including the molar ratio of IL to metathesis reagent and IL mass were optimized. The effects of HS oven temperature and the HS sample vial volume on the analyte response were also evaluated. The optimized in situ DLLME method exhibited good analytical precision, good linearity, and provided detection limits down to the low ppt level for PCBs and the low ppb level for acrylamide in aqueous samples. The matrix-compatibility of the developed method was also established by quantifying acrylamide in brewed coffee samples. This method is much simpler and faster compared to previously reported GC-MS methods using solid-phase microextraction (SPME) for the extraction/preconcentration of PCBs and acrylamide from complex food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-02-08

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

  3. Tank 24-C-103 headspace flammability

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1994-05-01

    Information regarding flammable vapors, gases, and aerosols is presented and interpreted to help resolve the tank 241-C-103 headspace flammability issue. Analyses of recent vapor and liquid samples, as well as visual inspections of the tank headspace, are discussed in the context of tank dynamics. Concern that the headspace of tank 241-C-103 may contain a flammable mixture of organic vapors and an aerosol of combustible organic liquid droplets arises from the presence of a layer of organic liquid in the tank. This organic liquid is believed to have originated in the plutonium-uranium extraction (PUREX) process, having been stored initially in tank 241-C-102 and apparently transferred to tank 241-C-103 in 1975 (Carothers 1988). Analyses of samples of the organic liquid collected in 1991 and 1993 indicate that the primary constituents are tributyl phosphate (TBP) and several semivolatile hydrocarbons (Prentice 1991, Pool and Bean 1994). This is consistent with the premise that the organic waste came from the PUREX process, because the PUREX process used a solution of TBP in a diluent composed of the n-C 11 H 24 to n-C 15 H 32 normal paraffinic hydrocarbons (NPH)

  4. Selected Ion Flow Tube-MS Analysis of Headspace Vapor from Gastric Content for the Diagnosis of Gastro-Esophageal Cancer

    Czech Academy of Sciences Publication Activity Database

    Kumar, S.; Huang, J.; Cushnir, J. R.; Španěl, Patrik; Smith, D.

    2012-01-01

    Roč. 84, č. 21 (2012), s. 9550-9557 ISSN 0003-2700 Institutional support: RVO:61388955 Keywords : SOLID-PHASE MICROEXTRACTION * TRACE GAS-ANALYSIS * CHROMATOGRAPHY-MASS SPECTROMETRY Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.695, year: 2012

  5. Integrated sampling and analysis unit for the determination of sexual pheromones in environmental air using fabric phase sorptive extraction and headspace-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Alcudia-León, M Carmen; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel; Kabir, Abuzar; Furton, Kenneth G

    2017-03-10

    This article presents a novel unit that integrates for the first time air sampling and preconcentration based on the use of fabric phase sorptive extraction principles. The determination of Tuta absoluta sexual pheromone traces in environmental air has been selected as analytical problem. For this aim, a novel laboratory-built unit made up of commercial brass elements as holder of the sol-gel coated fabric extracting phase has been designed and optimized. The performance of the integrated unit was evaluated analyzing environmental air sampled in tomato crops. The unit can work under sampling and analysis mode which eliminates any need for sorptive phase manipulation prior to instrumental analysis. In the sampling mode, the unit can be connected to a sampling pump to pass the air through the sorptive phase at a controlled flow-rate. In the analysis mode, it is placed in the gas chromatograph autosampler without any instrumental modification. It also diminishes the risk of cross contamination between sampling and analysis. The performance of the new unit has been evaluated using the main components of the sexual pheromone of Tuta absoluta [(3E,8Z,11Z)-tetradecatrien-1-yl acetate and (3E,8Z)-tetradecadien-1-yl acetate] as model analytes. The limits of detection for both compounds resulted to be 1.6μg and 0.8μg, respectively, while the precision (expressed as relative standard deviation) was better than 3.7%. Finally, the unit has been deployed in the field to analyze a number of real life samples, some of them were found positive. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Optimization of headspace solid-phase microextraction for analysis of {beta}-caryophyllene in a nanoemulsion dosage form prepared with copaiba (Copaifera multijuga Hayne) oil

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Daiane de O; Colombo, Mariana; Kelmann, Regina G. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Av. Ipiranga, 2752, CEP 90610-000 (Brazil); De Souza, Tatiane P. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Universidade Federal do Amazonas, Manaus, Amazonas (Brazil); Bassani, Valquiria L.; Teixeira, Helder F. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Av. Ipiranga, 2752, CEP 90610-000 (Brazil); Veiga, Valdir F. [Departamento de Quimica, Instituto de Ciencias Exatas, UFAM, Av. Gal. Rodrigo Octavio, 6.200 - Japiim, 69.079-000, Manaus - AM (Brazil); Limberger, Renata P. [Programa de Pos-Graduacao em Ciencias Farmaceuticas, Faculdade de Farmacia, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Av. Ipiranga, 2752, CEP 90610-000 (Brazil); and others

    2012-04-06

    Highlights: Black-Right-Pointing-Pointer A SPME-CG method is proposed for {beta}-caryophyllene assay in nanoemulsions containing copaiba oil. Black-Right-Pointing-Pointer SPME parameters were optimized for efficient {beta}-caryophyllene extraction. Black-Right-Pointing-Pointer The stability-indicating capability and specificity of the method were satisfied. Black-Right-Pointing-Pointer Nanoemulsions partially protected {beta}-caryophyllene under stressing conditions. Black-Right-Pointing-Pointer The proposed method presents linearity, lows LOD and LOQ, good precision, accuracy and robustness. - Abstract: Recent studies have shown the anti-inflammatory activity of Copaiba oils may be addressed to the high content of {beta}-caryophyllene, the most common sesquiterpene detected, especially in the Copaifera multijuga Hayne species. In the present study, nanoemulsions were proposed as a delivery system for copaiba oil in view to treat locally inflamed skin. This article describes the optimization and validation of a stability-indicating SPME-GC method, for {beta}-caryophyllene analysis in the nanoemulsions produced by high pressure homogenization. SPME methods are performed with PDMS (polydimethylsiloxane) fiber (100 {mu}m). Three SPME parameters were evaluated by a three-level-three-factor Box-Behnken factorial design as potentially affecting the technique efficiency. According to the results obtained, the best conditions to extract {beta}-caryophyllene were: (i) sampling temperature of 45 Degree-Sign C, (ii) sampling time of 20 min and (iii) no NaCl addition. Results coming from the forced degradation tests showed a reduction of {beta}-caryophyllene peak area when both caryophyllene methanolic solution and nanoemulsions were exposed to acid hydrolysis, UV-A irradiation, oxidative (H{sub 2}O{sub 2}) and thermolitic (60 Degree-Sign C) conditions. Such reduction occurred in lower extent in the nanoemulsions, suggesting a protective effect of the formulation to {beta

  7. Optimization of headspace solid-phase microextraction for analysis of β-caryophyllene in a nanoemulsion dosage form prepared with copaiba (Copaifera multijuga Hayne) oil

    International Nuclear Information System (INIS)

    Dias, Daiane de O; Colombo, Mariana; Kelmann, Regina G.; De Souza, Tatiane P.; Bassani, Valquiria L.; Teixeira, Helder F.; Veiga, Valdir F.; Limberger, Renata P.

    2012-01-01

    Highlights: ► A SPME-CG method is proposed for β-caryophyllene assay in nanoemulsions containing copaiba oil. ► SPME parameters were optimized for efficient β-caryophyllene extraction. ► The stability-indicating capability and specificity of the method were satisfied. ► Nanoemulsions partially protected β-caryophyllene under stressing conditions. ► The proposed method presents linearity, lows LOD and LOQ, good precision, accuracy and robustness. - Abstract: Recent studies have shown the anti-inflammatory activity of Copaiba oils may be addressed to the high content of β-caryophyllene, the most common sesquiterpene detected, especially in the Copaifera multijuga Hayne species. In the present study, nanoemulsions were proposed as a delivery system for copaiba oil in view to treat locally inflamed skin. This article describes the optimization and validation of a stability-indicating SPME-GC method, for β-caryophyllene analysis in the nanoemulsions produced by high pressure homogenization. SPME methods are performed with PDMS (polydimethylsiloxane) fiber (100 μm). Three SPME parameters were evaluated by a three-level-three-factor Box–Behnken factorial design as potentially affecting the technique efficiency. According to the results obtained, the best conditions to extract β-caryophyllene were: (i) sampling temperature of 45 °C, (ii) sampling time of 20 min and (iii) no NaCl addition. Results coming from the forced degradation tests showed a reduction of β-caryophyllene peak area when both caryophyllene methanolic solution and nanoemulsions were exposed to acid hydrolysis, UV-A irradiation, oxidative (H 2 O 2 ) and thermolitic (60 °C) conditions. Such reduction occurred in lower extent in the nanoemulsions, suggesting a protective effect of the formulation to β-caryophyllene content. Since no degradation products were detected in the same retention time of β-caryophyllene, the specificity of the method was demonstrated. The method was linear in

  8. GNS Castor V/21 Headspace Gas Sampling 2014

    Energy Technology Data Exchange (ETDEWEB)

    Winston, Philip Lon [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-01-01

    Prior to performing an internal visual inspection, samples of the headspace gas of the GNS Castor V/21 cask were taken on June 12, 2014. These samples were taken in support of the CREIPI/Japanese nuclear industry effort to validate fuel integrity without visual inspection by measuring the 85Kr content of the cask headspace

  9. Headspace profiling of cocaine samples for intelligence purposes.

    Science.gov (United States)

    Dujourdy, Laurence; Besacier, Fabrice

    2008-08-06

    A method for determination of residual solvents in illicit hydrochloride cocaine samples using static headspace-gas chromatography (HS-GC) associated with a storage computerized procedure is described for the profiling and comparison of seizures. The system involves a gas chromatographic separation of 18 occluded solvents followed by fully automatic data analysis and transfer to a PHP/MySQL database. First, a fractional factorial design was used to evaluate the main effects of some critical method parameters (salt choice, vial agitation intensity, oven temperature, pressurization and loop equilibration) on the results with a minimum of experiments. The method was then validated for tactical intelligence purposes (batch comparison) via several studies: selection of solvents and mathematical comparison tool, reproducibility and "cutting" influence studies. The decision threshold to determine the similarity of two samples was set and false positives and negatives evaluated. Finally, application of the method to distinguish geographical origins is discussed.

  10. Analysis of acrylonitrile, 1,3-butadiene, and related compounds in acrylonitrile-butadiene-styrene copolymers for kitchen utensils and children's toys by headspace gas chromatography/mass spectrometry.

    Science.gov (United States)

    Ohno, Hiroyuki; Kawamura, Yoko

    2010-01-01

    A headspace gas chromatography/mass spectrometry method was developed for the simultaneous determination of the residual levels of acrylonitrile (AN), 1,3-butadiene (1,3-BD), and their related compounds containing propionitrile (PN) and 4-vinyl-1-cyclohexene (4-VC) in acrylonitrile-butadiene-styrene (ABS) copolymers for kitchen utensils and children's toys. A sample was cut into small pieces, then N,N-dimethylacetamide and an internal standard were added in a sealed headspace vial. The vial was incubated for 1 h at 90 degrees C and the headspace gas was analyzed by gas chromatography/mass spectrometry. The recovery rates of the analytes were 93.3-101.8% and the coefficients of variation were 0.3-6.5%. In ABS copolymers, the levels were 0.3-50.4 microg/g for AN, ND-4.5 microg/g for PN, 0.06-1.58 microg/g for 1,3-BD, and 1.1-295 microg/g for 4-VC. The highest level was found for 4-VC, which is a dimer of 1,3-BD, and the next highest was for AN, which is one of the monomers of the ABS copolymer. Furthermore, the method was also applied to acrylonitrile-styrene (AS) copolymers and polystyrenes (PS) for kitchen utensils, and nitrile-butadiene rubber (NBR) gloves. In AS copolymers, AN and PN were detected at 16.8-54.5 and 0.8-6.9 microg/g, respectively. On the other hand, the levels in PS and NBR samples were all low.

  11. Analysis of Odorants in Marking Fluid of Siberian Tiger (Panthera tigris altaica) Using Simultaneous Sensory and Chemical Analysis with Headspace Solid-Phase Microextraction and Multidimensional Gas Chromatography-Mass Spectrometry-Olfactometry.

    Science.gov (United States)

    Soso, Simone B; Koziel, Jacek A

    2016-06-25

    Scent-marking is the most effective method of communication in the presence or absence of a signaler. These complex mixtures result in a multifaceted interaction triggered by the sense of smell. The objective was to identify volatile organic compound (VOC) composition and odors emitted by total marking fluid (MF) associated with Siberian tigers (Panthera tigris altaica). Siberian tiger, an endangered species, was chosen because its MF had never been analyzed. Solid phase microextraction (SPME) for headspace volatile collection combined with multidimensional gas chromatography-mass spectrometry-olfactometry for simultaneous chemical and sensory analyses were used. Thirty-two VOCs emitted from MF were identified. 2-acetyl-1-pyrroline, the sole previously identified compound responsible for the "characteristic" odor of P. tigris MF, was identified along with two additional compounds confirmed with standards (urea, furfural) and four tentatively identified compounds (3-methylbutanamine, (R)-3-methylcyclopentanone, propanedioic acid, and 3-hydroxybutanal) as being responsible for the characteristic aroma of Siberian tiger MF. Simultaneous chemical and sensory analyses improved characterization of scent-markings and identified compounds not previously reported in MF of other tiger species. This research will assist animal ecologists, behaviorists, and zookeepers in understanding how scents from specific MF compounds impact tiger and wildlife communication and improve management practices related to animal behavior. Simultaneous chemical and sensory analyses is applicable to unlocking scent-marking information for other species.

  12. Analysis of Odorants in Marking Fluid of Siberian Tiger (Panthera tigris altaica Using Simultaneous Sensory and Chemical Analysis with Headspace Solid-Phase Microextraction and Multidimensional Gas Chromatography-Mass Spectrometry-Olfactometry

    Directory of Open Access Journals (Sweden)

    Simone B. Soso

    2016-06-01

    Full Text Available Scent-marking is the most effective method of communication in the presence or absence of a signaler. These complex mixtures result in a multifaceted interaction triggered by the sense of smell. The objective was to identify volatile organic compound (VOC composition and odors emitted by total marking fluid (MF associated with Siberian tigers (Panthera tigris altaica. Siberian tiger, an endangered species, was chosen because its MF had never been analyzed. Solid phase microextraction (SPME for headspace volatile collection combined with multidimensional gas chromatography-mass spectrometry-olfactometry for simultaneous chemical and sensory analyses were used. Thirty-two VOCs emitted from MF were identified. 2-acetyl-1-pyrroline, the sole previously identified compound responsible for the “characteristic” odor of P. tigris MF, was identified along with two additional compounds confirmed with standards (urea, furfural and four tentatively identified compounds (3-methylbutanamine, (R-3-methylcyclopentanone, propanedioic acid, and 3-hydroxybutanal as being responsible for the characteristic aroma of Siberian tiger MF. Simultaneous chemical and sensory analyses improved characterization of scent-markings and identified compounds not previously reported in MF of other tiger species. This research will assist animal ecologists, behaviorists, and zookeepers in understanding how scents from specific MF compounds impact tiger and wildlife communication and improve management practices related to animal behavior. Simultaneous chemical and sensory analyses is applicable to unlocking scent-marking information for other species.

  13. Determination of 3-chloro-1,2-propanediol in polyamideamine epichlorohydrin resin solution by reaction-based headspace gas chromatography.

    Science.gov (United States)

    Yan, Ning; Wan, Xiao-Fang; Chai, Xin-Sheng; Chen, Run-Quan

    2018-04-01

    We report on a headspace gas chromatographic method for determining the content of 3-chloro-1,2-propanediol in polyamideamine epichlorohydrin resin solution. It was based on quantitatively converting 3-chloro-1,2-propanediol to formaldehyde by periodate oxidation in a closed headspace sample vial at a room temperature for 10 min, and then to methanol by borohydride reduction at 90°C for 40 min followed by the headspace gas chromatographic measurement. The results showed that the present method has an excellent measurement precision (relative standard deviation < 2.60%) and accuracy (recoveries from 96.4-102%) in 3-chloro-1,2-propanediol analysis. The limit of quantitation was 0.031 mg/mL. It is simple and suitable for determining the 3-chloro-1,2-propanediol content in polyamideamine epichlorohydrin resin solution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Tank vapor characterization project - Tank 241-U-112 headspace gas and vapor characterization: Results for homogeneity samples collected on December 6, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Sklarew, D.S.; Pool, K.H.; Evans, J.C.; Hayes, J.C. [and others

    1997-09-01

    This report presents the results of analyses of samples taken from the headspace of waste storage tank 241-U-112 (Tank U-112) at the Hanford Site in Washington State. Samples were collected to determine the homogeneity of selected inorganic and organic headspace constitutents. Two risers (Riser 3 and Riser 6) were sampled at three different elevations (Bottom, Middle, and Top) within the tank. Tank headspace samples were collected by SGN Eurisys Service Corporation (SESC) and were analyzed by Pacific Northwest National Laboratory (PNNL) to determine headspace concentrations of selected non-radioactive analytes. Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Ammonia was determined to be above the immediate notification limit specified by the sampling and analysis plan.

  15. Headspace vapor characterization of Hanford waste tank 241-U-108: Results from samples collected on 8/29/95

    International Nuclear Information System (INIS)

    Thomas, B.L.; Clauss, T.W.; Evans, J.C.; McVeety, B.D.; Pool, K.H.; Olsten, K.B.; Fruchter, J.S.; Ligotke, M.W.

    1996-05-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-U-108 (Tank U-108) at the Hanford Site in Washington State. The results described in the report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC

  16. Test plan for headspace gas concentration measurement and headspace ventilation rate measurement for DCRTs 241-A-244, 241-BX-244, 241-S-244, 241-TX-244

    International Nuclear Information System (INIS)

    Bauer, R.E.

    1998-01-01

    This test plan provides the directions to characterize the headspace gas concentrations and the headspace ventilation rate for double contained receiver tanks 241-A-244, 241-BX-244, 241-S-244, and 241-TX-244

  17. Determination of sulfur dioxide in wine using headspace gas chromatography and electron capture detection.

    Science.gov (United States)

    Aberl, A; Coelhan, M

    2013-01-01

    Sulfites are routinely added as preservatives and antioxidants in wine production. By law, the total sulfur dioxide content in wine is restricted and therefore must be monitored. Currently, the method of choice for determining the total content of sulfur dioxide in wine is the optimised Monier-Williams method, which is time consuming and laborious. The headspace gas chromatographic method described in this study offers a fast and reliable alternative method for the detection and quantification of the sulfur dioxide content in wine. The analysis was performed using an automatic headspace injection sampler, coupled with a gas chromatograph and an electron capture detector. The method is based on the formation of gaseous sulfur dioxide subsequent to acidification and heating of the sample. In addition to free sulfur dioxide, reversibly bound sulfur dioxide in carbonyl compounds, such as acetaldehyde, was also measured with this method. A total of 20 wine samples produced using diverse grape varieties and vintages of varied provenance were analysed using the new method. For reference and comparison purposes, 10 of the results obtained by the proposed method were compared with those acquired by the optimised Monier-Williams method. Overall, the results from the headspace analysis showed good correlation (R = 0.9985) when compared with the conventional method. This new method requires minimal sample preparation and is simple to perform, and the analysis can also be completed within a short period of time.

  18. Headspace gas and vapor characterization summary for the 43 vapor program suspect tanks

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    During the time period between February 1994 and September 1995, Westinghouse Hanford Company (WHC) sampled the waste tank headspace of 43 single-shell tanks for a variety of gaseous and/or volatile and semi-volatile compounds. This report summarizes the results of analyses of those sampling activities with respect to both the Priority 1 Safety Issues and relative to the detection in the headspace of significant concentrations of target analytes relating to worker breathing space consideration as recommended by the Pacific Northwest Laboratory (PNL) Toxicology Review Panel. The information contained in the data tables was abstracted from the vapor sampling and analysis tank characterization reports. Selected results are tabulated and summarized. Sampling equipment and methods, as well as sample analyses, are briefly described. Vapor sampling of passively ventilated single-shell tanks (tanks C-105, C-106, and SX-106 were sampled and are actively ventilated) has served to highlight or confirm tank headspace conditions associated with both priority 1 safety issues and supports source term analysis associated with protecting worker health and safety from noxious vapors

  19. [Determination of olive oil content in olive blend oil by headspace gas chromatography-mass spectrometry].

    Science.gov (United States)

    Jiang, Wanfeng; Zhang, Ning; Zhang, Fengyan; Yang, Zhao

    2017-07-08

    A method for the determination of the content of olive oil in olive blend oil by headspace gas chromatography-mass spectrometry (SH-GC/MS) was established. The amount of the sample, the heating temperature, the heating time, the amount of injection, the injection mode and the chromatographic column were optimized. The characteristic compounds of olive oil were found by chemometric method. A sample of 1.0 g was placed in a 20 mL headspace flask, and heated at 180℃ for 2700 s. Then, 1.0 mL headspace gas was taken into the instrument. An HP-88 chromatographic column was used for the separation and the analysis was performed by GC/MS. The results showed that the linear range was 0-100%(olive oil content). The linear correlation coefficient ( r 2 ) was more than 0.995, and the limits of detection were 1.26%-2.13%. The deviations of olive oil contents in the olive blend oil were from -0.65% to 1.02%, with the relative deviations from -1.3% to 6.8% and the relative standard deviations from 1.18% to 4.26% ( n =6). The method is simple, rapid, environment friendly, sensitive and accurate. It is suitable for the determination of the content of olive oil in olive blend oil.

  20. Tank 241-U-104 headspace gas and vapor characterization results from samples collected on July 16, 1996

    International Nuclear Information System (INIS)

    Pool, K.H.; Evans, J.C.; Hayes, J.C.; Mitroshkov, A.V.; Edwards, J.A.; Julya, J.L.; Thornton, B.M.; Fruchter, J.S.; Silvers, K.L.

    1997-08-01

    This report presents the results from analyses of samples taken from the headspace of waste storage tank 241-U-104 (Tank U-104) at the Hanford Site in Washington State. Tank headspace samples collected by Westinghouse Hanford Company (WHC) were analyzed by Pacific Northwest National Laboratory (PNNL) to determine headspace concentrations of selected non-radioactive analytes. Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Vapor concentrations from sorbent trap samples are based on measured sample volumes provided by WHC. No analytes were determined to be above the immediate notification limits specified by the sampling and analysis plan. None of the flammable constituents were present at concentrations above the analytical instrument detection limits. Total headspace flammability was estimated to be <0.108% of the lower flammability limit. Average measured concentrations of targeted gases, inorganic vapors, and selected organic vapors are provided in a table. A summary of experimental methods, including sampling methodology, analytical procedures, and quality assurance and control methods are presented in Section 2.0. Detailed descriptions of the analytical results are provided in Section 3.0

  1. Rapid determination of the volatile components in tobacco by ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Yang, Yanqin; Chu, Guohai; Zhou, Guojun; Jiang, Jian; Yuan, Kailong; Pan, Yuanjiang; Song, Zhiyu; Li, Zuguang; Xia, Qian; Lu, Xinbo; Xiao, Weiqiang

    2016-03-01

    An ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction was first employed to determine the volatile components in tobacco samples. The method combined the advantages of ultrasound, microwave, and headspace solid-phase microextraction. The extraction, separation, and enrichment were performed in a single step, which could greatly simplify the operation and reduce the whole pretreatment time. In the developed method, several experimental parameters, such as fiber type, ultrasound power, and irradiation time, were optimized to improve sampling efficiency. Under the optimal conditions, there were 37, 36, 34, and 36 components identified in tobacco from Guizhou, Hunan, Yunnan, and Zimbabwe, respectively, including esters, heterocycles, alkanes, ketones, terpenoids, acids, phenols, and alcohols. The compound types were roughly the same while the contents were varied from different origins due to the disparity of their growing conditions, such as soil, water, and climate. In addition, the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method was compared with the microwave-assisted extraction coupled to headspace solid-phase microextraction and headspace solid-phase microextraction methods. More types of volatile components were obtained by using the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method, moreover, the contents were high. The results indicated that the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction technique was a simple, time-saving and highly efficient approach, which was especially suitable for analysis of the volatile components in tobacco. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Otimização e validação de métodos analíticos para determinação de BTEX em água utilizando extração por headspace e microextração em fase sólida Evaluation of analytical methods for BTEX analysis in water using extraction by headspace (HS and solid phase microextraction (SPME

    Directory of Open Access Journals (Sweden)

    Fernanda F. Heleno

    2010-01-01

    Full Text Available Three analytical methods for the determination of BTEX in water were optimized and validated. With the best method the analytes were extracted of 10 mL of sample with 2.50 g of NaCl in headspace vial of 20 mL by HS and SPME to 40 ºC for 30 min for adsorption and to 250 ºC for 4 min for desorption and were analyzed by GC-MS. The recovery was between 97.9% and 104.3%, and the limit of detection was 2.4 ng L-1 for o-xylene. This method was using to analyze BTEX in water supply and surface water in Ouro Preto city. No sample had concentrations of BTEX above the legislation.

  3. Headspace vapor characterization of Hanford Waste Tank 241-S-112: Results from samples collected on July 11, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    Clauss, T.W.; Pool, K.H.; Evans, J.C.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage Tank 241-S-112 (Tank S-112) at the Hanford. Pacific Northwest National Laboratory (PNNL) is contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5044. Samples were collected by WHC on July 11, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  4. Headspace vapor characterization of Hanford Waste Tank SX-102: Results from samples collected on July 19, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    McVeety, B.D.; Evans, J.C.; Clauss, T.W.; Pool, K.H.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-SX-102 (Tank SX-102) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed under the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5046. Samples were collected by WHC on July 19, 1995, using the vapor sampling system (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  5. Headspace vapor characterization of Hanford Waste Tank 241-T-110: Results from samples collected on August 31, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    McVeety, B.D.; Thomas, B.L.; Evans, J.C.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-T-110 (Tank T-110) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5056. Samples were collected by WHC on August 31, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  6. Headspace vapor characterization of Hanford Waste Tank 241-TX-111: Results from samples collected on October 12, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    Pool, K.H.; Clauss, T.W.; Evans, J.C.

    1996-06-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-TX-111 (Tank TX-111) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5069. Samples were collected by WHC on October 12, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  7. Headspace vapor characterization of Hanford Waste Tank AX-103: Results from samples collected on June 21, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    Ligotke, M.W.; Pool, K.H.; Clauss, T.W.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-AX-103 (Tank AX-103) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5029. Samples were collected by WHC on June 21, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  8. Headspace vapor characterization of Hanford Waste Tank AX-101: Results from samples collected on June 15, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    Pool, K.H.; Clauss, T.W.; Evans, J.C.; McVeety, B.D.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-AX-101 (Tank AX-101) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) under the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5028. Samples were collected by WHC on June 15, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  9. Headspace vapor characterization of Hanford Waste Tank 241-SX-109: Results from samples collected on August 1, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    Pool, K.H.; Clauss, T.W.; Evans, J.C.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-SX-109 (Tank SX-109) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5048. Samples were collected by WHC on August 1, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  10. Headspace vapor characterization of Hanford Waste Tank 241-SX-104: Results from samples collected on July 25, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    Thomas, B.L.; Clauss, T.W.; Evans, J.C.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-SX-104 (Tank SX-104) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5049. Samples were collected by WHC on July 25, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  11. Headspace vapor characterization of Hanford Waste Tank 241-SX-105: Results from samples collected on July 26, 1995. Tank Vapor Characterization Project

    International Nuclear Information System (INIS)

    Pool, K.H.; Clauss, T.W.; Evans, J.C.

    1996-05-01

    This report describes the results of vapor samples taken from the headspace of waste storage tank 241-SX-105 (Tank SX-105) at the Hanford Site in Washington State. Pacific Northwest National Laboratory (PNNL) contracted with Westinghouse Hanford Company (WHC) to provide sampling devices and analyze samples for inorganic and organic analytes collected from the tank headspace and ambient air near the tank. The analytical work was performed by the PNNL Vapor Analytical Laboratory (VAL) by the Tank Vapor Characterization Project. Work performed was based on a sample and analysis plan (SAP) prepared by WHC. The SAP provided job-specific instructions for samples, analyses, and reporting. The SAP for this sample job was open-quotes Vapor Sampling and Analysis Planclose quotes, and the sample job was designated S5047. Samples were collected by WHC on July 26, 1995, using the Vapor Sampling System (VSS), a truck-based sampling method using a heated probe inserted into the tank headspace

  12. Authentication of pineapple (Ananas comosus [L.] Merr.) fruit maturity stages by quantitative analysis of γ- and δ-lactones using headspace solid-phase microextraction and chirospecific gas chromatography-selected ion monitoring mass spectrometry (HS-SPME-GC-SIM-MS).

    Science.gov (United States)

    Steingass, Christof B; Langen, Johannes; Carle, Reinhold; Schmarr, Hans-Georg

    2015-02-01

    Headspace solid phase microextraction and chirospecific gas chromatography-mass spectrometry in selected ion monitoring mode (HS-SPME-GC-SIM-MS) allowed quantitative determination of δ-lactones (δ-C8, δ-C10) and γ-lactones (γ-C6, γ-C8, γ-C10). A stable isotope dilution assay (SIDA) with d7-γ-decalactone as internal standard was used for quantitative analysis of pineapple lactones that was performed at three progressing post-harvest stages of fully ripe air-freighted and green-ripe sea-freighted fruits, covering the relevant shelf-life of the fruits. Fresh pineapples harvested at full maturity were characterised by γ-C6 of high enantiomeric purity remaining stable during the whole post-harvest period. In contrast, the enantiomeric purity of γ-C6 significantly decreased during post-harvest storage of sea-freighted pineapples. The biogenetical background and the potential of chirospecific analysis of lactones for authentication and quality evaluation of fresh pineapple fruits are discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Headspace vapor characterization of Hanford waste tank 241-B-107: Results from samples collected on 7/23/96

    International Nuclear Information System (INIS)

    Evans, J.C.; Pool, K.H.; Thomas, B.L.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-B-107 (Tank B-107) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwestern National Laboratory (PNNL). A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in a table. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples are also listed in the same table. Detailed descriptions of the analytical results appear in the appendices

  15. Headspace vapor characterization of Hanford waste tank 241-S-106: Results from samples collected on 06/13/96

    International Nuclear Information System (INIS)

    Evans, J.C.; Pool, K.H.; Thomas, B.L.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-S-106 (Tank S-106) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in a table. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples are also listed in the same table. Detailed descriptions of the analytical results appear in the appendices

  16. Headspace vapor characterization of Hanford waste Tank 241-C-201: Results from samples collected on 06/19/96

    International Nuclear Information System (INIS)

    Thomas, B.L.; Evans, J.C.; Pool, K.H.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-C-201 (Tank C-201) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, on sample volumes provided by WHC. A summary, of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in a table. Detailed descriptions of the analytical results appear in the appendices

  17. Characterization and classification of pequi trees (Caryocar brasiliense Camb. based on the profile of volatile constituents using headspace solid-phase microextraction - gas chromatography - mass spectrometry and multivariate analysis Caracterização e classificação de pequizeiros (Caryocar brasiliense Camb. baseadas no perfil de constituintes voláteis usando microextração em fase sólida no modo headspace - cromatografia a gás - espectrometria de massas e análise multivariada

    Directory of Open Access Journals (Sweden)

    Renata França Cassimiro Belo

    2013-02-01

    Full Text Available In order to determine the variability of pequi tree (Caryocar brasiliense Camb. populations, volatile compounds from fruits of eighteen trees representing five populations were extracted by headspace solid-phase microextraction and analyzed by gas chromatography-mass spectrometry. Seventy-seven compounds were identified, including esters, hydrocarbons, terpenoids, ketones, lactones, and alcohols. Several compounds had not been previously reported in the pequi fruit. The amount of total volatile compounds and the individual compound contents varied between plants. The volatile profile enabled the differentiation of all of the eighteen plants, indicating that there is a characteristic profile in terms of their origin. The use of Principal Component Analysis and Cluster Analysis enabled the establishment of markers (dendrolasin, ethyl octanoate, ethyl 2-octenoate and β-cis-ocimene that discriminated among the pequi trees. According to the Cluster Analysis, the plants were classified into three main clusters, and four other plants showed a tendency to isolation. The results from multivariate analysis did not always group plants from the same population together, indicating that there is greater variability within the populations than between pequi tree populations.A fim de determinar a variabilidade de populações de pequizeiro (Caryocar brasiliense Camb., compostos voláteis de frutos de dezoito árvores representando cinco populações foram extraídos por microextração em fase sólida no modo headspace e analisados por cromatografia a gás acoplada à espectrometria de massas. Setenta e sete compostos foram identificados, incluindo ésteres, hidrocarbonetos, terpenoides, cetonas, lactonas e álcoois. Vários compostos não haviam sido encontrados anteriormente no fruto. A quantidade total e a composição de voláteis variaram entre as plantas. O perfil volátil permitiu a diferenciação de todas as dezoito plantas, indicando que há um

  18. Quantification of liquid products from the electroreduction of CO2 and CO using static headspace-gas chromatography and nuclear magnetic resonance spectroscopy

    DEFF Research Database (Denmark)

    Bertheussen, Erlend; Abghoui, Younes; Jovanov, Zarko P.

    2017-01-01

    Static headspace-gas chromatography (HS-GC) useful for ex-situ liquid product analysis. Could complement high-performance liquid chromatography and NMR spectroscopy. Particularly high sensitivity towards compounds with high vapor pressure. Detection limits below 0.5μM were shown for acetaldehyde...

  19. Evaluation of peroxidative stress of cancer cells in vitro by real-time quantification of volatile aldehydes in culture headspace.

    Science.gov (United States)

    Shestivska, Violetta; Rutter, Abigail V; Sulé-Suso, Josep; Smith, David; Španěl, Patrik

    2017-08-30

    Peroxidation of lipids in cellular membranes results in the release of volatile organic compounds (VOCs), including saturated aldehydes. The real-time quantification of trace VOCs produced by cancer cells during peroxidative stress presents a new challenge to non-invasive clinical diagnostics, which as described here, we have met with some success. A combination of selected ion flow tube mass spectrometry (SIFT-MS), a technique that allows rapid, reliable quantification of VOCs in humid air and liquid headspace, and electrochemistry to generate reactive oxygen species (ROS) in vitro has been used. Thus, VOCs present in the headspace of CALU-1 cancer cell line cultures exposed to ROS have been monitored and quantified in real time using SIFT-MS. The CALU-1 lung cancer cells were cultured in 3D collagen to mimic in vivo tissue. Real-time SIFT-MS analyses focused on the volatile aldehydes: propanal, butanal, pentanal, hexanal, heptanal and malondialdehyde (propanedial), that are expected to be products of cellular membrane peroxidation. All six aldehydes were identified in the culture headspace, each reaching peak concentrations during the time of exposure to ROS and eventually reducing as the reactants were depleted in the culture. Pentanal and hexanal were the most abundant, reaching concentrations of a few hundred parts-per-billion by volume, ppbv, in the culture headspace. The results of these experiments demonstrate that peroxidation of cancer cells in vitro can be monitored and evaluated by direct real-time analysis of the volatile aldehydes produced. The combination of adopted methodology potentially has value for the study of other types of VOCs that may be produced by cellular damage. Copyright © 2017 John Wiley & Sons, Ltd.

  20. Rapid determination of methanol in black liquors by full evaporation headspace gas chromatography.

    Science.gov (United States)

    Li, Hailong; Zhan, Huaiyu; Fu, Shiyu; Liu, Mengru; Chai, Xin-Sheng

    2007-12-14

    This paper reported a full evaporation headspace gas chromatographic (GC) technique for determination of methanol content in black liquors (pulping spent liquor). In this method, a very small volume (10-20 microL) of liquor sample is introduced into a headspace sample vial (20 mL) and heated up to a temperature of 105 degrees C. A near-complete mass transfer of methanol from the liquid phase to vapor phase (headspace), i.e., a full evaporation, can be achieved within 3 min. The methanol in the headspace of the vial is then measured by GC. The present method is simple, rapid and accurate.

  1. Headspace screening: A novel approach for fast quality assessment of the essential oil from culinary sage.

    Science.gov (United States)

    Cvetkovikj, Ivana; Stefkov, Gjoshe; Acevska, Jelena; Karapandzova, Marija; Dimitrovska, Aneta; Kulevanova, Svetlana

    2016-07-01

    Quality assessment of essential oil (EO) from culinary sage (Salvia officinalis L., Lamiaceae) is limited by the long pharmacopoeial procedure. The aim of this study was to employ headspace (HS) sampling in the quality assessment of sage EO. Different populations (30) of culinary sage were assessed using GC/FID/MS analysis of the hydrodistilled EO (pharmacopoeial method) and HS sampling directly from leaves. Compound profiles from both procedures were evaluated according to ISO 9909 and GDC standards for sage EO quality, revealing compliance for only 10 populations. Factors to convert HS values, for the target ISO and GDC components, into theoretical EO values were calculated. Statistical analysis revealed a significant relationship between HS and EO values for seven target components. Consequently, HS sampling could be used as a complementary extraction technique for rapid screening in quality assessment of sage EOs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Olive Oil Headspace Characterization by a Gas Sensor Array

    International Nuclear Information System (INIS)

    Santonico, Marco; Capuano, Rosamaria; Catini, Alexandro; Dini, Francesca; Martinelli, Eugenio; Gianni, Giacomo; Migliorini, Marzia; Paolesse, Roberto; D'Amico, Arnaldo; Di Natale, Corrado

    2011-01-01

    Olive oil quality is strictly correlated to the volatile compounds profile. Both quality and defects can be connected to the presence of specific volatile compounds in the oil headspace. In this paper, olive oil samples have been artificially modified by adding a number of compounds known to be typical of the more frequent defects: fusty, musty, muddy and rancid. Results demonstrate the sensitivity of the electronic nose to the compounds characterizing the defects and then the capability of the instrument to identify the defects in real samples.

  3. Effects of headspace fraction and aqueous alkalinity on subcritical hydrothermal gasification of cellulose

    Energy Technology Data Exchange (ETDEWEB)

    Dolan, Ryan; Yin, Sudong; Tan, Zhongchao [Department of Mechanical and Manufacturing Engineering, Centre for Environmental Engineering Research and Education, Schulich School of Engineering, University of Calgary, 2500 University Dr. N.W. Calgary, AB (Canada)

    2010-07-15

    In order to better understand the pathways of hydrothermal gasification of cellulose, the effect of headspace fraction and alkalinity on the hydrothermal gasification of cellulose has been studied at 315 C in the presence of Pt/Al{sub 2}O{sub 3} as catalyst. It was found that regardless of alkalinity the headspace fraction had a large impact on gasification yield, with larger headspace fractions resulting in considerably more gas product. Without the addition of sodium carbonate, the effect of headspace fraction became more pronounced, with gas increasing by approximately a factor of forty from the lowest to highest headspace fraction. On the other hand, for the same residence time the addition of sodium carbonate co-catalyst dampened the magnitude of the effect, to a factor of 2.5 and 1.5, for 50 and 100 mM sodium carbonate solutions, respectively. These results indicated that the headspace fraction affected the phase behaviour, and that this altered the pathway of the cellulose decomposition. While furfural alcohol was the major product obtained with a 49% headspace fraction, it was effectively suppressed by using 78% or greater headspace fractions. Based on the effects of phase behaviour and previous literature, the reduced effect occurring upon the addition of sodium carbonate may relate to catalysis of the Lobry de-bruyn Van Eckenstein transform to produce lactic acid rather than intermediates proceeding through glycolaldehyde. (author)

  4. Bepaling van tetrachloor- en trichloorethyleen in olijfolie met behulp van headspace - gaschromatografie

    NARCIS (Netherlands)

    Roos, A.H.; Mazijk, van R.J.; Tuinstra, L.G.M.Th.

    1990-01-01

    De resultaten van de EEG headspace methode wijzen uit dat de herhaalbaarheid en nauwkeurigheid voldoende zijn om tetrachloor- en trichloorethyleen in olijfolie te bepalen tot een niveau van 0,01 mg/kg op produkt. De headspace techniek is door de eenvoudige procedure zeer geschikt voor routine

  5. Simplex Optimization of Headspace-Enrichment Conditions of Residual Petroleum Distillates Used by Arsonists

    Science.gov (United States)

    Warnke, Molly M.; Erickson, Angela E.; Smith, Eugene T.

    2005-01-01

    A forensic project is described that is suitable for an undergraduate instrumental methods lab. Accelerants commonly used by arsonists are analyzed by static headspace enrichment followed by gas chromatography. The conditions used for headspace enrichment (e.g., time and temperature) are known to influence the distribution of hydrocarbons…

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-04-03

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

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  8. A simple headspace equilibration method for measuring dissolved methane

    Science.gov (United States)

    Magen, C; Lapham, L.L.; Pohlman, John W.; Marshall, Kristin N.; Bosman, S.; Casso, Michael; Chanton, J.P.

    2014-01-01

    Dissolved methane concentrations in the ocean are close to equilibrium with the atmosphere. Because methane is only sparingly soluble in seawater, measuring it without contamination is challenging for samples collected and processed in the presence of air. Several methods for analyzing dissolved methane are described in the literature, yet none has conducted a thorough assessment of the method yield, contamination issues during collection, transport and storage, and the effect of temperature changes and preservative. Previous extraction methods transfer methane from water to gas by either a "sparge and trap" or a "headspace equilibration" technique. The gas is then analyzed for methane by gas chromatography. Here, we revisit the headspace equilibration technique and describe a simple, inexpensive, and reliable method to measure methane in fresh and seawater, regardless of concentration. Within the range of concentrations typically found in surface seawaters (2-1000 nmol L-1), the yield of the method nears 100% of what is expected from solubility calculation following the addition of known amount of methane. In addition to being sensitive (detection limit of 0.1 ppmv, or 0.74 nmol L-1), this method requires less than 10 min per sample, and does not use highly toxic chemicals. It can be conducted with minimum materials and does not require the use of a gas chromatograph at the collection site. It can therefore be used in various remote working environments and conditions.

  9. Approaches of aroma extraction dilution analysis (AEDA) for headspace solid phase microextraction and gas chromatography-olfactometry (HS-SPME-GC-O): Altering sample amount, diluting the sample or adjusting split ratio?

    Science.gov (United States)

    Feng, Yunzi; Cai, Yu; Sun-Waterhouse, Dongxiao; Cui, Chun; Su, Guowan; Lin, Lianzhu; Zhao, Mouming

    2015-11-15

    Aroma extract dilution analysis (AEDA) is widely used for the screening of aroma-active compounds in gas chromatography-olfactometry (GC-O). In this study, three aroma dilution methods, (I) using different test sample volumes, (II) diluting samples, and (III) adjusting the GC injector split ratio, were compared for the analysis of volatiles by using HS-SPME-AEDA. Results showed that adjusting the GC injector split ratio (III) was the most desirable approach, based on the linearity relationships between Ln (normalised peak area) and Ln (normalised flavour dilution factors). Thereafter this dilution method was applied in the analysis of aroma-active compounds in Japanese soy sauce and 36 key odorants were found in this study. The most intense aroma-active components in Japanese soy sauce were: ethyl 2-methylpropanoate, ethyl 2-methylbutanoate, ethyl 3-methylbutanoate, ethyl 4-methylpentanoate, 3-(methylthio)propanal, 1-octen-3-ol, 2-methoxyphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-vinylphenol, 2-phenylethanol, and 4-hydroxy-5-ethyl-2-methyl-3(2H)-furanone. Copyright © 2015. Published by Elsevier Ltd.

  10. Systematic comparison of static and dynamic headspace sampling techniques for gas chromatography.

    Science.gov (United States)

    Kremser, Andreas; Jochmann, Maik A; Schmidt, Torsten C

    2016-09-01

    Six automated, headspace-based sample preparation techniques were used to extract volatile analytes from water with the goal of establishing a systematic comparison between commonly available instrumental alternatives. To that end, these six techniques were used in conjunction with the same gas chromatography instrument for analysis of a common set of volatile organic carbon (VOC) analytes. The methods were thereby divided into three classes: static sampling (by syringe or loop), static enrichment (SPME and PAL SPME Arrow), and dynamic enrichment (ITEX and trap sampling). For PAL SPME Arrow, different sorption phase materials were also included in the evaluation. To enable an effective comparison, method detection limits (MDLs), relative standard deviations (RSDs), and extraction yields were determined and are discussed for all techniques. While static sampling techniques exhibited sufficient extraction yields (approx. 10-20 %) to be reliably used down to approx. 100 ng L(-1), enrichment techniques displayed extraction yields of up to 80 %, resulting in MDLs down to the picogram per liter range. RSDs for all techniques were below 27 %. The choice on one of the different instrumental modes of operation (aforementioned classes) was thereby the most influential parameter in terms of extraction yields and MDLs. Individual methods inside each class showed smaller deviations, and the least influences were observed when evaluating different sorption phase materials for the individual enrichment techniques. The option of selecting specialized sorption phase materials may, however, be more important when analyzing analytes with different properties such as high polarity or the capability of specific molecular interactions. Graphical Abstract PAL SPME Arrow during the extraction of volatile analytes from the headspace of an aqueous sample.

  11. Determination of microstickies in recycled whitewater by headspace gas chromatography.

    Science.gov (United States)

    Chai, X-S; Samp, J C; Yang, Q F; Song, H N; Zhang, D C; Zhu, J Y

    2006-03-03

    This study proposed a novel headspace gas chromatographic (HS-GC) method for determination of adhesive contaminants (microstickies) in recycled whitewater, a fiber containing process stream, in the paper mill. It is based on the adsorption behavior of toluene (as a tracer) on the hydrophobic surface of microstickies, which affects the apparent vapor-liquid equilibration partitioning of toluene. It was found that the equilibrium concentration of toluene in the vapor phase is inversely proportional to the apparent effective surface area of microstickies that remain in the corresponding solution. Thus, the amount of microsticky materials in the recycled whitewater can be quantified by HS-GC via indirect measurement of the toluene content in the vapor phase of the sample without any pretreatment. The presented method is simple, rapid and automated.

  12. Screening for γ-Nonalactone in the Headspace of Freshly Cooked Non-Scented Rice Using SPME/GC-O and SPME/GC-MS

    Directory of Open Access Journals (Sweden)

    Jie Yu Chen

    2009-08-01

    Full Text Available The determination of γ-nonalactone as one of the important odor-active compounds in freshly cooked non-scented rice is reported. It was evaluated by gas chromatography-olfactometry (GC-O analysis and identified by gas chromatography-mass spectrometry (GC-MS analysis in the headspace above the freshly cooked non-scented rice samples extracted by using a modified headspace solid-phase microextraction (SPME method. This component had a mass spectrum with a characteristic ion peak at m/z 85 (100% and a linear retention index (RI of 2,023 on a DB Wax column, consistent with those of an authentic sample of γ-nonalactone. The odor characterization of a strong, sweet, coconut-like aroma of this compound was also validated by GC-O comparison with the authentic compound.

  13. Volatiles in Breath and Headspace Analysis - Diagnostic Markers

    Science.gov (United States)

    2017-07-24

    Tuberculosis; Gastric Cancer; Peptic Ulcer; Atrophic Gastritis; Intestinal Metaplasia; Gastric Dysplasia; Colorectal Cancer; Colorectal Polyp; Colorectal Adenoma; Pancreatic Cancer; Pancreatitis, Chronic; Liver Cancer; Liver Cirrhosis; Flu, Human; Other Infectious Diseases; Inflammatory Bowel Diseases

  14. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford Waste Tank U-203, Results from samples collected on August 8, 1995

    International Nuclear Information System (INIS)

    Pool, K.H.; Clauss, T.W.; Evans, J.C.; McVeety, B.D.; Thomas, B.L.; Olsen, K.B.; Fruchter, J.S.; Ligotke, M.W.

    1995-11-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-U-203 (Tank U-203) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank-farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest Laboratory (PNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the results is listed. Detailed descriptions of the analytical results appear in the text

  15. Tank Vapor Characterization Project. Headspace vapor characterization of Hanford Waste Tank AX-102: Results from samples collected on June 27, 1995

    International Nuclear Information System (INIS)

    Clauss, T.W.; Pool, K.H.; Evans, J.C.; McVeety, B.D.; Thomas, B.L.; Olsen, K.B.; Fruchter, J.S.; Ligotke, M.W.

    1995-11-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-AX-102 (Tank AX-102) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank-farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest Laboratory (PNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. Detailed descriptions of the analytical results appear in the text

  16. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford Tank 241-S-107: Results from samples collected on 06/18/96

    International Nuclear Information System (INIS)

    Pool, K.H.; Evans, J.C.; Thomas, B.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-S-107 (Tank S-107) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National. Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, on sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in Table S.1. Detailed descriptions of the analytical results appear in the appendices

  17. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford Waste Tank U-204, Results from samples collected on August 8, 1995

    International Nuclear Information System (INIS)

    Clauss, T.W.; Evans, J.C.; McVeety, B.D.; Pool, K.H.; Thomas, B.L.; Olsen, K.B.; Fruchter, J.S.; Ligotke, M.W.

    1995-11-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-U-204 (Tank U-204) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank-farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the results is listed. Detailed descriptions of the analytical results appear in the text

  18. Polyaniline-nylon-6 electrospun nanofibers for headspace adsorptive microextraction

    International Nuclear Information System (INIS)

    Bagheri, Habib; Aghakhani, Ali

    2012-01-01

    Highlights: ► Polyaniline–polyamide nanofiber mat was fabricated by electrospinning technology. ► Electrospun nanofiber was used for extraction of chlorobenzenes from aquatic media. ► A method based on headspace adsorptive microextraction and GC–MS was developed. - Abstract: A headspace adsorptive microextraction technique was developed using a novel polyaniline-nylon-6 (PANI-N6) nanofiber sheet, fabricated by electrospinning. The homogeneity and the porosity of the prepared PANI-N6 sheet were studied using the scanning electron microscopy (SEM) and nanofibers diameters were found to be around 200 nm. The novel nanofiber sheet was examined as an extracting medium to isolate some selected chlorobenzenes (CBs), as model compounds, from aquatic media. The extracted analytes were desorbed using μL-amounts of solvent and eventually an aliquot of extractant was injected into gas chromatography–mass spectrometry (GC–MS). Various parameters affecting the extraction and desorption processes were optimized. The developed method proved to be convenient and offers sufficient sensitivity and a good reproducibility. Limits of detection achieved for CBs with the developed analytical procedure ranged from 19 to 33 ng L −1 , while limits of quantification were from 50 to 60 ng L −1 . The relative standard deviations (RSD) at a concentration level of 0.1 ng mL −1 and 1 ng mL −1 were in the range of 8–14% and 5–11% (n = 3), respectively. The calibration curves of analytes were investigated in the range of 50–1000 ng L −1 and R 2 between 0.9739 and 0.9932 were obtained. The developed method was successfully applied to the extraction of selected CBs from tap and river water samples. The relative recovery (RR) percentage obtained for the spiked real water samples at 0.1 ng mL −1 and 1 ng mL −1 level were 93–103% and 95–104%, respectively. The whole procedure showed to be conveniently applicable and quite easy to handle.

  19. Polyaniline-nylon-6 electrospun nanofibers for headspace adsorptive microextraction

    Energy Technology Data Exchange (ETDEWEB)

    Bagheri, Habib, E-mail: bagheri@sharif.edu [Environmental and Bio-Analytical Laboratories, Department of Chemistry, Sharif University of Technology, P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of); Aghakhani, Ali [Environmental and Bio-Analytical Laboratories, Department of Chemistry, Sharif University of Technology, P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of)

    2012-02-03

    Highlights: Black-Right-Pointing-Pointer Polyaniline-polyamide nanofiber mat was fabricated by electrospinning technology. Black-Right-Pointing-Pointer Electrospun nanofiber was used for extraction of chlorobenzenes from aquatic media. Black-Right-Pointing-Pointer A method based on headspace adsorptive microextraction and GC-MS was developed. - Abstract: A headspace adsorptive microextraction technique was developed using a novel polyaniline-nylon-6 (PANI-N6) nanofiber sheet, fabricated by electrospinning. The homogeneity and the porosity of the prepared PANI-N6 sheet were studied using the scanning electron microscopy (SEM) and nanofibers diameters were found to be around 200 nm. The novel nanofiber sheet was examined as an extracting medium to isolate some selected chlorobenzenes (CBs), as model compounds, from aquatic media. The extracted analytes were desorbed using {mu}L-amounts of solvent and eventually an aliquot of extractant was injected into gas chromatography-mass spectrometry (GC-MS). Various parameters affecting the extraction and desorption processes were optimized. The developed method proved to be convenient and offers sufficient sensitivity and a good reproducibility. Limits of detection achieved for CBs with the developed analytical procedure ranged from 19 to 33 ng L{sup -1}, while limits of quantification were from 50 to 60 ng L{sup -1}. The relative standard deviations (RSD) at a concentration level of 0.1 ng mL{sup -1} and 1 ng mL{sup -1} were in the range of 8-14% and 5-11% (n = 3), respectively. The calibration curves of analytes were investigated in the range of 50-1000 ng L{sup -1} and R{sup 2} between 0.9739 and 0.9932 were obtained. The developed method was successfully applied to the extraction of selected CBs from tap and river water samples. The relative recovery (RR) percentage obtained for the spiked real water samples at 0.1 ng mL{sup -1} and 1 ng mL{sup -1} level were 93-103% and 95-104%, respectively. The whole procedure showed

  20. Determination of residual acetone and acetone related impurities in drug product intermediates prepared as Spray Dried Dispersions (SDD) using gas chromatography with headspace autosampling (GCHS).

    Science.gov (United States)

    Quirk, Emma; Doggett, Adrian; Bretnall, Alison

    2014-08-05

    Spray Dried Dispersions (SDD) are uniform mixtures of a specific ratio of amorphous active pharmaceutical ingredient (API) and polymer prepared via a spray drying process. Volatile solvents are employed during spray drying to facilitate the formation of the SDD material. Following manufacture, analytical methodology is required to determine residual levels of the spray drying solvent and its associated impurities. Due to the high level of polymer in the SDD samples, direct liquid injection with Gas Chromatography (GC) is not a viable option for analysis. This work describes the development and validation of an analytical approach to determine residual levels of acetone and acetone related impurities, mesityl oxide (MO) and diacetone alcohol (DAA), in drug product intermediates prepared as SDDs using GC with headspace (HS) autosampling. The method development for these analytes presented a number of analytical challenges which had to be overcome before the levels of the volatiles of interest could be accurately quantified. GCHS could be used after two critical factors were implemented; (1) calculation and application of conversion factors to 'correct' for the reactions occurring between acetone, MO and DAA during generation of the headspace volume for analysis, and the addition of an equivalent amount of polymer into all reference solutions used for quantitation to ensure comparability between the headspace volumes generated for both samples and external standards. This work describes the method development and optimisation of the standard preparation, the headspace autosampler operating parameters and the chromatographic conditions, together with a summary of the validation of the methodology. The approach has been demonstrated to be robust and suitable to accurately determine levels of acetone, MO and DAA in SDD materials over the linear concentration range 0.008-0.4μL/mL, with minimum quantitation limits of 20ppm for acetone and MO, and 80ppm for DAA. Copyright

  1. Multiple responses optimization in the development of a headspace gas chromatography method for the determination of residual solvents in pharmaceuticals

    Directory of Open Access Journals (Sweden)

    Carla M. Teglia

    2015-10-01

    Full Text Available An efficient generic static headspace gas chromatography (HSGC method was developed, optimized and validated for the routine determination of several residual solvents (RS in drug substance, using a strategy with two sets of calibration. Dimethylsulfoxide (DMSO was selected as the sample diluent and internal standards were used to minimize signal variations due to the preparative step. A gas chromatograph from Agilent Model 6890 equipped with flame ionization detector (FID and a DB-624 (30 m×0.53 mm i.d., 3.00 µm film thickness column was used. The inlet split ratio was 5:1. The influencing factors in the chromatographic separation of the analytes were determined through a fractional factorial experimental design. Significant variables: the initial temperature (IT, the final temperature (FT of the oven and the carrier gas flow rate (F were optimized using a central composite design. Response transformation and desirability function were applied to find out the optimal combination of the chromatographic variables to achieve an adequate resolution of the analytes and short analysis time. These conditions were 30 °C for IT, 158 °C for FT and 1.90 mL/min for F. The method was proven to be accurate, linear in a wide range and very sensitive for the analyzed solvents through a comprehensive validation according to the ICH guidelines. Keywords: Headspace gas chromatography, Residual solvents, Pharmaceuticals, Surface response methodology, Desirability function

  2. Headspace vapor characterization of Hanford waste tank 241-U-109: Results from samples collected on 8/10/95

    International Nuclear Information System (INIS)

    Evans, J.C.; Thomas, B.L.; Pool, K.H.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1996-05-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-U-109 (Tank U-109) At the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. This tank is on the Hydrogen Waste List. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases and total non-methane hydrocarbons is listed in a table. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples is also listed in the table. Detailed descriptions of the analytical results appear in the text

  3. Headspace vapor characterization of Hanford waste Tank 241-BX-110: Results from samples collected on 04/30/96

    International Nuclear Information System (INIS)

    Evans, J.C.; Pool, K.H.; Thomas, B.L.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-BX-110 (Tank BX-110) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in a table. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples are also listed in the table. Detailed descriptions of the analytical results appear in the appendices

  4. Determination of volatile organic compounds in eucalyptus fast pyrolysis bio-oil by full evaporation headspace gas chromatography.

    Science.gov (United States)

    Kosinski Lima, Nathalya; Romualdo Lopes, André; Gimenes Guerrero, Palimecio; Itsuo Yamamoto, Carlos; Augusto Hansel, Fabricio

    2018-01-01

    This paper reports a full evaporation (FE) headspace gas chromatographic (HS-GC) method for the determination of the volatile organic compounds (VOCs) in bio-oil (i.e. methanol, ethanol, acetone, acetic acid and furfural). The method uses a 4μL sample of bio-oil in a headspace vial (ca. 20mL). Complete evaporation of the compounds was achieved after seven minutes at 90°C. The method showed good precision and accuracy for methanol, ethanol, acetone and acetic acid. The recovery of furfural was low (74.3%). The results showed that the protocol can be applied for the determination of methanol, ethanol, acetone and acetic acid in bio-oil. Detection limits ranged from 0.13 to 0.16μg. Acetic acid was the dominant analyte in the heavy bio-oil and light bio-oil analysis (113. 3 and 85.1µgmg -1 , respectively), followed by methanol, ethanol, and acetone. The polymerisation of furfural was suspected as the cause of its poor quantification. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2013-04-03

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

  6. A short review of headspace extraction and ultrasonic solvent extraction for honey volatiles fingerprinting

    Directory of Open Access Journals (Sweden)

    Z. Marijanović

    2009-01-01

    Full Text Available Honey volatiles exhibit a potential role in distinguishing honeys as a function of botanical origin, but heating of honey generates artefacts such as compounds of Strecker degradation and Maillard reaction products. This short review is focused on the most recently applied methods for honey volatiles fingerprinting (without generation of thermal artefacts: headspace extraction (dynamic headspace extraction (DHE, headspace solid-phase microextraction (HS-SPME and ultrasonic solvent extraction (USE. These methods display a varying degree of selectivity and effectiveness depending upon the compounds involved and the extraction conditions. Recent developments of these methods are discussed, with application examples drawn from the literature as well from our own research. Flavour qualities of the honey are very much dependent on the volatile and semivolatile organic compounds present in both the sample matrix and the headspace aroma. Therefore the use of one single technique is not adequate for reliable honey volatiles profiling, but combined use of headspace extraction and ultrasonic solvent extraction could be a useful tool for the characterization of the honey and identification of its botanical source through typical volatile marker compounds.

  7. headspace - Australia's innovation in youth mental health: who are the clients and why are they presenting?

    Science.gov (United States)

    Rickwood, Debra J; Telford, Nic R; Parker, Alexandra G; Tanti, Chris J; McGorry, Patrick D

    2014-02-03

    To provide the first national profile of the characteristics of young people (aged 12-25 years) accessing headspace centre services - the Australian Government's innovation in youth mental health service delivery - and investigate whether headspace is providing early service access for adolescents and young adults with emerging mental health problems. Census of all young people accessing a headspace centre across the national network of 55 centres comprising a total of 21 274 headspace clients between 1 January and 30 June 2013. Reason for presentation, Kessler Psychological Distress Scale, stage of illness, diagnosis, functioning. Young people were most likely to present with mood and anxiety symptoms and disorders, self-reporting their reason for attendance as problems with how they felt. Client demographic characteristics tended to reflect population-level distributions, although clients from regional areas and of Aboriginal and Torres Strait Islander background were particularly well represented, whereas those who were born outside Australia were underrepresented. headspace centres are providing a point of service access for young Australians with high levels of psychological distress and need for care in the early stages of the development of mental disorder.

  8. The utilisation of two detectors for the determination of water in honey using headspace gas chromatography.

    Science.gov (United States)

    Frink, Lillian A; Armstrong, Daniel W

    2016-08-15

    A headspace gas chromatography (HSGC) method was developed for the determination of water content in honey. This method was shown to work with five different honey varieties which had a range of water from 14-16%. It also utilised two different detectors, the thermal conductivity detector (TCD) and the barrier discharge ionisation detector (BID). This method needs no heating pretreatment step as in the current leading method, (i.e. the measurement of refractive index). The solvent-free procedure negates the possibility of solvent-compound interactions as well as solubility limitations, as is common with Karl Fischer titrations. It was also apparent that the classic loss on drying method consistently and substantially produced results that were lower than the correct values. This approach is shown to be rapid, with an analysis time of 4 min when using the TCD detector and under 3 min when utilising the BID detector. HSGC is feasible for the determination of water due to the new PEG-linked geminal dicationic ionic-liquid-coated GC capillary column. In addition it provides accurate and precise determinations of the water content in honey. When using the sensitive BID detector, other trace volatile compounds are observed as well. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Headspace gas chromatographic method for the measurement of difluoroethane in blood.

    Science.gov (United States)

    Broussard, L A; Broussard, A; Pittman, T; Lafferty, D; Presley, L

    2001-01-01

    To develop a gas chromatographic assay for the analysis of difluoroethane, a volatile substance, in blood and to determine assay characteristics including linearity, limit of quantitation, precision, and specificity. Referral toxicology laboratory Difluoroethane, a colorless, odorless, highly flammable gas used as a refrigerant blend component and aerosol propellant, may be abused via inhalation. A headspace gas chromatographic procedure for the identification and quantitation of difluoroethane in blood is presented. A methanolic stock standard prepared from pure gaseous difluoroethane was used to prepare whole blood calibrators. Quantitation of difluoroethane was performed using a six-point calibration curve and an internal standard of 1-propanol. The assay is linear from 0 to 115 mg/L including a low calibrator at 4 mg/L, the limit of quantitation. Within-run coefficients of variation at mean concentrations of 13.8 mg/L and 38.5 mg/L were 5.8% and 6.8% respectively. Between-run coefficients of variation at mean concentrations of 15.9 mg/L and 45.7 mg/L were 13.4% and 9.8% respectively. Several volatile substances were tested as potential interfering compounds with propane having a retention time identical to that of difluoroethane. This method requires minimal sample preparation, is rapid and reproducible, can be modified for the quantitation of other volatiles, and could be automated using an automatic sampler/injector system.

  10. Headspace liquid-phase microextraction of methamphetamine and amphetamine in urine by an aqueous drop

    International Nuclear Information System (INIS)

    He Yi; Vargas, Angelica; Kang, Youn-Jung

    2007-01-01

    This study developed a headspace liquid-phase microextraction (LPME) method by using a single aqueous drop in combination with high performance liquid chromatography (HPLC)-UV detection for the determination of methamphetamine (MAP) and amphetamine (AP) in urine samples. The analytes, volatile and basic, were released from sample matrix into the headspace first, and then protonated and dissolved in an aqueous H 3 PO 4 drop hanging in the headspace by a HPLC syringe. After extraction, this drop was directly injected into HPLC. Parameters affecting extraction efficiency were investigated and optimized. This method showed good linearity in the investigated concentration range of 1.0-1500 μg L -1 , repeatability of the extraction (R.S.D. -1 for both analytes). Enrichment factors of about 400-fold and 220-fold were achieved for MAP and AP, respectively, at optimum conditions. The feasibility of the method was demonstrated by analyzing human urine samples

  11. Lab-In-Syringe automation of stirring-assisted room-temperature headspace extraction coupled online to gas chromatography with flame ionization detection for determination of benzene, toluene, ethylbenzene, and xylenes in surface waters.

    Science.gov (United States)

    Horstkotte, Burkhard; Lopez de Los Mozos Atochero, Natalia; Solich, Petr

    2018-06-22

    Online coupling of Lab-In-Syringe automated headspace extraction to gas chromatography has been studied. The developed methodology was successfully applied to surface water analysis using benzene, toluene, ethylbenzene, and xylenes as model analytes. The extraction system consisted of an automatic syringe pump with a 5 mL syringe into which all solutions and air for headspace formation were aspirated. The syringe piston featured a longitudinal channel, which allowed connecting the syringe void directly to a gas chromatograph with flame ionization detector via a transfer capillary. Gas injection was achieved via opening a computer-controlled pinch valve and compressing the headspace, upon which separation was initialized. Extractions were performed at room temperature; yet sensitivity comparable to previous work was obtained by high headspace to sample ratio V HS /V Sample of 1.6:1 and injection of about 77% of the headspace. Assistance by in-syringe magnetic stirring yielded an about threefold increase in extraction efficiency. Interferences were compensated by using chlorobenzene as an internal standard. Syringe cleaning and extraction lasting over 10 min was carried out in parallel to the chromatographic run enabling a time of analysis of <19 min. Excellent peak area repeatabilities with RSD of <4% when omitting and <2% RSD when using internal standard corrections on 100 μg L -1 level were achieved. An average recovery of 97.7% and limit of detection of 1-2 μg L -1 were obtained in analyses of surface water. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. Comparison of direct, headspace and headspace cold fiber modes in solid phase microextraction of polycyclic aromatic hydrocarbons by a new coating based on poly(3,4-ethylenedioxythiophene)/graphene oxide composite.

    Science.gov (United States)

    Banitaba, Mohammad Hossein; Hosseiny Davarani, Saied Saeed; Kazemi Movahed, Siyavash

    2014-01-17

    A novel nanocomposite coating made of poly(3,4-ethylenedioxythiophene) (PEDOT) and graphene oxide was electrochemically prepared on gold wire. The prepared fiber was applied to the solid-phase microextraction (SPME) and gas chromatographic analysis of six polycyclic aromatic hydrocarbons (PAHs). Three modes of extraction i.e. direct immersion (DI), headspace (HS) and headspace cold fiber (HS-CF) in SPME were investigated. The results were compared under optimized conditions of each mode, considering the effects of the three most important parameters which are extraction temperature, extraction time and ionic strength. The comparison showed that HS-CF-SPME results in the best outcome for the extraction of PAHs from water samples. Under the optimized conditions of this mode, the calibration curves were linear within the range of 0.4-600μgL(-1) and the detection limits were between 0.05 and 0.13μgL(-1). The intra-day and inter-day relative standard deviations obtained at 10μgL(-1) (n=5), using a single fiber, were 4.1-6.8% and 4.8-8.4%, respectively. The fiber-to-fiber repeatabilities (n=4), expressed as the relative standard deviations (RSD%), were between 6.5% and 10.7% at a 10μgL(-1) concentration level. The method was successfully applied to the analysis of PAHs in seawater samples showing recoveries from 85% to 107%. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Determination of the solubility of low volatility liquid organic compounds in water using volatile-tracer assisted headspace gas chromatography.

    Science.gov (United States)

    Zhang, Shu-Xin; Chai, Xin-Sheng; Barnes, Donald G

    2016-02-26

    This study reports a new headspace gas chromatographic method (HS-GC) for the determination of water solubility of low volatility liquid organic compounds (LVLOs). The HS-GC analysis was performed on a set of aqueous solutions containing a range of concentrations of toluene-spiked (as a tracer) LVLOs, from under-saturation to over-saturation. A plot of the toluene tracer GC signal vs. the concentration of the LVLO results in two lines of different slopes that intersect at the concentration corresponding to the compound's solubility in water. The results showed that the HS-GC method has good precision (RSD waters of environmental and biological systems. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. The potential of head-space gas chromatography for VLE measurements

    International Nuclear Information System (INIS)

    Luis, Patricia; Wouters, Christine; Sweygers, Nick; Creemers, Claude; Van der Bruggen, Bart

    2012-01-01

    Highlights: ► HS-GC is a potential technique to obtain VLE data in a high throughput scenario. ► We applied HS-GC and evaluate the main issues to consider. ► Four azeotropic mixtures of industrial interest are studied. ► The thermodynamic analysis of VLE shows the strong non-ideality of the mixtures. - Abstract: Head-space gas chromatography (HS-GC) is thought to allow the performance of (vapour + liquid) equilibrium (VLE) measurements in a fast and automated way. However, two decades after the first applications of HS-GC for this purpose, the potential of this technique is not fully developed yet. Measurements of isothermal VLE and activity coefficients of mixtures can be obtained in a high throughput scenario. However, several considerations have to be taken into account before starting the analysis, such as the equilibration time or the minimum sample volume and the GC response factors. These aspects can strongly influence on the validity of the results and should therefore be determined for each mixture. In this paper, four azeotropic mixtures of interest in the pharmaceutical and chemical industry, i.e., (ethylacetate + water), which forms a heterogeneous azeotrope, (ethylacetate + isooctane), (acetonitrile + toluene) and the ternary mixture (acetonitrile + toluene + tetrahydrofuran), are considered to show the potential of HS-GC for VLE measurements. The thermodynamic analysis of VLE data leads to activity coefficients for the mixtures at (35, 50, and 70) °C. In addition, the experimental data are compared with thermodynamic models and data from the literature, when available.

  15. Comparação entre injeção na coluna ("on-column" e headspace dinâmico na determinação de benzeno, tolueno e xilenos (BTX em amostras de água

    Directory of Open Access Journals (Sweden)

    Gobato Elaine A. A. F.

    2001-01-01

    Full Text Available The analysis of water samples containing volatile organic compounds has become an important task in analytical chemistry. Gas chromatography has been widely used for the analysis of volatile organic compounds in water. The headspace analysis shows as a principal characteristic the possibility of determination of the volatile components in drinking water. Benzene, Toluene and Xylene (BTX are important compounds usually present in drinking water, from contamination by petroleum derivatives. Since they are toxic compounds even when present in low concentration levels, their determination is important in order to define the quality of the water. The sampling technique using headspace, coupled with gas chromatography as the separation method, showed to be suitable for BTX analysis in several samples at the mug/L (ppb level.

  16. Flight attraction of Spodoptera littoralis (Lepidoptera, Noctuidae to cotton headspace and synthetic volatile blends

    Directory of Open Access Journals (Sweden)

    Felipe eBorrero-Echeverry

    2015-06-01

    Full Text Available The insect olfactory system discriminates odor signals of different biological relevance, which drive innate behavior. Identification of stimuli that trigger upwind flight attraction towards host plants is a current challenge, and is essential in developing new, sustainable plant protection methods, and for furthering our understanding of plant-insect interactions. Using behavioral, analytical and electrophysiological studies, we here show that both females and males of the Egyptian cotton leafworm, Spodoptera littoralis (Lepidoptera, Noctuidae, use blends of volatile compounds to locate their host plant, cotton, Gossypium hirsutum (Malvales, Malvaceae. Female S. littoralis were engaged in upwind orientation flight in a wind tunnel when headspace collected from cotton plants was delivered through a piezoelectric sprayer. Although males took off towards cotton headspace significantly fewer males than females flew upwind towards the sprayed headspace. Subsequent assays with antennally active synthetic compounds revealed that a blend of nonanal, (Z-3 hexenyl acetate, (E-β-ocimene, and (R-(+-limonene was as attractive as cotton headspace to females and more attractive to males. DMNT and (R-(--linalool, both known plant defense compounds may have reduced the flight attraction of both females and males; more moths were attracted to blends without these two compounds. Our findings provide a platform for further investigations on host plant signals mediating innate behavior, and for the development of novel insect plant protection strategies against S. littoralis.

  17. Determination of carboxyl groups in wood fibers by headspace gas chromatography

    Science.gov (United States)

    X.-S. Chai; Q.X. Hou; J.Y. Zhu; S.-L. Chen; S.F. Wang; L. Lucia

    2003-01-01

    The phase reaction conversion (PRC) headspace gas chromatographic (HSGC) technique was employed to develop a method for the determination of the content of carboxyl groups in wood fibers. Acid treatment of the wood fibers using hydrochloric was applied to convert carboxyl groups to carboxyl acids. Bicarbonate solution is then used to react with carboxyl acids on the...

  18. Tank 241-B-103 headspace gas and vapor characterization results for samples collected in February 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  19. Tank 241-BX-104 headspace gas and vapor characterization results for samples collected in December 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  20. Measurement of water absorption capacity in wheat flour by a headspace gas chromatographic technique.

    Science.gov (United States)

    Xie, Wei-Qi; Yu, Kong-Xian; Gong, Yi-Xian

    2018-04-17

    The purpose of this work is to introduce a new method for quantitatively analyzing water absorption capacity in wheat flour by a headspace gas chromatographic technique. This headspace gas chromatographic technique was based on measuring the water vapor released from a series of wheat flour samples with different contents of water addition. According to the different trends between the vapor and wheat flour phase before and after the water absorption capacity in wheat flour, a turning point (corresponding to water absorption capacity in wheat flour) can be obtained by fitting the data of the water gas chromatography peak area from different wheat flour samples. The data showed that the phase equilibrium in the vial can be achieved in 25 min at desired temperature (35°C). The relative standard deviation of the reaction headspace gas chromatographic technique in water absorption capacity determination was within 3.48%, the relative differences has been determined by comparing the water absorption capacity obtained from this new analytical technique with the data from the reference technique (i.e., the filtration method), which are less than 8.92%. The new headspace gas chromatographic method is automated, accurate and be a reliable tool for quantifying water absorption capacity in wheat flour in both laboratory research and mill applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Isolation and quantification of volatiles in fish by dynamic headspace sampling and mass spectrometry

    DEFF Research Database (Denmark)

    Refsgaard, Hanne; Haahr, Anne-Mette; Jensen, Benny

    1999-01-01

    A dynamic headspace sampling method for isolation of volatiles in fish has been developed. The sample preparation involved freezing of fish tissue in liquid nitrogen, pulverizing the tissue, and sampling of volatiles from an aqueous slurry of the fish powder. Similar volatile patterns were...

  2. Tank 241-U-203 headspace gas and vapor characterization results for samples collected in August 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  3. Tank 241-C-106 headspace gas and vapor characterization results for samples collected in February 1994

    International Nuclear Information System (INIS)

    Hackaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  4. Tank 241-S-111 headspace gas and vapor characterization results for samples collected in March 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  5. Tank 241-U-103 headspace gas and vapor characterization results for samples collected in February 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  6. Tank 241-SX-106 headspace gas and vapor characterization results for samples collected in March 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  7. Tank 241-TX-105 headspace gas and vapor characterization results for samples collected in December 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  8. Tank 241-C-102 headspace gas and vapor characterization results for samples collected in August 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  9. Tank 241-BY-112 headspace gas and vapor characterization results for samples collected in November 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  10. Tank 241-T-111 headspace gas and vapor characterization results for samples collected in January 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  11. Tank 241-SX-103 headspace gas and vapor characterization results for samples collected in March 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  12. Tank 241-TY-104 headspace gas and vapor characterization results for samples collected in April 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  13. Tank 241-C-110 headspace gas and vapor characterization results for samples collected in August 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  14. Tank 241-C-101 headspace gas and vapor characterization results for samples collected in September 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  15. Tank 241-C-107 headspace gas and vapor characterization results for samples collected in September 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  16. Tank 241-C-104 headspace gas and vapor characterization results for samples collected in March 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

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

    Science.gov (United States)

    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⁻¹ to μg mL⁻¹ 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 80°C using 3 L of purge gas allows complete vaporization of 100 μL 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 25°C: log0.54-5.65 mg L⁻¹, vapor pressure at 25°C: 0.011-3.2 mm Hg) and leaving most of the low volatile matrix behind. The FEDHS-GC-MS method showed good linearity (r²>0.9909) and high sensitivity (limit of detection: 0.21-5.2 ng mL⁻¹) 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 μg mL⁻¹ (RSDfuraneol, indole, maltol, and pyrazine congeners) were determined in the range of 0.21-110 ng mL⁻¹ (RSD<10%, n=6). Copyright © 2012 Elsevier B.V. All rights reserved.

  18. An analytical method for trifluoroacetic Acid in water and air samples using headspace gas chromatographic determination of the methyl ester.

    Science.gov (United States)

    Zehavi, D; Seiber, J N

    1996-10-01

    An analytical method has been developed for the determination of trace levels of trifluoroacetic acid (TFA), an atmospheric breakdown product of several of the hydrofluorocarbon (HFC) and hydrochlorofluorocarbon (HCFC) replacements for the chlorofluorocarbon (CFC) refrigerants, in water and air. TFA is derivatized to the volatile methyl trifluoroacetate (MTFA) and determined by automated headspace gas chromatography (HSGC) with electron-capture detection or manual HSGC using GC/MS in the selected ion monitoring (SIM) mode. The method is based on the reaction of an aqueous sample containing TFA with dimethyl sulfate (DMS) in concentrated sulfuric acid in a sealed headspace vial under conditions favoring distribution of MTFA to the vapor phase. Water samples are prepared by evaporative concentration, during which TFA is retained as the anion, followed by extraction with diethyl ether of the acidified sample and then back-extraction of TFA (as the anion) in aqueous bicarbonate solution. The extraction step is required for samples with a relatively high background of other salts and organic materials. Air samples are collected in sodium bicarbonate-glycerin-coated glass denuder tubes and prepared by rinsing the denuder contents with water to form an aqueous sample for derivatization and analysis. Recoveries of TFA from spiked water, with and without evaporative concentration, and from spiked air were quantitative, with estimated detection limits of 10 ng/mL (unconcentrated) and 25 pg/mL (concentrated 250 mL:1 mL) for water and 1 ng/m(3) (72 h at 5 L/min) for air. Several environmental air, fogwater, rainwater, and surface water samples were successfully analyzed; many showed the presence of TFA.

  19. Headspace volume and percentage of carbon monoxide affects carboxymyoglobin layer development of modified atmosphere packaged beef steaks.

    Science.gov (United States)

    Raines, Christopher R; Hunt, Melvin C

    2010-01-01

    Carboxymyoglobin (COMb) development of beef Longissimus lumborum as related to molecular CO availability and package headspace volume was evaluated. Steaks from six pairs of USDA Select strip loins were packaged in modified atmosphere packages with 0.2%, 0.4%, or 0.8% CO and 30% CO(2) and balanced with N(2) to obtain meat-to-gas ratios of 0.4, 0.7, and 1.1, and CO molar concentrations of 0.07, 0.10, and 0.20 mMol. Steak redness (CIE a*), COMb layer thickness, percentage of CO in the headspace, visual display color, and bloom intensity scores were evaluated 4 and 7 d after packaging. Greater concentration of CO in a smaller headspace resulted in a thicker COMb layer compared with lesser concentration of CO in a larger headspace, regardless of moles CO available. The combined effects of concentration of CO and headspace volume had a greater impact on COMb development than millimoles of CO in the package headspace. Package headspace can be reduced and the concentration of CO can be increased without detriment to fresh beef color or consumer safety.

  20. Determination of suspected allergens in cosmetic products by headspace-programmed temperature vaporization-fast gas chromatography-quadrupole mass spectrometry.

    Science.gov (United States)

    del Nogal Sánchez, Miguel; Pérez-Pavón, José Luis; Moreno Cordero, Bernardo

    2010-07-01

    In the present work, a strategy for the qualitative and quantitative analysis of 24 volatile compounds listed as suspected allergens in cosmetics by the European Union is reported. The list includes benzyl alcohol, limonene, linalool, methyl 2-octynoate, beta-citronellol, geraniol, citral (two isomers), 7-hydroxycitronellal, anisyl alcohol, cinnamal, cinnamyl alcohol, eugenol, isoeugenol (two isomers), coumarin, alpha-isomethyl ionone, lilial, alpha-amylcinnamal, lyral, alpha-amylcinnamyl alcohol, farnesol (three isomers), alpha-hexyl cinnamal, benzyl cinnamate, benzyl benzoate, and benzyl salicylate. The applicability of a headspace (HS) autosampler in combination with a gas chromatograph (GC) equipped with a programmable temperature vaporizer (PTV) and a quadrupole mass spectrometry (qMS) detector is explored. By using a headspace sampler, sample preparation is reduced to introducing the sample into the vial. This reduces the analysis time and the experimental errors associated with this step of the analytical process. Two different injection techniques were used: solvent-vent injection and hot-split injection. The first offers a way to improve sensitivity at the same time maintaining the simple headspace instrumentation and it is recommended for compounds at trace levels. The use of a liner packed with Tenax-TA allowed the compounds of interest to be retained during the venting process. The signals obtained when hot-split injection was used allowed quantification of all the compounds according to the thresholds of the European Cosmetics Directive. Monodimensional gas chromatography coupled to a conventional quadrupole mass spectrometry detector was used and the 24 analytes were separated appropriately along a run time of about 12 min. Use of the standard addition procedure as a quantification technique overcame the matrix effect. It should be emphasized that the method showed good precision and accuracy. Furthermore, it is rapid, simple, and--in view of the

  1. Investigations on the emission of fragrance allergens from scented toys by means of headspace solid-phase microextraction gas chromatography-mass spectrometry.

    Science.gov (United States)

    Masuck, Ines; Hutzler, Christoph; Luch, Andreas

    2010-04-30

    In the revised European toy safety directive 2009/48/EC the application of fragrance allergens in children's toys is restricted. The focus of the present work lies on the instrumental analytics of 13 banned fragrance allergens, as well as on 11 fragrance allergens that require declaration when concentrations surpass 100 microg per gram material. Applying a mixture of ethyl acetate and toluene solid/liquid extraction was performed prior to quantitative analysis of mass contents of fragrances in scented toys. In addition, an easy-to-perform method for the determination of emitted fragrances at 23 degrees C (handling conditions) or at 40 degrees C (worst case scenario) has been worked out to allow for the evaluation of potential risks originating from inhalation of these compounds during handling of or playing with toys. For this purpose a headspace solid-phase microextraction (HS-SPME) technique was developed and coupled to subsequent gas chromatography-mass spectrometry (GC-MS) analysis. Fragrance allergens were adsorbed (extracted) from the gas phase onto an 85 microm polyacrylate fiber while incubating pieces of the scented toys in sealed headspace vials at 23 degrees C and 40 degrees C. Quantification of compounds was performed via external calibration. The newly developed headspace method was subsequently applied to five perfumed toys. As expected, the emission of fragrance allergens from scented toys depends on the temperature and on the content of fragrance allergens present in those samples. In particular at conditions mimicking worst case (40 degrees C), fragrance allergens in toys may pose a risk to children since considerable amounts of compound might be absorbed by lung tissue via breathing of contaminated air. 2010 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-12-01

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

  3. Headspace vapor characterization of Hanford Waste Tank 241-U-112: Results from samples collected on 7/09/96

    International Nuclear Information System (INIS)

    Evans, J.C.; Pool, K.H.; Thomas, B.L.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-U-112 at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company

  4. Simultaneous Determination of Alkoxyalcohols in Wet Wipes Using Static Headspace Gas Chromatography and Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lee, So Jin; Pyo, Hee Soo; Chung, Bong Chul; Lee, Jeon Gae [KIST, Seoul (Korea, Republic of); Kim, Hai Dong [Kyung Hee University, Seoul (Korea, Republic of)

    2014-09-15

    Alkoxyalcohols are used as solvents or preservatives in various consumer products such as wet wipes. The metabolites of alkoxyalcohols are known to be chronically toxic and carcinogenic to animals. Thus, an analytical method is needed to monitor alkoxyalcohols in wet wipes. The aim of this study was to develop a simultaneous analytical method for 14 alkoxyalcohols using headspace gas chromatography coupled with mass spectrometry to analyze the wet wipes. This method was developed by comparing with various headspace extraction parameters. The linear calibration curves were obtained for the method (r2 > 0.995). The limit of detection of alkoxyalcohols ranged from 2 to 200 ng mL-1. The precision of the determinative method was less than 18.20% coefficient of variation both intra and inter days. The accuracy of the method ranged from 82.86% to 119.83%. (2-Methoxymethylethoxy)propanol, 2-phenoxyethanol, and 1-phenoxy-2-propanol were mainly detected in wet wipes.

  5. Determination of ketone bodies in blood by headspace gas chromatography-mass spectrometry

    DEFF Research Database (Denmark)

    Holm, Karen Marie Dollerup; Linnet, Kristian; Rasmussen, Brian Schou

    2010-01-01

    A gas chromatography-mass spectrometry (GC-MS) method for determination of ketone bodies (ß-hydroxybutyrate, acetone, and acetoacetate) in blood is presented. The method is based on enzymatic oxidation of D-ß-hydroxybutyrate to acetoacetate, followed by decarboxylation to acetone, which...... was quantified by the use of headspace GC-MS using acetone-(13)C(3) as an internal standard. The developed method was found to have intra- and total interday relative standard deviations

  6. Tank 241-C-111 headspace gas and vapor sample results - August 1993 samples

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1994-01-01

    Tank 241-C-111 is on the ferrocyanide Watch List. Gas and vapor samples were collected to assure safe conditions before planned intrusive work was performed. Sample analyses showed that hydrogen is about ten times higher in the tank headspace than in ambient air. Nitrous oxide is about sixty times higher than ambient levels. The hydrogen cyanide concentration was below 0.04 ppbv, and the average NO x concentration was 8.6 ppmv

  7. Headspace liquid-phase microextraction of methamphetamine and amphetamine in urine by an aqueous drop

    Energy Technology Data Exchange (ETDEWEB)

    He Yi [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States)]. E-mail: yhe@jjay.cuny.edu; Vargas, Angelica [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States); Kang, Youn-Jung [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States)

    2007-04-25

    This study developed a headspace liquid-phase microextraction (LPME) method by using a single aqueous drop in combination with high performance liquid chromatography (HPLC)-UV detection for the determination of methamphetamine (MAP) and amphetamine (AP) in urine samples. The analytes, volatile and basic, were released from sample matrix into the headspace first, and then protonated and dissolved in an aqueous H{sub 3}PO{sub 4} drop hanging in the headspace by a HPLC syringe. After extraction, this drop was directly injected into HPLC. Parameters affecting extraction efficiency were investigated and optimized. This method showed good linearity in the investigated concentration range of 1.0-1500 {mu}g L{sup -1}, repeatability of the extraction (R.S.D. < 5%, n = 6), and low detection limits (0.3 {mu}g L{sup -1} for both analytes). Enrichment factors of about 400-fold and 220-fold were achieved for MAP and AP, respectively, at optimum conditions. The feasibility of the method was demonstrated by analyzing human urine samples.

  8. Headspace mass spectrometry methodology: application to oil spill identification in soils

    Energy Technology Data Exchange (ETDEWEB)

    Perez Pavon, J.L.; Garcia Pinto, C.; Moreno Cordero, B. [Universidad de Salamanca, Departamento de Quimica Analitica, Nutricion y Bromatologia, Facultad de Ciencias Quimicas, Salamanca (Spain); Guerrero Pena, A. [Universidad de Salamanca, Departamento de Quimica Analitica, Nutricion y Bromatologia, Facultad de Ciencias Quimicas, Salamanca (Spain); Laboratorio de Suelos, Plantas y Aguas, Campus Tabasco, Colegio de Postgraduados, Cardenas, Tabasco (Mexico)

    2008-05-15

    In the present work we report the results obtained with a methodology based on direct coupling of a headspace generator to a mass spectrometer for the identification of different types of petroleum crudes in polluted soils. With no prior treatment, the samples are subjected to the headspace generation process and the volatiles generated are introduced directly into the mass spectrometer, thereby obtaining a fingerprint of volatiles in the sample analysed. The mass spectrum corresponding to the mass/charge ratios (m/z) contains the information related to the composition of the headspace and is used as the analytical signal for the characterization of the samples. The signals obtained for the different samples were treated by chemometric techniques to obtain the desired information. The main advantage of the proposed methodology is that no prior chromatographic separation and no sample manipulation are required. The method is rapid, simple and, in view of the results, highly promising for the implementation of a new approach for oil spill identification in soils. (orig.)

  9. Determination of methanol in pulp washing filtrates by desiccated full evaporation headspace gas chromatography.

    Science.gov (United States)

    Hu, Hui-Chao; Chai, Xin-Sheng

    2012-01-27

    This paper reports on a desiccated full evaporation headspace gas chromatographic (FE HS-GC) technique for determination of the methanol content in dilute mill effluents. Anhydrous K(2)CO(3) was selected as the preferred salt for eliminating the water in the sample in the headspace sample vial. The results showed that the addition of 12 g K(2)CO(3) made it possible to introduce a larger sample size (up to 1 mL) into the FE HS-GC measurement, thereby increasing the sensitivity of the technique. At the given equilibration temperature (105°C), a near-complete mass transfer of methanol from the liquid phase to vapor phase (headspace) was achieved within 10 min. Replicate samples showed that the relative standard deviation of the method was less than 1.5%. Further, the limit of quantification (LOQ) was 0.12 μg and the recovery ranged from 95 to 104%. The present method greatly improves the methanol detection sensitivity in the FE HS-GC method and has the added advantage of being simple, rapid and accurate. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Comparison of Three Methods for Extraction of Volatile Lipid Oxidation Products from Food Matrices for GC-MS Analysis

    DEFF Research Database (Denmark)

    Jacobsen, Charlotte; Yesiltas, B.; Berner, Lis

    headspace extraction has been performed manually. Recently, automated dynamic headspace methods have become available. This presentation will summarize the principles of the different extraction methods. Moreover, results from fish oil, oil-in-water emulsion and milk obtained with SPME, manual dynamic...... headspace or automated dynamic headspace (TDU/DHS) extraction followed by GC-MS analysis will be compared. In all cases, concentrations of volatiles were quantified by calibration curves by addition of selected standards to oil, emulsion or milk. The results show that the linearity of calibration curves...

  11. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford Tank 241-TY-102: Results from samples collected on 04/12/96

    International Nuclear Information System (INIS)

    Evans, J.C.; Pool, K.H.; Thomas, B.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-TY-102 (Tank TY-102) at the Hanford Site in Washington State. The results described in this report were obtained to'characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes, and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in Table S.1. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples are also listed in Table S.1. Detailed descriptions of the analytical results appear in the appendices

  12. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford Tank 241-B-105: Results from samples collected on 07/30/96

    International Nuclear Information System (INIS)

    Pool, K.H.; Evans, J.C.; Thomas, B.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-B-105 (Tank B-105) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in Table S.1. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples are also listed in Table S.1. Detailed descriptions of the analytical results appear in the appendices

  13. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford Waste Tank 241-S-103: Results from samples collected on 06/12/96

    International Nuclear Information System (INIS)

    Evans, J.C.; Pool, K.H.; Thomas, B.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-S-103 (Tank S-103) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in Table S.1. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples are also listed in Table S.1. Detailed descriptions of the analytical results appear in the appendices

  14. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford Waste Tank 241-C-204: Results from samples collected on 07/02/96

    International Nuclear Information System (INIS)

    Thomas, B.L.; Evans, J.C.; Pool, K.H.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-C-204 (Tank C-204) at the Hanford Site in Washington State. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained by Westinghouse Hanford Company (WHC) and provided for analysis to Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed in Table S.1. The three highest concentration analytes detected in SUMMA trademark canister and triple sorbent trap samples are also listed in Table S.1. Detailed descriptions of the analytical results appear in the appendices

  15. Performance evaluation of a thermal desorption/gas chromatographic/mass spectrometric method for the characterization of waste tank headspace samples

    International Nuclear Information System (INIS)

    Ma, C.Y.; Skeen, J.T.; Dindal, A.B.; Bayne, C.K.; Jenkins, R.A.

    1997-01-01

    A thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS) method was validated for the determination of volatile organic compounds collected on carbonaceous triple sorbent traps and applied to characterize samples of headspace gases collected from underground nuclear waste storage tanks at the U.S. Department of Energy's Hanford site, in Richland, WA. Method validation used vapor-phase standards generated from 25 target analytes, including alkanes, alkyl alcohols, alkyl ketones, alkylated aromatics, and alkyl nitriles. The target analytes represent a group of compounds identified in one of the most problematic tanks. TD/GC/MS was carried out with modified injectors. Performance was characterized based on desorption efficiency, reproducibility, stability, and linearity of the calibration, method detection limits, preanalytical holding time, and quality control limits for surrogate standard recoveries. Desorption efficiencies were all greater than 82%, and the majority of the analytes (23 out of 25) had reproducibility values less than 24% near the method detection levels. The method was applied to the analysis of a total of 305 samples collected from the headspaces of 48 underground waste storge tanks. Quality control procedures were implemented to monitor sampling and TD/GC/MS method. 33 refs., 2 figs., 4 tabs

  16. Determination of tetrachloroethylene and other volatile halogenated organic compounds in oil wastes by headspace SPME GC-MS

    Energy Technology Data Exchange (ETDEWEB)

    Fabbri, D.; Bezzi, R.; Torri, C.; Galletti, P.; Tagliavini, E. [Bologna Univ., Ravenna (Italy). Lab. of Chemistry, C.I.R.S.A

    2007-09-15

    Oil wastes and slops are complex mixtures of hydrocarbons, which may contain a variety of contaminants including tetrachloroethylene (perchloroethylene, PCE) and other volatile halogenated organic compounds (VHOCs). The analytical determination of PCE at trace levels in petroleum-derived matrices is difficult to carry out in the presence of large amounts of hydrocarbon matrix components. In the following study, we demonstrate that headspace solid-phase microextraction (HS-SPME) combined with GC-MS analysis can be applied for the rapid measurement of PCE concentration in oil samples. The HS-SPME method was developed using liquid paraffin as matrix matching reference material for external and internal calibration and optimisation of experimental parameters. The limit of quantitation was 0.05 mg kg{sup -1}, and linearity was established up to 25 mg kg{sup -1}. The HS-SPME method was extended to several VHOCs, including trichloroethylene (TCE) in different matrices and was applied to the quantitative analysis of PCE and TCE in real samples.

  17. Determination of Lactones in Wines by Headspace Solid-Phase Microextraction and Gas Chromatography Coupled with Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    S. J. Pérez-Olivero

    2014-01-01

    Full Text Available Application of headspace solid-phase microextraction (HS-SPME coupled with high-resolution gas chromatographic (HRGC analysis was studied for determining lactones in wines. Six different SPME fibers were tested, and the influence of different factors such as temperature and time of desorption, ionic strength, time of extraction, content of sugar, ethanol, tannins and anthocyanins, and pH and influence of SO2 were studied. The proposed HS-SPME-GC method is an appropriate technique for the quantitative analysis of γ-butyrolactone, γ-hexalactone, trans-whiskey lactone, γ-octalactone, cis-whiskey lactone, γ-nonalactone, γ-decalactone, δ-decalactone, and γ-undecalactone in wines. Method reproducibility and repeatability ranged between 0.6 and 5.2% for all compounds. Detection limit for γ-butyrolactone was 0.17 mg/L and a few μg/L for the rest of the compounds. The optimized method has been applied to several wine samples.

  18. Tank 241-U-106 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-U-106. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedures that were presented in other reports. The vapor and headspace gas samples were collected to determine the potential risks to tank farm workers due to fugitive emissions from the tank

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

    Directory of Open Access Journals (Sweden)

    Đurović-Pejčev Rada

    2016-01-01

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

  20. Determination of roasted pistachio (Pistacia vera L.) key odorants by headspace solid-phase microextraction and gas chromatography-olfactometry.

    Science.gov (United States)

    Aceña, Laura; Vera, Luciano; Guasch, Josep; Busto, Olga; Mestres, Montserrat

    2011-03-23

    Key odorants in roasted pistachio nuts have been determined for the first time. Two different pistachio varieties (Fandooghi and Kerman) have been analyzed by means of headspace solid-phase microextraction (HS-SPME) and gas chromatography-olfactometry (GCO). The aroma extract dilution analyses (AEDA) applied have revealed 46 and 41 odor-active regions with a flavor dilution (FD) factor≥64 for the Fandooghi and the Kerman varieties, respectively, and 39 of them were related to precisely identified compounds. These included esters, pyrazines, aldehydes, acids, furans, and phenols. The results show that the Fandooghi variety presents, not only more odor-active regions but also higher FD factors than the Kerman variety that can lead to the conclusion that the first variety has a richer aromatic profile than the second one. The descriptive sensory analysis (DSA) showed that the roasted, chocolate/coffee, and nutty attributes were rated significantly higher in the Fandooghi variety, whereas the green attribute was significantly higher in the Kerman one.

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

    Directory of Open Access Journals (Sweden)

    Jiyuan Zhang

    2014-09-01

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

  2. [A novel vapor dynamic headspace enrichment equipment for nontarget screening of volatile organic compounds in drinking water].

    Science.gov (United States)

    Ma, Huilian; Zhang, Haijun; Tian, Yuzeng; Wang, Longxing; Chen, Jiping

    2011-09-01

    A novel vapor dynamic headspace enrichment device was set up for nontarget screening of volatile organic compounds (VOCs) in drinking water. The main operating parameters of this device, such as length of distillation tube, volume of collected condensate, and choice of absorbent, were optimized. In this device, vapor was utilized as a purge gas and water was utilized as a absorbent. With the help of the device, one liter of water sample could be concentrated to 5 mL and the sensitivity of traditional purge and trap-gas chromatography-mass spectrometry (P&T-GC-MS) could be improved 1-2 orders of magnitude. Source and disinfected water samples from a water treatment plant were analyzed with this method. Compared with the traditional P&T-GC-MS analysis without pre-enrichment, the numbers of identified VOCs were improved from 0 to 16 for source water and 5 to 35 for disinfected water samples. It is also shown that there are many halide compounds in VOCs in disinfected water which do not exist in source water.

  3. Microwave-assisted headspace single-drop microextration of chlorobenzenes from water samples

    Energy Technology Data Exchange (ETDEWEB)

    Vidal, Lorena [Departamento de Quimica Analitica, Nutricion y Bromatologia, Universidad de Alicante, P.O. Box 99, E-03080 Alicante (Spain); Domini, Claudia E. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Universidad de Alicante, P.O. Box 99, E-03080 Alicante (Spain); Grane, Nuria [Departamento de Quimica Analitica, Nutricion y Bromatologia, Universidad de Alicante, P.O. Box 99, E-03080 Alicante (Spain); Psillakis, Elefteria [Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania, Crete (Greece); Canals, Antonio [Departamento de Quimica Analitica, Nutricion y Bromatologia, Universidad de Alicante, P.O. Box 99, E-03080 Alicante (Spain)]. E-mail: a.canals@ua.es

    2007-05-29

    A one-step and in-situ sample preparation method used for quantifying chlorobenzene compounds in water samples has been developed, coupling microwave and headspace single-drop microextraction (MW-HS-SDME). The chlorobenzenes in water samples were extracted directly onto an ionic liquid single-drop in headspace mode under the aid of microwave radiation. For optimization, a Plackett-Burman screening design was initially used, followed by a mixed-level factorial design. The factors considered were: drop volume, aqueous sample volume, stirring speed, ionic strength, extraction time, ionic liquid type, microwave power and length of the Y-shaped glass-tube. The optimum experimental conditions found from this statistical evaluation were: a 5 {mu}L microdrop of 1-hexyl-3-methylimidazolium hexafluorophosphate exposed for 20 min to the headspace of a 30 mL aqueous sample, irradiated by microwaves at 200 W and placed in a 50 mL spherical flask connected to a 25 cm Y-shaped glass-tube. Under the optimised experimental conditions, the response of a high performance liquid chromatographic system was found to be linear over the range studied and with correlation coefficients ranging between 0.9995 and 0.9999. The method showed a good level of repeatability, with relative standard deviations varying between 2.3 and 8.3% (n = 5). Detection limits were found in the low {mu}g L{sup -1} range varying between 0.016 and 0.039 {mu}g L{sup -1}. Overall, the performance of the proposed method demonstrated the favourable effect of microwave sample irradiation upon HS-SDME. Finally, recovery studies from different types of environmental water samples revealed that matrix had little effect upon extraction.

  4. Microwave-assisted headspace single-drop microextration of chlorobenzenes from water samples

    International Nuclear Information System (INIS)

    Vidal, Lorena; Domini, Claudia E.; Grane, Nuria; Psillakis, Elefteria; Canals, Antonio

    2007-01-01

    A one-step and in-situ sample preparation method used for quantifying chlorobenzene compounds in water samples has been developed, coupling microwave and headspace single-drop microextraction (MW-HS-SDME). The chlorobenzenes in water samples were extracted directly onto an ionic liquid single-drop in headspace mode under the aid of microwave radiation. For optimization, a Plackett-Burman screening design was initially used, followed by a mixed-level factorial design. The factors considered were: drop volume, aqueous sample volume, stirring speed, ionic strength, extraction time, ionic liquid type, microwave power and length of the Y-shaped glass-tube. The optimum experimental conditions found from this statistical evaluation were: a 5 μL microdrop of 1-hexyl-3-methylimidazolium hexafluorophosphate exposed for 20 min to the headspace of a 30 mL aqueous sample, irradiated by microwaves at 200 W and placed in a 50 mL spherical flask connected to a 25 cm Y-shaped glass-tube. Under the optimised experimental conditions, the response of a high performance liquid chromatographic system was found to be linear over the range studied and with correlation coefficients ranging between 0.9995 and 0.9999. The method showed a good level of repeatability, with relative standard deviations varying between 2.3 and 8.3% (n = 5). Detection limits were found in the low μg L -1 range varying between 0.016 and 0.039 μg L -1 . Overall, the performance of the proposed method demonstrated the favourable effect of microwave sample irradiation upon HS-SDME. Finally, recovery studies from different types of environmental water samples revealed that matrix had little effect upon extraction

  5. Magnetic headspace adsorptive extraction of chlorobenzenes prior to thermal desorption gas chromatography-mass spectrometry

    International Nuclear Information System (INIS)

    Vidal, Lorena; Ahmadi, Mazaher; Fernández, Elena; Madrakian, Tayyebeh; Canals, Antonio

    2017-01-01

    This study presents a new, user-friendly, cost-effective and portable headspace solid-phase extraction technique based on graphene oxide decorated with iron oxide magnetic nanoparticles as sorbent, located on one end of a small neodymium magnet. Hence, the new headspace solid-phase extraction technique has been called Magnetic Headspace Adsorptive Extraction (Mag-HSAE). In order to assess Mag-HSAE technique applicability to model analytes, some chlorobenzenes were extracted from water samples prior to gas chromatography-mass spectrometry determination. A multivariate approach was employed to optimize the experimental parameters affecting Mag-HSAE. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; extraction time, 30 min; sorbent amount, 10 mg; stirring speed, 1500 rpm, and ionic strength, non-significant), obtaining a linear response from 0.5 to 100 ng L −1 for 1,3-DCB, 1,4-DCB, 1,2-DCB, 1,3,5-TCB, 1,2,4-TCB and 1,2,3-TCB; from 0.5 to 75 ng L −1 for 1,2,4,5-TeCB, and PeCB; and from 1 to 75 ng L −1 for 1,2,3,4-TeCB. The repeatability of the proposed method was evaluated at 10 ng L −1 and 50 ng L −1 spiking levels, and coefficients of variation ranged between 1.5 and 9.5% (n = 5). Limits of detection values were found between 93 and 301 pg L −1 . Finally, tap, mineral and effluent water were selected as real water samples to assess method applicability. Relative recoveries varied between 86 and 110% showing negligible matrix effects. - Highlights: • A new extraction technique named Magnetic Headspace Adsorptive Extraction is presented. • Graphene oxide/iron oxide composite deposited on a neodymiun magnet as sorbent. • Sorbent of low cost, rapid and simple synthesis, easy manipulation and portability options. • Fast and efficient extraction and sensitive determination of chlorobenzenes in water samples.

  6. Determination of binding-dioxygen in dioxygen complexes by headspace gas chromatography.

    Science.gov (United States)

    Wang, Wei; Feng, Shun; Li, Ya-ni; Wu, Meiying; Wang, Jide

    2008-06-06

    Dioxygen complexes play important roles in organisms' bodies, so the determination of binding-dioxygen has practical significance. A simple and robust method based on headspace gas chromatography was proposed to determine the binding-dioxygen in dioxygen complexes. By measuring the content change of nitrogen gas in a vial, the amount of oxygen released from dixoygen complexes can be determined. The method was validated using potassium chlorate as model sample, and the results exhibited good recoveries (90-99%) with the relative standard deviation less than 8%. It was also used to analyze dioxygen complex of cobalt bis(salicylaldehyde) ethylenediimine and polyamine cobalt complexes prepared by solid-phase reaction.

  7. Magnetic headspace adsorptive extraction of chlorobenzenes prior to thermal desorption gas chromatography-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Vidal, Lorena, E-mail: lorena.vidal@ua.es [Department of Analytical Chemistry, Nutrition and Food Sciences and University Institute of Materials, University of Alicante, P.O. Box 99, E-03080, Alicante (Spain); Ahmadi, Mazaher [Faculty of Chemistry, Bu-Ali Sina University, Hamedan (Iran, Islamic Republic of); Fernández, Elena [Department of Analytical Chemistry, Nutrition and Food Sciences and University Institute of Materials, University of Alicante, P.O. Box 99, E-03080, Alicante (Spain); Madrakian, Tayyebeh [Faculty of Chemistry, Bu-Ali Sina University, Hamedan (Iran, Islamic Republic of); Canals, Antonio, E-mail: a.canals@ua.es [Department of Analytical Chemistry, Nutrition and Food Sciences and University Institute of Materials, University of Alicante, P.O. Box 99, E-03080, Alicante (Spain)

    2017-06-08

    This study presents a new, user-friendly, cost-effective and portable headspace solid-phase extraction technique based on graphene oxide decorated with iron oxide magnetic nanoparticles as sorbent, located on one end of a small neodymium magnet. Hence, the new headspace solid-phase extraction technique has been called Magnetic Headspace Adsorptive Extraction (Mag-HSAE). In order to assess Mag-HSAE technique applicability to model analytes, some chlorobenzenes were extracted from water samples prior to gas chromatography-mass spectrometry determination. A multivariate approach was employed to optimize the experimental parameters affecting Mag-HSAE. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; extraction time, 30 min; sorbent amount, 10 mg; stirring speed, 1500 rpm, and ionic strength, non-significant), obtaining a linear response from 0.5 to 100 ng L{sup −1} for 1,3-DCB, 1,4-DCB, 1,2-DCB, 1,3,5-TCB, 1,2,4-TCB and 1,2,3-TCB; from 0.5 to 75 ng L{sup −1} for 1,2,4,5-TeCB, and PeCB; and from 1 to 75 ng L{sup −1} for 1,2,3,4-TeCB. The repeatability of the proposed method was evaluated at 10 ng L{sup −1} and 50 ng L{sup −1} spiking levels, and coefficients of variation ranged between 1.5 and 9.5% (n = 5). Limits of detection values were found between 93 and 301 pg L{sup −1}. Finally, tap, mineral and effluent water were selected as real water samples to assess method applicability. Relative recoveries varied between 86 and 110% showing negligible matrix effects. - Highlights: • A new extraction technique named Magnetic Headspace Adsorptive Extraction is presented. • Graphene oxide/iron oxide composite deposited on a neodymiun magnet as sorbent. • Sorbent of low cost, rapid and simple synthesis, easy manipulation and portability options. • Fast and efficient extraction and sensitive determination of chlorobenzenes in water samples.

  8. A volatile tracer-assisted headspace analytical technique for determining the swelling capacity of superabsorbent polymers.

    Science.gov (United States)

    Zhang, Shu-Xin; Jiang, Ran; Chai, Xin-Sheng

    2017-09-01

    This paper reports on a new method for the determination of swelling capacity of superabsorbent polymers by a volatile tracer-assisted headspace gas chromatography (HS-GC). Toluene was used as a tracer and added to the solution for polymers swelling test. Based on the differences of the tracer partitioned between the vapor and hydrogel phase before and after the polymer's swelling capacity, a transition point (corresponding to the material swelling capacity) can be observed when plotting the GC signal of toluene vs. the ratio of solution added to polymers. The present method has good precision (RSDpolymers at the elevated temperatures. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Vented spikes improve delivery from intravenous bags with no air headspace.

    Science.gov (United States)

    Galush, William J; Horst, Travis A

    2015-07-01

    Flexible plastic bags are the container of choice for most intravenous (i.v.) infusions. Under certain circumstances, however, the air-liquid interface present in these i.v. bags can lead to physical instability of protein biopharmaceuticals, resulting in product aggregation. In principle, the air headspace present in the bags can be removed to increase drug stability, but experiments described here show that this can result in incomplete draining of solution from the bag using gravity delivery, or generation of negative pressure in the bag when an infusion pump is used. It is expected that these issues could lead to incomplete delivery of medication to patients or pump-related problems, respectively. However, here it is shown that contrary to the standard pharmacy practice of using nonvented spikes with i.v. bags, the use of vented spikes with i.v. bags that lack air headspace allows complete delivery of the dose solution without impacting the physical stability of a protein-based drug. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  10. Efficient quantification of water content in edible oils by headspace gas chromatography with vapour phase calibration.

    Science.gov (United States)

    Xie, Wei-Qi; Gong, Yi-Xian; Yu, Kong-Xian

    2018-06-01

    An automated and accurate headspace gas chromatographic (HS-GC) technique was investigated for rapidly quantifying water content in edible oils. In this method, multiple headspace extraction (MHE) procedures were used to analyse the integrated water content from the edible oil sample. A simple vapour phase calibration technique with an external vapour standard was used to calibrate both the water content in the gas phase and the total weight of water in edible oil sample. After that the water in edible oils can be quantified. The data showed that the relative standard deviation of the present HS-GC method in the precision test was less than 1.13%, the relative differences between the new method and a reference method (i.e. the oven-drying method) were no more than 1.62%. The present HS-GC method is automated, accurate, efficient, and can be a reliable tool for quantifying water content in edible oil related products and research. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  11. Headspace single-drop microextraction coupled to microvolume UV-vis spectrophotometry for iodine determination

    International Nuclear Information System (INIS)

    Pena-Pereira, Francisco; Lavilla, Isela; Bendicho, Carlos

    2009-01-01

    Headspace single-drop microextraction has been combined with microvolume UV-vis spectrophotometry for iodine determination. Matrix separation and preconcentration of iodide following in situ volatile iodine generation and extraction into a microdrop of N,N'-dimethylformamide is performed. An exhaustive characterization of the microextraction system and the experimental variables affecting iodine generation from iodide was carried out. The procedure employed consisted of exposing 2.5 μL of N,N'-dimethylformamide to the headspace of a 10 mL acidic (H 2 SO 4 2 mol L -1 ) aqueous solution containing 1.7 mol L -1 Na 2 SO 4 for 7 min. Addition of 1 mL of H 2 O 2 1 mol L -1 for in situ iodine generation was performed. The limit of detection was determined as 0.69 μg L -1 . The repeatability, expressed as relative standard deviation, was 4.7% (n = 6). The calibration working range was from 5 to 200 μg L -1 (r 2 = 0.9991). The large preconcentration factor obtained, ca. 623 in only 7 min, compensate for the 10-fold loss in sensitivity caused by the decreased optical path, which results in improved detection limits as compared to spectrophotometric measurements carried out with conventional sample cells. The method was successfully applied to the determination of iodine in water, pharmaceutical and food samples

  12. Australian young people's awareness of headspace, beyondblue and other mental health organizations.

    Science.gov (United States)

    Jorm, Anthony F

    2009-12-01

    Objective: The aim of this paper is to assess young people's awareness of mental health organizations supporting their age group. Of particular interest was awareness of headspace, which was created in 2006 to provide youth-oriented mental health services, and of beyondblue, which aims to raise community awareness of depression, anxiety and related disorders. Method: A telephone survey was carried out on a national sample of young people who were part of a 2-year follow-up study of youth mental health literacy. Data were analysed for those aged 13-25 years. Results: Awareness was highest for beyondblue and telephone helplines; headspace had established some awareness, particularly in areas where its services operate. However, awareness was unrelated to the participant's psychological symptoms in the past year. Conclusions: If youth-oriented services are to be successful, young people need to know about them. Awareness campaigns need to be targeted at the sub-group who have greatest need for these services, namely those with mental health problems.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-06-01

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

  14. Data on changes in red wine phenolic compounds, headspace aroma compounds and sensory profile after treatment of red wines with activated carbons with different physicochemical characteristics

    Directory of Open Access Journals (Sweden)

    Luís Filipe-Ribeiro

    2017-06-01

    Full Text Available Data in this article presents the changes on phenolic compounds, headspace aroma composition and sensory profile of a red wine spiked with 4-ethylphenol and 4-ethylguaiacol and treated with seven activated carbons with different physicochemical characteristics, namely surface area, micropore volume and mesopore volume (“Reduction of 4-ethylphenol and 4-ethylguaiacol in red wine by activated carbons with different physicochemical characteristics: impact on wine quality” Filipe-Ribeiro et al. (2017 [1]. Data on the physicochemical characteristics of the activated carbons are shown. Statistical data on the sensory expert panel consistency by General Procrustes Analysis is shown. Statistical data is also shown, which correlates the changes in chemical composition of red wines with the physicochemical characteristics of activated carbons used.

  15. Data on changes in red wine phenolic compounds, headspace aroma compounds and sensory profile after treatment of red wines with activated carbons with different physicochemical characteristics.

    Science.gov (United States)

    Filipe-Ribeiro, Luís; Milheiro, Juliana; Matos, Carlos C; Cosme, Fernanda; Nunes, Fernando M

    2017-06-01

    Data in this article presents the changes on phenolic compounds, headspace aroma composition and sensory profile of a red wine spiked with 4-ethylphenol and 4-ethylguaiacol and treated with seven activated carbons with different physicochemical characteristics, namely surface area, micropore volume and mesopore volume ("Reduction of 4-ethylphenol and 4-ethylguaiacol in red wine by activated carbons with different physicochemical characteristics: impact on wine quality" Filipe-Ribeiro et al. (2017) [1]). Data on the physicochemical characteristics of the activated carbons are shown. Statistical data on the sensory expert panel consistency by General Procrustes Analysis is shown. Statistical data is also shown, which correlates the changes in chemical composition of red wines with the physicochemical characteristics of activated carbons used.

  16. Tank 241-TY-103 headspace gas and vapor characterization results for samples collected in August 1994 and April 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  17. Tank 241-TX-118 headspace gas and vapor characterization results for samples collected in September 1994 and December 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  18. Tank 241-C-108 headspace gas and vapor characterization results for samples collected in July 1993 and August 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  19. Tank 241-BY-107 headspace gas and vapor characterization results for samples collected in March 1994 and October 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  20. Tank 241-BY-104 headspace gas and vapor characterization results for samples collected in April 1994 and June 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  1. Tank 241-BY-106 headspace gas and vapor characterization results for samples collected in May 1994 and July 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  2. Tank 241-C-112 headspace gas and vapor characterization results for samples collected in June 1994 and August 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  3. Tank 241-BY-103 headspace gas and vapor characterization results for samples collected in May 1994 and November 1994

    International Nuclear Information System (INIS)

    Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  4. Tank 241-C-109 headspace gas and vapor characterization results for samples collected in August 1994. Revision 2

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  5. Tank 241-C-111 headspace gas and vapor characterization results for samples collected in August 1993 and September 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  6. Tank 241-BY-108 headspace gas and vapor characterization results for samples collected in March 1994 and October 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  7. Tank 241-BY-110 Headspace Gas and Vapor Characterization Results for Samples Collected in November 1994. Revision 2

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  8. Tank 241-C-105 headspace gas and vapor characterization results for samples collected in February 1994. Revision 1

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  9. Tank 241-BY-111 headspace gas and vapor characterization results for samples collected in May 1994 and November 1994

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-01-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  10. Tank 241-TY-101 headspace gas and vapor characterization results for samples collected in August 1994 and April 1995

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

  11. Hydride generation coupled to microfunnel-assisted headspace liquid-phase microextraction for the determination of arsenic with UV-Vis spectrophotometry.

    Science.gov (United States)

    Hashemniaye-Torshizi, Reihaneh; Ashraf, Narges; Arbab-Zavar, Mohammad Hossein

    2014-12-01

    In this research, a microfunnel-assisted headspace liquid-phase microextraction technique has been used in combination with hydride generation to determine arsenic (As) by UV-Vis spectrophotometry. The method is based on the reduction of As to arsine (AsH3) in acidic media by sodium tetrahydroborate (NaBH4) followed by its subsequent reaction with silver diethyldithiocarbamate (AgDDC) to give an absorbing complex at 510 nm. The complexing reagent (AgDDC) has been dissolved in a 1:1 (by the volume ratio) mixture of chloroform/chlorobenzene microdroplet and exposed to the generated gaseous arsine via a reversed microfunnel in the headspace of the sample solution. Several operating parameters affecting the performance of the method have been examined and optimized. Acetonitrile solvent has been added to the working samples as a sensitivity enhancement agent. Under the optimized operating conditions, the detection limit has been measured to be 0.2 ng mL(-1) (based on 3sb/m criterion, n b = 8), and the calibration curve was linear in the range of 0.5-12 ng mL(-1). The relative standard deviation for eight replicate measurements was 1.9 %. Also, the effects of several potential interferences have been studied. The accuracy of the method was validated through the analysis of JR-1 geological standard reference material. The method has been successfully applied for the determination of arsenic in raw and spiked soft drink and water samples with the recoveries that ranged from 91 to 106 %.

  12. Determination of ammonium in aqueous samples using new headspace dynamic in-syringe liquid-phase microextraction with in situ derivitazation coupled with liquid chromatography-fluorescence detection.

    Science.gov (United States)

    Muniraj, Sarangapani; Yan, Cheing-Tong; Shih, Hou-Kung; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

    2012-11-19

    A new simultaneous derivatization and extraction method for the preconcentration of ammonia using new one-step headspace dynamic in-syringe liquid-phase microextraction with in situ derivatization was developed for the trace determination of ammonium in aqueous samples by liquid chromatography with fluorescence detection (LC-FLD). The acceptor phase (as derivatization reagent) containing o-phthaldehyde and sodium sulfite was held within a syringe barrel and immersed in the headspace of sample container. The gaseous ammonia from the alkalized aqueous sample formed a stable isoindole derivative with the acceptor phase inside the syringe barrel through the reciprocated movements of plunger. After derivatization-cum-extraction, the acceptor phase was directly injected into LC-FLD for analysis. Parameters affecting the ammonia evolution and the extraction/derivatization efficiency such as sample matrix, pH, temperature, sampling time, and the composition of derivatization reagent, reaction temperature, and frequency of reciprocated plunger, were studied thoroughly. Results indicated that the maximum extraction efficiency was obtained by using 100μL derivatization reagent in a 1-mL gastight syringe under 8 reciprocated movements of plunger per min to extract ammonia evolved from a 20mL alkalized aqueous solution at 70°C (preheated 4min) with 380rpm stirring for 8min. The detection was linear in the concentration range of 0.625-10μM with the correlation coefficient of 0.9967 and detection limit of 0.33μM (5.6ng mL(-1)) based on SN(-1)=3. The method was applied successfully to determine ammonium in real water samples without any prior cleanup of the samples, and has been proved to be a simple, sensitive, efficient and cost-effective procedure for trace ammonium determination in aqueous samples. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    Llop, Anna; Pocurull, Eva; Borrull, Francesc

    2010-01-22

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

  14. Expanding the use of polymeric ionic liquids in headspace solid-phase microextraction: Determination of ultraviolet filters in water samples.

    Science.gov (United States)

    Trujillo-Rodríguez, María J; Nan, He; Anderson, Jared L

    2018-03-09

    Three crosslinked polymeric ionic liquid (PIL) sorbent coatings were used in headspace solid-phase microextraction for the determination of a group of ultraviolet filters. The developed crosslinked PIL-based materials include two polycations and a double confined PIL. The method, in combination with gas chromatography-mass spectrometry, is simple, solvent free, and does not require of any derivatization step. After proper optimization of the methodologies with each developed fiber, the analytical performance was compared with a commercial polyacrylate fiber. A study of the normalized calibration slopes, obtained by dividing the calibration slope of each analyte by the coating volume, revealed that the crosslinked fibers can be used as alternatives to commercial fibers for the determination of the selected group of compounds. In particular, the coating nature of the PIL containing the 1-vinylbenzyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide IL as monomer and the 1,12-di(3-vinylbenzylimidazolium)dodecane bis[(trifluoromethyl)sulfonyl]imide IL as crosslinker is the most suitable for the extraction of the selected compounds despite their coating volume, being 3.6 times lower than the commercial polyacrylate fiber. For this fiber, wide linear ranges, correlation coefficients higher than 0.990, limits of detection ranging from 2.8 ng L -1 to 26 ng L -1 and relative standard deviations ranging from 2.5 to 15% were achieved. Finally, all proposed PIL-based fibers were applied towards the analysis of tap water, pool water and lake water, with the majority of the ultraviolet filters being detected and quantified in the last two types of samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Novel proton-type ionic liquid doped polyaniline for the headspace solid-phase microextraction of amines

    International Nuclear Information System (INIS)

    Ai, Youhong; Zhao, Faqiong; Zeng, Baizhao

    2015-01-01

    Graphical abstract: The novel proton-type ionic liquid (1-sulfobutyl-3-methylimidazolium hydrosulfate) doped polyaniline coating showed granular porous nanostructure and it had high self-EF values and extraction efficiency for amines. - Highlights: • A proton-type ionic liquid-doped polyaniline was fabricated by electrodeposition. • It showed porous granular nanostructure and had large specific surface. • It had high extraction capacity to aromatic amines. • A reasonable self-enrichment factor of SPME fiber has been proposed. - Abstract: A novel proton-type ionic liquid doped polyaniline (HIL-doped PANI) coating was presented, which was prepared on a stainless steel wire by electrodeposition in an aqueous solution containing aniline and 1-sulfobutyl-3-methylimidazolium hydrosulfate. The HIL-doped PANI coating showed granular nanostructure and had large specific surface. When it was applied to the headspace solid-phase microextraction of several amines (i.e., aniline, N-methylaniline, 3-methylaniline, 2-chloroaniline and 3-chloroaniline), it showed high extraction efficiency. The enrichment factors were 191.8–343.9 for different amines, much higher than those of common PANI and commercial polydimethylsiloxane/divinylbenzene coatings. Coupled with gas chromatographic analysis, the linear ranges were 0.097–100 μg/L with correlation coefficients above 0.9942, and the detection limits were 0.012–0.048 μg/L (S/N = 3) for different amines. The relative standard deviations (RSD) were smaller than 8.1% for five successive measurements with single fiber and the fiber-to-fiber RSDs were 8.6–13.8% (n = 5) for these amines. The proposed method was successfully applied to the extraction and determination of amines in organic waste water samples, and the recoveries were 78.3–112.8% for different analytes

  16. Novel proton-type ionic liquid doped polyaniline for the headspace solid-phase microextraction of amines

    Energy Technology Data Exchange (ETDEWEB)

    Ai, Youhong [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials & Key Laboratory for the Synthesis and Application of Organic Functional Molecules (Ministry of Education), College of Chemistry & Chemical Engineering, Hubei University, Wuhan 430062 (China); Zhao, Faqiong [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Zeng, Baizhao, E-mail: bzzeng@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China)

    2015-06-23

    Graphical abstract: The novel proton-type ionic liquid (1-sulfobutyl-3-methylimidazolium hydrosulfate) doped polyaniline coating showed granular porous nanostructure and it had high self-EF values and extraction efficiency for amines. - Highlights: • A proton-type ionic liquid-doped polyaniline was fabricated by electrodeposition. • It showed porous granular nanostructure and had large specific surface. • It had high extraction capacity to aromatic amines. • A reasonable self-enrichment factor of SPME fiber has been proposed. - Abstract: A novel proton-type ionic liquid doped polyaniline (HIL-doped PANI) coating was presented, which was prepared on a stainless steel wire by electrodeposition in an aqueous solution containing aniline and 1-sulfobutyl-3-methylimidazolium hydrosulfate. The HIL-doped PANI coating showed granular nanostructure and had large specific surface. When it was applied to the headspace solid-phase microextraction of several amines (i.e., aniline, N-methylaniline, 3-methylaniline, 2-chloroaniline and 3-chloroaniline), it showed high extraction efficiency. The enrichment factors were 191.8–343.9 for different amines, much higher than those of common PANI and commercial polydimethylsiloxane/divinylbenzene coatings. Coupled with gas chromatographic analysis, the linear ranges were 0.097–100 μg/L with correlation coefficients above 0.9942, and the detection limits were 0.012–0.048 μg/L (S/N = 3) for different amines. The relative standard deviations (RSD) were smaller than 8.1% for five successive measurements with single fiber and the fiber-to-fiber RSDs were 8.6–13.8% (n = 5) for these amines. The proposed method was successfully applied to the extraction and determination of amines in organic waste water samples, and the recoveries were 78.3–112.8% for different analytes.

  17. A screening method for polycyclic aromatic hydrocarbons determination in water by headspace SPME with GC-FID

    Energy Technology Data Exchange (ETDEWEB)

    Zuazagoitia, D.; Millan, E.; Garcia, R. [Univ. of Pais Vasco, Donostia-San Sebastian (Spain). Dept. of Applied Chemistry

    2007-11-15

    A simple method for determination of polycyclic aromatic hydrocarbons (PAHs) in water using headspace solid-phase microextraction (HS-SPME) with gas chromatography-flame ionisation detector (GC-FID) was developed. In order to obtain the convenient experimental conditions for HS-SPME extraction an experimental design with two steps was accomplished. A 2{sup 6-2} fractional factorial design and central composite design (CCD) considering three significant factors were used. Naphthalene, anthracene and fluoranthene were chosen as representatives of two, three and four aromatic rings, and the global response of three PAHs was used for the results, evaluation. The chosen extraction conditions were: 85 {mu}m polyacrylate fibre; 50 C temperature; 60 min time; 20 mL-dissolution volume (in 40 mL glass vial); without salt addition; and 2 min desorption time. The procedure was extended to other seven PAHs (acenaphthylene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene and benzo(a)anthracene) and the analytical characteristics were checked. The limit of detection (LOD) was from 0.08 (anthracene) to 0.20 {mu}g L{sup -1} (naphthalene). The precision expressed as relative standard deviation (RSD in %) using 50 {mu}g L{sup -1} of each analyte ranged from 6.8 to 17 %. The method was applied to the analysis of the surface waters and leaching waters of contaminated soils from Gipuzkoa (North Spain). The PAHs were not detected in surface water samples. Most of the PAHs were found in the leachates from contaminated soils showing a maximum global value of 75.5 {mu}g L{sup -1}. (orig.)

  18. Determination of perfluorobutane in rat blood by automatic headspace capillary gas chromatography and selected ion monitoring mass spectrometry.

    Science.gov (United States)

    Hvattum, E; Normann, P T; Oulie, I; Uran, S; Ringstad, O; Skotland, T

    2001-01-01

    A new contrast agent (Sonazoid; NC100100) for ultrasound imaging has been developed. It is an aqueous suspension of lipid stabilised perfluorobutane (PFB) gas microbubbles. An automatic headspace capillary gas-chromatographic mass spectrometric method using electron impact ionisation was developed for analysis of Sonazoid PFB in rat blood. The calibration standards were gaseous PFB dissolved in ethanol in the range of 0.5-5000 ng PFB. Fluorotrichloromethane (CFC 11) was used as an internal standard of the method and the MS detector was set to single ion monitoring of the base fragment ions of PFB (m/z 69 and 119) and CFC 11 (m/z 101). The calibration graph, made by plotting the peak area ratios of PFB (m/z 69) to CFC 11(m/z 101) against the amount of PFB, was fitted to a second-order polynomial equation with weighting 1/y2 and found to be reproducible. The limit of quantification of the method was set to 0.4 ng PFB. The between-day variation of the method was below 9.2% relative standard deviation (RSD) and the within-day variation of the method was below 7.6% RSD. The accuracy of the method, as compared to Coulter counter, was estimated by determination of PFB in samples where Sonazoid was added to saline and found to range from 91.5% to 105.2%. PFB, added as Sonazoid, was found to be stable for at least 7 months in rat blood samples when stored at -20 degrees C.

  19. (Vapour + liquid) equilibria of ternary systems with ionic liquids using headspace gas chromatography

    International Nuclear Information System (INIS)

    Mokhtarani, Babak; Gmehling, Juergen

    2010-01-01

    (Vapour + liquid) equilibrium (VLE) data for the ternary systems (hexane + benzene), (hexane + cyclohexane), (benzene + cyclohexane), and (ethanol + water) with an ionic liquid as entrainer for extractive distillation were measured by headspace gas chromatography. As ionic liquids, 1-hexyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [HMIM][BTI], 1-octyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [OMIM][BTI], 1-octyl-3-methyl-imidazolium trifluoro-methanesulfonate [OMIM][OTF], and 1-butyl-3-methyl-imidazolium trifluoro-methanesulfonate [BMIM][OTF] were used. The experimental data show that the ionic liquids investigated have a great influence on the separation factors of the systems (hexane + benzene), (hexane + cyclohexane), and (benzene + cyclohexane). The experimental data were compared with the predicted results using mod. UNIFAC (Do). The predicted results are in good agreement with the experimental data.

  20. Headspace Solid Phase Micro Extraction Gas Chromatographic Determination of Fenthion in Human Serum

    Directory of Open Access Journals (Sweden)

    Kyriaki Machera

    2008-05-01

    Full Text Available A simple and effective analytical procedure was developed for the determination of fenthion residues in human serum samples. The sample treatment was performed using the headspace solid-phase micro extraction with polyacrylate fiber, which has the advantage to require low amount of serum (1 mL without tedious pre-treatment. The quantification of fenthion was carried out by gas chromatography-mass spectrometry and the recoveries ranged from 79 to 104% at two spiking levels for 6 replicates. Detection and quantification limits were calculated as 1.51 and 4.54 ng/mL of serum respectively. Two fenthion metabolites − fenoxon and fenthion–sulfoxide − were also identified.

  1. Identification of volatiles by headspace gas chromatography with simultaneous flame ionization and mass spectrometric detection.

    Science.gov (United States)

    Tiscione, Nicholas B; Yeatman, Dustin Tate; Shan, Xiaoqin; Kahl, Joseph H

    2013-10-01

    Volatiles are frequently abused as inhalants. The methods used for identification are generally nonspecific if analyzed concurrently with ethanol or require an additional analytical procedure that employs mass spectrometry. A previously published technique utilizing a capillary flow technology splitter to simultaneously quantitate and confirm ethyl alcohol by flame ionization and mass spectrometric detection after headspace sampling and gas chromatographic separation was evaluated for the detection of inhalants. Methanol, isopropanol, acetone, acetaldehyde, toluene, methyl ethyl ketone, isoamyl alcohol, isobutyl alcohol, n-butyl alcohol, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane (Norflurane, HFC-134a), chloroethane, trichlorofluoromethane (Freon®-11), dichlorodifluoromethane (Freon®-12), dichlorofluoromethane (Freon®-21), chlorodifluoromethane (Freon®-22) and 1,2-dichlorotetrafluoroethane (Freon®-114) were validated for qualitative identification by this method. The validation for qualitative identification included evaluation of matrix effects, sensitivity, carryover, specificity, repeatability and ruggedness/robustness.

  2. (Vapour + liquid) equilibria of ternary systems with ionic liquids using headspace gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtarani, Babak [Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran (Iran, Islamic Republic of); Gmehling, Juergen, E-mail: gmehling@tech.chem.uni-oldenburg.d [Carl von Ossietzky Universitaet Oldenburg, Technische Chemie, D-26111 Oldenburg (Germany)

    2010-08-15

    (Vapour + liquid) equilibrium (VLE) data for the ternary systems (hexane + benzene), (hexane + cyclohexane), (benzene + cyclohexane), and (ethanol + water) with an ionic liquid as entrainer for extractive distillation were measured by headspace gas chromatography. As ionic liquids, 1-hexyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [HMIM][BTI], 1-octyl-3-methyl-imidazolium bis (trifluoromethyl-sulfonyl) imide [OMIM][BTI], 1-octyl-3-methyl-imidazolium trifluoro-methanesulfonate [OMIM][OTF], and 1-butyl-3-methyl-imidazolium trifluoro-methanesulfonate [BMIM][OTF] were used. The experimental data show that the ionic liquids investigated have a great influence on the separation factors of the systems (hexane + benzene), (hexane + cyclohexane), and (benzene + cyclohexane). The experimental data were compared with the predicted results using mod. UNIFAC (Do). The predicted results are in good agreement with the experimental data.

  3. Measurement of activity coefficients of mixtures by head-space gas chromatography: general procedure.

    Science.gov (United States)

    Luis, Patricia; Wouters, Christine; Van der Bruggen, Bart; Sandler, Stanley I

    2013-08-09

    Head-space gas chromatography (HS-GC) is an applicable method to perform vapor-liquid equilibrium measurements and determine activity coefficients. However, the reproducibility of the data may be conditioned by the experimental procedure concerning to the automated pressure-balanced system. The study developed in this work shows that a minimum volume of liquid in the vial is necessary to ensure the reliability of the activity coefficients since it may become a parameter that influences the magnitude of the peak areas: the helium introduced during the pressurization step may produce significant variations of the results when too small volume of liquid is selected. The minimum volume required should thus be evaluated prior to obtain experimentally the concentration in the vapor phase and the activity coefficients. In this work, the mixture acetonitrile-toluene is taken as example, requiring a sample volume of more than 5mL (about more than 25% of the vial volume). The vapor-liquid equilibrium and activity coefficients of mixtures at different concentrations (0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 molar fraction) and four temperatures (35, 45, 55 and 70°C) have been determined. Relative standard deviations (RSD) lower than 5% have been obtained, indicating the good reproducibility of the method when a sample volume larger than 5mL is used. Finally, a general procedure to measure activity coefficients by means of pressure-balanced head-space gas chromatography is proposed. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Volatile profile of the headspace fraction of "assa-peixe" (Vernonia sp. honeys Perfil dos compostos voláteis presentes na fração "headspace" de méis de assa-peixe

    Directory of Open Access Journals (Sweden)

    Mariana Carvalho Ribeiro

    2008-03-01

    Full Text Available The volatile compounds were isolated from the headspace fraction of "assa-peixe" honeys by adsorptive column chromatography, eluted with acetone and analysed by GC-FID and GC-MS. Volatile compounds were separated using a polar phase column. Low- and medium-boiling point volatile compounds predominated in the headspace. A large proportion of 3-penten-2-one (80.5 ± 13.9 µg.kg-1 and benzaldehyde (25.9 ± 4.2 µg.kg-1 was found in the headspace fraction, while 2-penten-1-ol, 3-hexenyl butanoate, octadecane and hexanoic acid (Os compostos voláteis da fração "Headspace" de méis de assa-peixe foram adsorvidos pela técnica de cromatografia de adsorção, eluídos com acetona e analisados através da CG/DIC e CG/EM usando coluna polar de sílica fundida. Os compostos voláteis de baixo e médio ponto de ebulição predominaram na fração "headspace". Foi achada uma grande proporção de 3-penten-2-ona (80,5 ± 13,9 µg.kg-1 e benzaldeído (25,9 ± 4,2 µg.kg-1, enquanto o 2-penten-1-ol, o hexanoato de 3-hexenila, o octadecano e o ácido hexanóico (<0,01 µg.kg-1 foram compostos minoritários. Um total de doze compostos voláteis foi identificado, sendo cinco descritos pela primeira vez no mel de assa-peixe. Destes cinco, a 3-penten-2-ona, o dodecano, o tridecano e o benzaldeído foram definitivamente identificados na fração "headspace" dos méis de assa-peixe brasileiro.

  5. Use of a holder-vacuum tube device to save on-site hands in preparing urine samples for head-space gas-chromatography, and its application to determine the time allowance for sample sealing.

    Science.gov (United States)

    Kawai, Toshio; Sumino, Kimiaki; Ohashi, Fumiko; Ikeda, Masayuki

    2011-01-01

    To facilitate urine sample preparation prior to head-space gas-chromatographic (HS-GC) analysis. Urine samples containing one of the five solvents (acetone, methanol, methyl ethyl ketone, methyl isobutyl ketone and toluene) at the levels of biological exposure limits were aspirated into a vacuum tube via holder, a device commercially available for venous blood collection (the vacuum tube method). The urine sample, 5 ml, was quantitatively transferred to a 20-ml head-space vial prior to HS-GC analysis. The loaded tubes were stored at +4 ℃ in dark for up to 3 d. The vacuum tube method facilitated on-site procedures of urine sample preparation for HS-GC with no significant loss of solvents in the sample and no need of skilled hands, whereas on-site sample preparation time was significantly reduced. Furthermore, no loss of solvents was detected during the 3-d storage, irrespective of hydrophilic (acetone) or lipophilic solvent (toluene). In a pilot application, high performance of the vacuum tube method in sealing a sample in an air-tight space succeeded to confirm that no solvent will be lost when sealing is completed within 5 min after urine voiding, and that the allowance time is as long as 30 min in case of toluene in urine. The use of the holder-vacuum tube device not only saves hands for transfer of the sample to air-tight space, but facilitates sample storage prior to HS-GC analysis.

  6. Factors controlling headspace pressure in a manual manometric BMP method can be used to produce a methane output comparable to AMPTS.

    Science.gov (United States)

    Himanshu, H; Voelklein, M A; Murphy, J D; Grant, J; O'Kiely, P

    2017-08-01

    The manual manometric biochemical methane potential (mBMP) test uses the increase in pressure to calculate the gas produced. This gas production may be affected by the headspace volume in the incubation bottle and by the overhead pressure measurement and release (OHPMR) frequency. The biogas and methane yields of cellulose, barley, silage and slurry were compared with three incubation bottle headspace volumes (50, 90 and 180ml; constant 70ml total medium) and four OHPMR frequencies (daily, each third day, weekly and solely at the end of experiment). The methane yields of barley, silage and slurry were compared with those from an automated volumetric method (AMPTS). Headspace volume and OHPMR frequency effects on biogas yield were mediated mainly through headspace pressure, with the latter having a negative effect on the biogas yield measured and relatively little effect on methane yield. Two mBMP treatments produced methane yields equivalent to AMPTS. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Effect of headspace CO2 concentration on toxin production by Clostridium botulinum in MAP, irradiated fresh pork

    International Nuclear Information System (INIS)

    Lambert, A.D.; Smith, J.P.; Dodds, K.L.

    1991-01-01

    The effects of five initial levels of CO2 (15, 30, 45, 60, and 75%) and three irradiation doses (0, 0.5, and 1.0 kGy) on toxin production by Clostridium botulinum in inoculated fresh pork were studied using factorial design experiments. Headspace CO2 levels increased in all samples during storage at 15 degrees C. In most treatments, spoilage preceded toxigenesis. Toxin production occurred faster in samples initially packaged with 15 to 30% of CO2 while higher levels of CO2 (45-75%) delayed toxin production. Low-dose irradiation delayed toxin production at all levels of CO2 in the package headspace. Contrary to expectations, including a CO2 absorbent in the package enhanced toxin production by C. botulinum. This was attributed to production of H2 by the CO2 absorbent, possibly resulting in a decrease in the oxido-reduction potential of the meat

  8. [Determination of flavor compounds in foxtail millet wine by gas chromatography-mass spectrometry coupled with headspace solid phase microextraction].

    Science.gov (United States)

    Liu, Jingke; Zhang, Aixia; Li, Shaohui; Zhao, Wei; Zhang, Yuzong; Xing, Guosheng

    2017-11-08

    To comprehensively understand flavor compounds and aroma characteristics of foxtail millet wine, extraction conditions were optimized with 85 μm polyacrylate (PA), 100 μm polydimethylsiloxane (PDMS), 75 μm carboxen (CAR)/PDMS and 50/30 μm divinylbenzene (DVB)/CAR/PDMS fibers. The flavor compounds in foxtail millet wine were investigated by gas chromatography-mass spectrometry (GC-MS) coupled with headspace solid phase microextraction (HS-SPME), and the odor characteristics and intensity were analyzed by odor active values (OAVs). The samples of 8 mL were placed in headspace vials with 1.5 g NaCl, then the headspace vials were heated at 60℃ for 40 min. Using HS-SPME with different fibers, a total of 55 flavor compounds were identified from the samples, including alcohols, esters, benzene derivatives, hydrocarbons, acids, aldehydes, ketones, terpenes, phenols and heterocycle compounds. The main flavor compounds were alcohols compounds. According to their OAVs, phenylethyl alcohol, styrene, 1-methyl-naphthalene, 2-methyl-naphthalene, benzaldehyde, benzeneacetaldehyde and 2-methoxy-phenol were established to be odor-active compounds. Phenylethyl alcohol and benzeneacetaldehyde were the most prominent odor-active compounds. PA and PDMS fibers had good extraction effect for polar and nonpolar compounds, respectively. CAR/PDMS and DVB/CAR/PDMS provided a similar compounds profile for moderate polar compounds. This research comprehensively determined flavor compounds of foxtail millet wine, and provided theoretical basis for product development and quality control.

  9. A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

    Science.gov (United States)

    Chai, Xin-Sheng; Zhong, Jin-Feng; Hu, Hui-Chao

    2012-05-18

    This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Full evaporation headspace gas chromatography for sensitive determination of high boiling point volatile organic compounds in low boiling matrices.

    Science.gov (United States)

    Mana Kialengila, Didi; Wolfs, Kris; Bugalama, John; Van Schepdael, Ann; Adams, Erwin

    2013-11-08

    Determination of volatile organic components (VOC's) is often done by static headspace gas chromatography as this technique is very robust and combines easy sample preparation with good selectivity and low detection limits. This technique is used nowadays in different applications which have in common that they have a dirty matrix which would be problematic in direct injection approaches. Headspace by nature favors the most volatile compounds, avoiding the less volatile to reach the injector and column. As a consequence, determination of a high boiling solvent in a lower boiling matrix becomes challenging. Determination of VOCs like: xylenes, cumene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), benzyl alcohol (BA) and anisole in water or water soluble products are an interesting example of the arising problems. In this work, a headspace variant called full evaporation technique is worked out and validated for the mentioned solvents. Detection limits below 0.1 μg/vial are reached with RSD values below 10%. Mean recovery values ranged from 92.5 to 110%. The optimized method was applied to determine residual DMSO in a water based cell culture and DMSO and DMA in tetracycline hydrochloride (a water soluble sample). Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Headspace sorptive solid phase microextraction (HS-SPME) combined with a spectrophotometry system: A simple glass devise for extraction and simultaneous determination of cyanide and thiocyanate in environmental and biological samples.

    Science.gov (United States)

    Al-Saidi, H M; Al-Harbi, Sami A; Aljuhani, E H; El-Shahawi, M S

    2016-10-01

    A simple, low cost and efficient headspace sorptive solid phase microextraction (HS-SPME) method for determination of cyanide has been developed. The system comprises of a glass tube with two valves and a moveable glass slide fixed at its centre. It includes an acceptor phase polyurethane foam treated mercury (II) dithizonate [Hg(HDz)2-PUF] complex fixed inside by a septum cap in a cylindrical configuration (5.0cm length and 1.0cm diameter). The extraction is based upon the contact of the acceptor phase to the headspace and subsequently measuring the absorbance of the recovered mercury (II) dithizonate from PUFs sorbent. Unlike other HSSE, extraction and back - extractions was carried out in a closed system, thereby improving the analytical performance by preventing the analyte loss. Under the optimized conditions, a linear calibration plot in the range of 1.0-50.0µmolL(-1) was achieved with limits of detection (LOD) and quantification (LOQ) of 0.34, 1.2µmolL(-1) CN(-), respectively. Simultaneous analysis of cyanide and thiocyanate in saliva was also performed with satisfactory recoveries. Copyright © 2016. Published by Elsevier B.V.

  12. Application of headspace for research volatile organic compounds emitted from building materials

    Directory of Open Access Journals (Sweden)

    Kultys Beata

    2018-01-01

    Full Text Available Headspace technique and gas chromatography method with mas detector has been used for the determination of volatile organic compounds (VOC emitted from various building and finishing materials, such as sealing foams, mounting strips, paints, varnishes, floor coverings. The tests were carried out for different temperatures (in the temperature range of 60 to 180 °C and the time of heated vials with tested materials inside. These tests were conducted to verify the possibility of use this method of determination the VOC emission. Interpretation of chromatograms and mass spectra allowed to identify the type of compounds emitted from the tested materials and the optimum time and temperature for each type of material was determined. The increase in heating temperature of the samples resulted in increase the type and number of identified compounds: for four materials the increase was in the whole temperature range, for others it was from 90 °C. On the other hand, emission from mineral wool was low in whole temperature range. 30-minutes heating of the samples was sufficient to identify emitted compounds for most of tested materials. Applying a longer time, i.e. 24 hours, significantly increased the sensitivity of the method.

  13. [Simultaneous determination of seven residual solvents in bovis calculus artifactus by headspace gas chromatography].

    Science.gov (United States)

    Chi, Shuyao; Wu, Dike; Sun, Jinhong; Ye, Ruhan; Wang, Xiaoyan

    2014-05-01

    A headspace gas chromatography (HS-GC) method was developed for the simultaneous determination of seven residual solvents (petroleum ether (60-90 degrees C), acetone, ethyl acetate, methanol, methylene chloride, ethanol and butyl acetate) in bovis calculus artifactus. The DB-WAX capillary column and flame ionization detector (FID) were used for the separation and detection of the residual solvents, and the internal standard method was used for the quantification. The chromatographic conditions, such as equilibrium temperature and equilibrium time, were optimized. Under the optimized conditions, all of the seven residual solvents showed good linear relationships with good correlation coefficients (not less than 0.999 3) in the prescribed concentration range. At three spiked levels, the recoveries for the seven residual solvents were 94.7%-105.2% with the relative standard deviations (RSDs) less than 3.5%. The limits of detection (LODs) of the method were 0.43-5.23 mg/L, and the limits of quantification (LOQs) were 1.25-16.67 mg/L. The method is simple, rapid, sensitive and accurate, and is suitable for the simultaneous determination of the seven residual solvents in bovis calculus artifactus.

  14. Developed a needle trap device with PDMS sorbent for microextraction of toluene and methyl ethyl ketone from aquatic samples using dynamic headspace

    Directory of Open Access Journals (Sweden)

    Sara Karimi Zeverdegani

    2016-09-01

    Full Text Available Introduction: Due to the widespread use of toxic chemicals in most workplaces that can lead to toxic effects on human, various chemical extraction technique have been defined for analysis these toxic substances in air, water and biological samples. The purpose of this research is extraction of  toluene and methyl ethyl ketone from aquatic samples with needle trap device and  one commercial sorbent. Methods: In this research, needle trap device was used to extraction of  toluene and methyl ethyl ketone in aquatic samples, so needles(size 20 were packed with PDMS and extraction was done with dynamic headspace needle trap device. Gas chromatography with - flame ionization detector was used to analysis and optimized extraction of two substances were obtained. Results: Results show that the optimum temperature and time extraction was similar for toluene and methyl ethyl ketone (30 ° C, 30 min, but the reproducibility of results and calibration curve that obtained for toluene was better than methyl ethyl ketone. Conclusion: Needle trap technique is inexpensive, sensitive and portable also this method has good recovery to extract small amounts of  toluene and methyl ethyketon from aquatic samples with polydimethylsiloxane.

  15. Selective determination of semi-volatile thiophene compounds in water by molecularly imprinted polymer thin films with direct headspace gas chromatography sulfur chemiluminescence detection.

    Science.gov (United States)

    Hijazi, Hassan Y; Bottaro, Christina S

    2018-02-26

    Water-compatible molecularly imprinted polymer (MIP) thin films are coupled with headspace gas chromatography sulfur chemiluminescence detection (HS-GC-SCD) to create a new approach for the determination of trace concentrations of thiophene compounds in water samples. Thiophene compounds are persistent, typically petrogenic, organic pollutants of concern due to their potential for biomagnification and bioaccumulation, mutagenicity, and carcinogenicity in terrestrial and aquatic fauna. Identification and quantitation in water, particularly following oil spills, is a priority. Following adsorption of the thiophenes to the MIPs, the MIP-bound analytes are analyzed directly by HS-GC-SCD, with minimal sample manipulation and virtually no organic solvent. Calibration curves of spiked seawater were linear from 5 μg L -1 to 100 μg L -1 and limits of detection (LOD) were in the range of 0.24-0.82 μg L -1 . Low matrix effects were observed in the analysis of thiophene compounds in seawater making the method suitable for use in fresh and saline waters without modification. Acceptable reproducibility was obtained for analysis of thiophene compounds from spiked seawater samples at RSDs ≤7.0% (n = 3).

  16. Determination of Muscone in Rats Plasma following Oral Administration of Artificial Musk: Using of Combined Headspace Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Qibiao Wu

    2014-01-01

    Full Text Available To develop an analytical method for determination of plasma concentrations of muscone in rats following oral administration of artificial musk, with the aim of investigating the pharmacokinetic profile of artificial musk. Plasma samples were pretreated with acetonitrile to precipitate proteins. Headspace injection coupled with gas chromatography-mass spectrometry was used for quantitative analysis of muscone concentrations. A strong linear relationship was obtained for plasma muscone concentrations ranging from 75.6 to 7560 ng·mL−1  R2=0.9998, with the minimum detectable concentration being 25 ng·mL−1. The within-day and interday precision for determination of three different concentrations of muscone were favorable (RSD < 25%. The average absolute recovery ranged from 83.7 to 88.6%, with an average relative recovery of 100.5 to 109.8%. The method described was characterized by stability and reliability, and in the present study showed significant specificity and high sensitivity. This method would be applicable to the analysis of plasma concentrations of muscone in preclinical contexts, where artificial musk is used.

  17. A pilot study combining a GC-sensor device with a statistical model for the identification of bladder cancer from urine headspace.

    Directory of Open Access Journals (Sweden)

    Tanzeela Khalid

    Full Text Available There is a need to reduce the number of cystoscopies on patients with haematuria. Presently there are no reliable biomarkers to screen for bladder cancer. In this paper, we evaluate a new simple in-house fabricated, GC-sensor device in the diagnosis of bladder cancer based on volatiles. Sensor outputs from 98 urine samples were used to build and test diagnostic models. Samples were taken from 24 patients with transitional (urothelial cell carcinoma (age 27-91 years, median 71 years and 74 controls presenting with urological symptoms, but without a urological malignancy (age 29-86 years, median 64 years; results were analysed using two statistical approaches to assess the robustness of the methodology. A two-group linear discriminant analysis method using a total of 9 time points (which equates to 9 biomarkers correctly assigned 24/24 (100% of cancer cases and 70/74 (94.6% controls. Under leave-one-out cross-validation 23/24 (95.8% of cancer cases were correctly predicted with 69/74 (93.2% of controls. For partial least squares discriminant analysis, the correct leave-one-out cross-validation prediction values were 95.8% (cancer cases and 94.6% (controls. These data are an improvement on those reported by other groups studying headspace gases and also superior to current clinical techniques. This new device shows potential for the diagnosis of bladder cancer, but the data must be reproduced in a larger study.

  18. Product Characterization and Headspace Analysis of Solar Irradiated Aqueous C60 Clusters

    OpenAIRE

    Su, Dan

    2013-01-01

    Buckminsterfullerene (C60) is an important fullerene material that has drawn much attention and is currently being applied in many different fields. It was discovered in 1985. As its production has largely increased to meet these industrial needs, it is obvious that its environmental occurrence, especially in aqueous systems, will occur. To further provide information for environmental toxicity studies and for its risk assessment, this thesis focuses on the photo transformation processes of a...

  19. Field Portable Low Temperature Porous Layer Open Tubular Cryoadsorption Headspace Sampling and Analysis Part II: Applications*

    Science.gov (United States)

    Harries, Megan; Bukovsky-Reyes, Santiago; Bruno, Thomas J.

    2016-01-01

    This paper details the sampling methods used with the field portable porous layer open tubular cryoadsorption (PLOT-cryo) approach, described in Part I of this two-part series, applied to several analytes of interest. We conducted tests with coumarin and 2,4,6-trinitrotoluene (two solutes that were used in initial development of PLOT-cryo technology), naphthalene, aviation turbine kerosene, and diesel fuel, on a variety of matrices and test beds. We demonstrated that these analytes can be easily detected and reliably identified using the portable unit for analyte collection. By leveraging efficiency-boosting temperature control and the high flow rate multiple capillary wafer, very short collection times (as low as 3 s) yielded accurate detection. For diesel fuel spiked on glass beads, we determined a method detection limit below 1 ppm. We observed greater variability among separate samples analyzed with the portable unit than previously documented in work using the laboratory-based PLOT-cryo technology. We identify three likely sources that may help explain the additional variation: the use of a compressed air source to generate suction, matrix geometry, and variability in the local vapor concentration around the sampling probe as solute depletion occurs both locally around the probe and in the test bed as a whole. This field-portable adaptation of the PLOT-cryo approach has numerous and diverse potential applications. PMID:26726934

  20. Field portable low temperature porous layer open tubular cryoadsorption headspace sampling and analysis part II: Applications.

    Science.gov (United States)

    Harries, Megan; Bukovsky-Reyes, Santiago; Bruno, Thomas J

    2016-01-15

    This paper details the sampling methods used with the field portable porous layer open tubular cryoadsorption (PLOT-cryo) approach, described in Part I of this two-part series, applied to several analytes of interest. We conducted tests with coumarin and 2,4,6-trinitrotoluene (two solutes that were used in initial development of PLOT-cryo technology), naphthalene, aviation turbine kerosene, and diesel fuel, on a variety of matrices and test beds. We demonstrated that these analytes can be easily detected and reliably identified using the portable unit for analyte collection. By leveraging efficiency-boosting temperature control and the high flow rate multiple capillary wafer, very short collection times (as low as 3s) yielded accurate detection. For diesel fuel spiked on glass beads, we determined a method detection limit below 1 ppm. We observed greater variability among separate samples analyzed with the portable unit than previously documented in work using the laboratory-based PLOT-cryo technology. We identify three likely sources that may help explain the additional variation: the use of a compressed air source to generate suction, matrix geometry, and variability in the local vapor concentration around the sampling probe as solute depletion occurs both locally around the probe and in the test bed as a whole. This field-portable adaptation of the PLOT-cryo approach has numerous and diverse potential applications. Published by Elsevier B.V.

  1. Effects of gas composition in headspace and bicarbonate concentrations in media on gas and methane production, degradability, and rumen fermentation using in vitro gas production techniques.

    Science.gov (United States)

    Patra, Amlan Kumar; Yu, Zhongtang

    2013-07-01

    Headspace gas composition and bicarbonate concentrations in media can affect methane production and other characteristics of rumen fermentation in in vitro gas production systems, but these 2 important factors have not been evaluated systematically. In this study, these 2 factors were investigated with respect to gas and methane production, in vitro digestibility of feed substrate, and volatile fatty acid (VFA) profile using in vitro gas production techniques. Three headspace gas compositions (N2+ CO2+ H2 in the ratio of 90:5:5, CO2, and N2) with 2 substrate types (alfalfa hay only, and alfalfa hay and a concentrate mixture in a 50:50 ratio) in a 3×2 factorial design (experiment 1) and 3 headspace compositions (N2, N2 + CO2 in a 50:50 ratio, and CO2) with 3 bicarbonate concentrations (80, 100, and 120 mM) in a 3×3 factorial design (experiment 2) were evaluated. In experiment 1, total gas production (TGP) and net gas production (NGP) was the lowest for CO2, followed by N2, and then the gas mixture. Methane concentration in headspace gas after fermentation was greater for CO2 than for N2 and the gas mixture, whereas total methane production (TMP) and net methane production (NMP) were the greatest for CO2, followed by the gas mixture, and then N2. Headspace composition did not affect in vitro digestibility or the VFA profile, except molar percentages of propionate, which were greater for CO2 and N2 than for the gas mixture. Methane concentration in headspace gas, TGP, and NGP were affected by the interaction of headspace gas composition and substrate type. In experiment 2, increasing concentrations of CO2 in the headspace decreased TGP and NGP quadratically, but increased the concentrations of methane, NMP, and in vitro fiber digestibility linearly, and TMP quadratically. Fiber digestibility, TGP, and NGP increased linearly with increasing bicarbonate concentrations in the medium. Concentrations of methane and NMP were unaffected by bicarbonate concentration, but

  2. An interior needle electropolymerized pyrrole-based coating for headspace solid-phase dynamic extraction

    Energy Technology Data Exchange (ETDEWEB)

    Bagheri, Habib [Department of Chemistry, Sharif University of Technology, Azadi Av., P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of)], E-mail: bagheri@sharif.edu; Babanezhad, Esmaeil; Khalilian, Faezeh [Department of Chemistry, Sharif University of Technology, Azadi Av., P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of)

    2009-02-23

    A headspace solid-phase dynamic extraction (HS-SPDE) technique was developed by the use of polypyrrole (PPy) sorbent, electropolymerized inside the surface of a needle, as a possible alternative to solid-phase microextraction (SPME). Thermal desorption was subsequently, employed to transfer the extracted analytes into the injection port of a gas chromatography-mass spectrometry (GC-MS). The PPy sorbent including polypyrrole-dodecyl sulfate (PPy-DS) was deposited on the interior surface of a stainless steel needle from the corresponding aqueous electrolyte by applying a constant deposition potential. The homogeneity and the porous surface structure of the coating were examined using the scanning electron microscopy (SEM). The developed method was applied to the trace level extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample. In order to enhance the extraction efficiency and increase the partition coefficient of analytes, the stainless steel needle was cooled at 5 deg. C, while the sample solution was kept at 80 deg. C. Optimization of influential experimental conditions including the voltage of power supply, the time of PPy electrodeposition, the extraction temperature, the ionic strength and the extraction time were also investigated. The detection limits of the method under optimized conditions were in the range of 0.002-0.01 ng mL{sup -1}. The relative standard deviations (R.S.D.) at a concentration level of 0.1 ng mL{sup -1} were obtained between 7.54 and 11.4% (n = 6). The calibration curves of PAHs showed linearity in the range of 0.01-10 ng mL{sup -1}. The proposed method was successfully applied to the extraction of some selected PAHs from real-life water samples and the relative recoveries were higher than 90% for all the analytes.

  3. Multivariate optimization of headspace trap for furan and furfural simultaneous determination in sponge cake.

    Science.gov (United States)

    Cepeda-Vázquez, Mayela; Blumenthal, David; Camel, Valérie; Rega, Barbara

    2017-03-01

    Furan, a possibly carcinogenic compound to humans, and furfural, a naturally occurring volatile contributing to aroma, can be both found in thermally treated foods. These process-induced compounds, formed by close reaction pathways, play an important role as markers of food safety and quality. A method capable of simultaneously quantifying both molecules is thus highly relevant for developing mitigation strategies and preserving the sensory properties of food at the same time. We have developed a unique reliable and sensitive headspace trap (HS trap) extraction method coupled to GC-MS for the simultaneous quantification of furan and furfural in a solid processed food (sponge cake). HS Trap extraction has been optimized using an optimal design of experiments (O-DOE) approach, considering four instrumental and two sample preparation variables, as well as a blocking factor identified during preliminary assays. Multicriteria and multiple response optimization was performed based on a desirability function, yielding the following conditions: thermostatting temperature, 65°C; thermostatting time, 15min; number of pressurization cycles, 4; dry purge time, 0.9min; water / sample amount ratio (dry basis), 16; and total amount (water + sample amount, dry basis), 10g. The performances of the optimized method were also assessed: repeatability (RSD: ≤3.3% for furan and ≤2.6% for furfural), intermediate precision (RSD: 4.0% for furan and 4.3% for furfural), linearity (R 2 : 0.9957 for furan and 0.9996 for furfural), LOD (0.50ng furan g sample dry basis -1 and 10.2ng furfural g sample dry basis -1 ), LOQ (0.99ng furan g sample dry basis -1 and 41.1ng furfural g sample dry basis -1 ). Matrix effect was observed mainly for furan. Finally, the optimized method was applied to other sponge cakes with different matrix characteristics and levels of analytes. Copyright © 2016. Published by Elsevier B.V.

  4. Graphene deposited onto aligned zinc oxide nanorods as an efficient coating for headspace solid-phase microextraction of gasoline fractions from oil samples.

    Science.gov (United States)

    Wen, Congying; Li, Mengmeng; Li, Wangbo; Li, Zizhou; Duan, Wei; Li, Yulong; Zhou, Jie; Li, Xiyou; Zeng, Jingbin

    2017-12-29

    The content of gasoline fraction in oil samples is not only an important indicator of oil quality, but also an indispensable fundamental data for oil refining and processing. Before its determination, efficient preconcentration and separation of gasoline fractions from complicated matrices is essential. In this work, a thin layer of graphene (G) was deposited onto oriented ZnO nanorods (ZNRs) as a SPME coating. By this approach, the surface area of G was greatly enhanced by the aligned ZNRs, and the surface polarity of ZNRs was changed from polar to less polar, which were both beneficial for the extraction of gasoline fractions. In addition, the ZNRs were well protected by the mechanically and chemically stable G, making the coating highly durable for use. With headspace SPME (HS-SPME) mode, the G/ZNRs coating can effectively extract gasoline fractions from various oil samples, whose extraction efficiency achieved 1.5-5.4 and 2.1-8.2 times higher than those of a G and commercial 7-μm PDMS coating respectively. Coupled with GC-FID, the developed method is sensitive, simple, cost effective and easily accessible for the analysis of gasoline fractions. Moreover, the method is also feasible for the detection of gasoline markers in simulated oil-polluted water, which provides an option for the monitoring of oil spill accident. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Determination of furfural and hydroxymethylfurfural from baby formula using headspace solid phase microextraction based on nanostructured polypyrrole fiber coupled with ion mobility spectrometry.

    Science.gov (United States)

    Kamalabadi, Mahdie; Ghaemi, Elham; Mohammadi, Abdorreza; Alizadeh, Naader

    2015-08-15

    Furfural (Fu) and hydroxymethylfurfural (HMFu) are extracted using a dodecylbenzenesulfonate-doped polypyrrole coating as a fiber for headspace solid phase microextraction (HS-SPME) method in baby formula samples and detected using ion mobility spectrometry (IMS). Sample pH, salt effect, extraction time and temperature were investigated and optimized as effective parameters in HS-SPME. The calibration curves were linear in the range of 20-300 ng g(-1) (R(2)>0.99). Limits of detection for Fu and HMFu were 6 ng g(-1) and 5 ng g(-1), respectively. The RSD% of Fu and HMFu for five analyses was 4.4 and 4.9, respectively. The proposed method was successfully applied to determine of Fu and HMFu in the different baby formula samples with satisfactory result. The results were in agreement with those obtained using HPLC analysis. The HS-SPME-IMS is precise, selective and sensitive analytical method for determination of Fu and HMFu in baby formula samples, without any derivatization process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Covering the different steps of the coffee processing: Can headspace VOC emissions be exploited to successfully distinguish between Arabica and Robusta?

    Science.gov (United States)

    Colzi, Ilaria; Taiti, Cosimo; Marone, Elettra; Magnelli, Susanna; Gonnelli, Cristina; Mancuso, Stefano

    2017-12-15

    This work was performed to evaluate the possible application of PTR-ToF-MS technique in distinguishing between Coffea arabica (Arabica) and Coffea canephora var. robusta (Robusta) commercial stocks in each step of the processing chain (green beans, roasted beans, ground coffee, brews). volatile organic compounds (VOC) spectra from coffee samples of 7 Arabica and 6 Robusta commercial stocks were recorded and submitted to multivariate statistical analysis. Results clearly showed that, in each stage of the coffee processing, the volatile composition of coffee is highly influenced by the species. Actually, with the exception of green beans, PTR-ToF-MS technique was able to correctly recognize Arabica and Robusta samples. Particularly, among 134 tentatively identified VOCs, some masses (16 for roasted coffee, 12 for ground coffee and 12 for brewed coffee) were found to significantly discriminate the two species. Therefore, headspace VOC analyses was showed to represent a valuable tool to distinguish between Arabica and Robusta. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Development of a headspace trap HRGC/MS method for the assessment of the relevance of certain aroma compounds on the sensorial characteristics of commercial apple juice.

    Science.gov (United States)

    Nikfardjam, Martin Pour; Maier, Daniel

    2011-06-15

    A reliable and simple method was developed for the completely automatised analysis of apple juice aroma compounds. In total 26 flavour compounds could be measured by headspace trap gas chromatography/mass spectrometry (GC/MS). We used the method to analyse 85 commercially available apple juices, of which 67 apple juices were not from concentrate. Our results show that apple juices not from concentrate are mainly characterised by flavour compounds responsible for fruity, ripe, and sweet aroma impressions, such as 1-butanol, 2-methyl-1-butanol, ethylbutyrate, and ethyl-2-methylbutyrate. On the contrary, apple juices made from concentrate were dominated by acetaldehyde, E-2-hexenal, 3-methyl-1-butanol, ethyl acetate, and hexanal, which are mainly responsible for sensory impressions, such as 'green, fresh, estery'. According to our data, neither of the single compounds nor indexes calculated thereof as suggested by some authors could be used for the reliable assessment of apple juice quality. Thus, these results suggest that sensory evaluation remains the ultimate mean to reliably assess apple juice quality. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    Tytgat, J; Daenens, P

    1996-01-01

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

  9. 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

    International Nuclear Information System (INIS)

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

    2013-01-01

    Graphical abstract: -- Highlights: •We developed a method for CO 2 analysis in cardiac samples and quantification by 13 CO 2 . •This method was fully validated by accuracy profile. •We have applied this method to perform CO 2 precise quantification for forensic applications. •Context of the death could be documented following CO 2 concentrations. -- Abstract: A novel approach to measure carbon dioxide (CO 2 ) in gaseous samples, based on a precise and accurate quantification by 13 CO 2 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 CO 2 . The main drawback of the GC methods discussed in the literature for CO 2 measurement is the lack of a specific internal standard necessary to perform quantification. CO 2 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 CO 2 ) on the basis of the stoichiometric formation of CO 2 by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH 13 CO 3 ). This method allows a precise measurement of CO 2 concentration and was validated on various human postmortem gas samples in order to study its efficiency

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

    Directory of Open Access Journals (Sweden)

    Jingke Liu

    2018-02-01

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

  11. A comparative study of three tissue-cultured Dendrobium species and their wild correspondences by headspace gas chromatography-mass spectrometry combined with chemometric methods.

    Science.gov (United States)

    Chen, Nai-Dong; You, Tao; Li, Jun; Bai, Li-Tao; Hao, Jing-Wen; Xu, Xiao-Yuan

    2016-10-01

    Plant tissue culture technique is widely used in the conservation and utilization of rare and endangered medicinal plants and it is crucial for tissue culture stocks to obtain the ability to produce similar bioactive components as their wild correspondences. In this paper, a headspace gas chromatography-mass spectrometry method combined with chemometric methods was applied to analyze and evaluate the volatile compounds in tissue-cultured and wild Dendrobium huoshanense Cheng and Tang, Dendrobium officinale Kimura et Migo and Dendrobium moniliforme (Linn.) Sw. In total, 63 volatile compounds were separated, with 53 being identified from the three Dendrobium spp. Different provenances of Dendrobiums had characteristic chemicals and showed remarkable quantity discrepancy of common compositions. The similarity evaluation disclosed that the accumulation of volatile compounds in Dendrobium samples might be affected by their provenance. Principal component analysis showed that the first three components explained 85.9% of data variance, demonstrating a good discrimination between samples. Gas chromatography-mass spectrometry techniques, combined with chemometrics, might be an effective strategy for identifying the species and their provenance, especially in the assessment of tissue-cultured Dendrobium quality for use in raw herbal medicines. Copyright © 2016. Published by Elsevier B.V.

  12. Neuro-genetic multioptimization of the determination of polychlorinated biphenyl congeners in human milk by headspace solid phase microextraction coupled to gas chromatography with electron capture detection

    International Nuclear Information System (INIS)

    Hoffmann Kowalski, Claudia; Silva, Gilmare Antonia da; Poppi, Ronei Jesus; Teixeira Godoy, Helena; Augusto, Fabio

    2007-01-01

    Polychlorinated biphenyls (PCB) can eventually contaminate breast milk, which is a serious issue to the newborn due to their high vulnerability. Solid phase microextraction (SPME) can be a very convenient technique for their isolation and pre-concentration prior chromatographic analysis. Here, a simultaneous multioptimization strategy based on a neuro-genetic approach was applied to a headspace SPME method for determination of 12 PCB in human milk. Gas chromatography with electron capture detection (ECD) was adopted for the separation and detection of the analytes. Experiments according to a Doehlert design were carried out with varied extraction time and temperature, media ionic strength and concentration of the methanol (co-solvent). To find the best model that simultaneously correlate all PCB peak areas and SPME extraction conditions, a multivariate calibration method based on a Bayesian Neural Network (BNN) was applied. The net output from the neural network was used as input in a genetic algorithm (GA) optimization operation (neuro-genetic approach). The GA pointed out that the best values of the overall SPME operational conditions were the saturation of the media with NaCl, extraction temperature of 95 deg. C, extraction time of 60 min and addition of 5% (v/v) methanol to the media. These optimized parameters resulted in the decrease of the detection limits and increase on the sensitivity for all tested analytes, showing that the use of neuro-genetic approach can be a promising way for optimization of SPME methods

  13. Tank 241-C-111 vapor sampling and analysis tank characterization report. Revision 1

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-C-111. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedures that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  14. Tank 241-BY-110 vapor sampling and analysis tank characterization report. Revision 1

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-BY-110. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedures that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to the tank farm workers due to fugitive emissions from the tank

  15. Tank 241-C-107 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-C-107. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedures that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  16. Tank 241-C-102 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-C-102. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedures that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  17. Tank 241-TY-101 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-TY-101. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedure that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  18. Tank 241-BX-104 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-BX-104. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedure that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  19. Tank 241-SX-106 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-SX-106. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedure that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  20. Tank 241-T-107 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-T-107. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedure that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  1. Tank 241-B-103 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    This report presents the details of the Hanford waste tank characterization study for tank 241-B-103. The drivers and objectives of the headspace vapor sampling and analysis were in accordance with procedure that were presented in other reports. The vapor and headspace gas samples were collected and analyzed to determine the potential risks to tank farm workers due to fugitive emissions from the tank

  2. A high-throughput headspace gas chromatographic technique for the determination of nitrite content in water samples.

    Science.gov (United States)

    Zhang, Shu-Xin; Peng, Rong; Jiang, Ran; Chai, Xin-Sheng; Barnes, Donald G

    2018-02-23

    This paper reports on a high-throughput headspace gas chromatographic method (HS-GC) for the determination of nitrite content in water sample, based on GC measurement of cyclohexene produced from the reaction between nitrite and cyclamate in a closed vial. The method has a relative standard deviation of water samples. In short, the present HS-GC method is simple, accurate, and sensitive, and it is very suitable to be used in the batch sample testing. Copyright © 2018 Elsevier B.V. All rights reserved.

  3. Determination of styrene migration from food-contact polymers into margarine, using azeotropic distillation and headspace gas chromatography.

    Science.gov (United States)

    Varner, S L; Breder, C V; Fazio, T

    1983-09-01

    Migration studies were conducted to determine the quantity of styrene that migrates from polymers into fatty foods, specifically margarine. Azeotropic distillation was used to isolate styrene from the margarine. Headspace gas chromatography with a Chromosorb 104 column and a flame ionization detector was used for quantitation. The quantitation limit for the method was about 25 ppb (wt/wt) styrene in margarine. On the average, greater than 90% of the styrene was recovered. Several commercial margarines were examined. The method and results of the migration studies are presented. There was no detectable migration of styrene into margarine.

  4. Data on changes in red wine phenolic compounds and headspace aroma compounds after treatment of red wines with chitosans with different structures

    Directory of Open Access Journals (Sweden)

    Luís Filipe-Ribeiro

    2018-04-01

    Full Text Available Data in this article presents the changes on phenolic compounds and headspace aroma abundance of a red wine spiked with 4-ethylphenol and 4-ethylguaiacol and treated with a commercial crustacean chitin (CHTN, two commercial crustacean chitosans (CHTB, CHTD, one fungal chitosan (CHTF, one additional chitin (CHTNA and one additional chitosan (CHTC produced by alkaline deacetylation of CHTN and CHTB, respectively. Chitin and chitosans presented different structural features, namely deacetylation degree (DD, average molecular weight (MW, sugar and mineral composition (“Reducing the negative sensory impact of volatile phenols in red wine with different chitosan: effect of structure on efficiency” (Filipe-Ribeiro et al., 2018 [1]. Statistical data is also shown, which correlates the changes in headspace aroma abundance of red wines with the chitosans structural features at 10 g/h L application dose. Keywords: Red wine, 4-Ethylphenol, 4-Ethylguaiacol, Chitosan, Chitin, Chromatic characteristics, Phenolic compounds, Headspace aroma abundance

  5. Tank Vapor Characterization Project: Headspace vapor characterization of Hanford waste tank 241-S-101: Results from samples collected on 06/06/96

    International Nuclear Information System (INIS)

    Thomas, B.L.; Evans, J.C.; Pool, K.H.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of the waste storage tank 241-S-101. The results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank farm operations. The results include air concentrations of selected inorganic and organic analytes and grouped compounds from samples obtained. Analyte concentrations were based on analytical results and sample volumes provided by WHC. A summary of the inorganic analytes, permanent gases, and total non-methane organic compounds is listed

  6. Determination of the content of alkyl ketene dimer in its latex by an ionic-liquid assisted headspace gas chromatography.

    Science.gov (United States)

    Yan, Ning; Wan, Xiao-Fang; Chai, Xin-Sheng; Chen, Run-Quan; Chen, Chun-Xia

    2017-12-29

    This paper reports on an ionic-liquid assisted headspace gas chromatographic (HS-GC) for the determination of the content of alkyl ketene dimer (AKD) in its latex samples, in which the GC system was equipped with a thermal conductivity detector (TCD). The method was based on the AKD hydrolysis conducted in 1-butyl-3-methylimidazolium chloride (ionic-liquid) added medium at 100°C for 10min in a closed headspace sample vial, and the measured CO 2 (the resulting product of the hydrolysis) by HS-GC. The results showed that the present method has a good measurement precision (RSD <2.3%) and accuracy (recoveries from 96 - 105%), and the limit of quantitation (LOQ) is 0.9%. The present method is very suitable to be used for the routine check of AKD content in its latex sample in mill applications. The study also showed that the content of AKD in the tested commercial latex samples were in the range of 3.5-12%. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Pini Gláucia F.

    2004-01-01

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

  8. Análise qualitativa de compostos voláteis do headspace de carne cozida de ovinos e caprinos

    Directory of Open Access Journals (Sweden)

    Jossiê Zamperetti Donadel

    2013-11-01

    Full Text Available Este estudo teve como objetivo caracterizar qualitativamente os compostos voláteis (CV do headspace de diferentes músculos de carne cozida de ovinos e caprinos da região do Alto Camaquã, Rio Grande do Sul - Brasil. Os CV do headspace dos músculos cozidos, L. dorsi e V. lateralis de cinco ovinos machos (idade de 6 meses e cinco cabritos machos castrados (idade de 8-9 meses foram analisados pela técnica de microextração em fase sólida (HS-SPME e cromatógrafo a gás acoplado a espectrômetro de massas (GC/MS. Foram encontrados 73 compostos voláteis, dentre eles aldeídos, cetonas e compostos sulfurados, característicos de carne processada termicamente. A partir da fração volátil, foi possível encontrar marcadores que discriminassem as espécies animais estudadas, caracterizando os caprinos por apresentarem, entre outros compostos, terpenos (β-pineno, α-gurjuneno, α-muuroleno, ausentes em ovinos. Alguns compostos discriminaram V. lateralis e L. dorsi de ovinos, como álcool isopropílico, α-pineno, o-xileno, porém não foi possível obter uma diferenciação entre os músculos de caprinos.

  9. Headspace concentrations of explosive vapors in containers designed for canine testing and training: theory, experiment, and canine trials.

    Science.gov (United States)

    Lotspeich, Erica; Kitts, Kelley; Goodpaster, John

    2012-07-10

    It is a common misconception that the amount of explosive is the chief contributor to the quantity of vapor that is available to trained canines. In fact, this quantity (known as odor availability) depends not only on the amount of explosive material, but also the container volume, explosive vapor pressure and temperature. In order to better understand odor availability, headspace experiments were conducted and the results were compared to theory. The vapor-phase concentrations of three liquid explosives (nitromethane, nitroethane and nitropropane) were predicted using the Ideal Gas Law for containers of various volumes that are in use for canine testing. These predictions were verified through experiments that varied the amount of sample, the container size, and the temperature. These results demonstrated that the amount of sample that is needed to saturate different sized containers is small, predictable and agrees well with theory. In general, and as expected, once the headspace of a container is saturated, any subsequent increase in sample volume will not result in the release of more vapors. The ability of canines to recognize and alert to differing amounts of nitromethane has also been studied. In particular, it was found that the response of trained canines is independent of the amount of nitromethane present, provided it is a sufficient quantity to saturate the container in which it is held. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  10. A rapid method for simultaneously determining ethanol and methanol content in wines by full evaporation headspace gas chromatography.

    Science.gov (United States)

    Zhang, Chun-Yun; Lin, Neng-Biao; Chai, Xin-Sheng; Zhong-Li; Barnes, Donald G

    2015-09-15

    This work reports on a full evaporation headspace gas chromatographic (FE HS-GC) method for simultaneously determining the ethanol (EtOH) and methanol (MeOH) content in wines. A small sample (10μL) was placed in a headspace sample vial, and a near-complete mass transfer of ethanol and methanol from the liquid sample to the vapor phase was obtained within three minutes at a temperature of 105°C, which allowed the measurement of the EtOH and MeOH content in the sample by GC. The results showed excellent precision and accuracy, as shown by the reproducibilities of 1.02% and 2.11% for EtOH and MeOH, respectively, and recoveries that ranged from 96.1% to 104% for both alcohols. The method is efficient, accurate and suitable for the determination of EtOH and MeOH in wine production and quality control. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Determination of Selected Aromas in Marquette and Frontenac Wine Using Headspace-SPME Coupled with GC-MS and Simultaneous Olfactometry

    Directory of Open Access Journals (Sweden)

    Somchai Rice

    2018-03-01

    Full Text Available Understanding the aroma profile of wines made from cold climate grapes is needed to help winemakers produce quality aromatic wines. The current study aimed to add to the very limited knowledge of aroma-imparting compounds in wines made from the lesser-known Frontenac and Marquette cultivars. Headspace solid-phase microextraction (SPME and gas chromatography-mass spectrometry (GC-MS with simultaneous olfactometry was used to identify and quantify selected, aroma-imparting volatile organic compounds (VOC in wines made from grapes harvested at two sugar levels (22° Brix and 24° Brix. Aroma-imparting compounds were determined by aroma dilution analysis (ADA. Odor activity values (OAV were also used to aid the selection of aroma-imparting compounds. Principal component analysis and hierarchical clustering analysis indicated that VOCs in wines produced from both sugar levels of Marquette grapes are similar to each other, and more similar to wines produced from Frontenac grapes harvested at 24° Brix. Selected key aroma compounds in Frontenac and Marquette wines were ethyl hexanoate, ethyl isobutyrate, ethyl octanoate, and ethyl butyrate. OAVs >1000 were reported for three aroma compounds that impart fruity aromas to the wines. This study provides evidence that aroma profiles in Frontenac wines can be influenced by timing of harvesting the berries at different Brix. Future research should focus on whether this is because of berry development or accumulation of aroma precursors and sugar due to late summer dehydration. Simultaneous chemical and sensory analyses can be useful for the understanding development of aroma profile perceptions for wines produced from cold-climate grapes.

  12. Identificação e quantificação de voláteis de café através de cromatografia gasosa de alta resolução / espectrometria de massas empregando um amostrador automático de "headspace" Identification and quantification of coffee volatile components through high resolution gas chromatoghaph/mass spectrometer using a headspace automatic sampler

    Directory of Open Access Journals (Sweden)

    Leonardo César AMSTALDEN

    2001-01-01

    Full Text Available Usando um amostrador automático, os "headspaces" de três marcas comerciais de café torrado e moído foram analisados qualitativa e quantitativamente quanto a composição dos voláteis responsáveis pelo aroma através da técnica de cromatografia gasosa/espectrometria de massas. Uma vez que a metodologia não envolveu isolamento ou concentração dos aromas, suas proporções naturais foram mantidas, além de simplificar o preparo das amostras. O emprego do amostrador automático permitiu também boa resolução dos picos cromatográficos sem o emprego de criogenia, contribuindo para redução no tempo de análise. Noventa e um componentes puderam ser identificados, sendo que alguns compostos conhecidos como presentes em café como o dimetilsulfeto, metional e furfuril mercaptana não foram detectados. Os voláteis presentes em maior concentração puderam ser quantificados com o auxílio de dois padrões internos. A técnica se provou viável, tanto para caracterização como para quantificação de voláteis de café.Employing an automatic headspace sampler, the headspaces of three commercial brands of ground roasted coffee were qualitatively and quantitatively analyzed by gas chromatography / mass spectrometry. Since the methodology did not involve aroma isolation or concentration, their natural proportions were maintained, providing a more accurate composition of the flavors, and simplifying sample preparation. The automatic sampler allowed good resolution of the chromatographic peaks without cryofocusing the samples at the head of the column during injection, reducing analysis time. Ninety one compounds were identified and some known coffee volatiles, such as dimethyl sulphide, methional and furfuryl mercaptan were not detected. The more concentrated volatiles could be identified using two internal standards. The technique proved viable, for both characterization and for quantification of coffee volatiles.

  13. Headspace-programmed temperature vaporization-mass spectrometry for the rapid determination of possible volatile biomarkers of lung cancer in urine.

    Science.gov (United States)

    Pérez Antón, Ana; Ramos, Álvaro García; Del Nogal Sánchez, Miguel; Pavón, José Luis Pérez; Cordero, Bernardo Moreno; Pozas, Ángel Pedro Crisolino

    2016-07-01

    We propose a new method for the rapid determination of five volatile compounds described in the literature as possible biomarkers of lung cancer in urine samples. The method is based on the coupling of a headspace sampler, a programmed temperature vaporizer in solvent-vent injection mode, and a mass spectrometer (HS-PTV-MS). This configuration is known as an electronic nose based on mass spectrometry. Once the method was developed, it was used for the analysis of urine samples from lung cancer patients and healthy individuals. Multivariate calibration models were employed to quantify the biomarker concentrations in the samples. The detection limits ranged between 0.16 and 21 μg/L. For the assignment of the samples to the patient group or the healthy individuals, the Wilcoxon signed-rank test was used, comparing the concentrations obtained with the median of a reference set of healthy individuals. To date, this is the first time that multivariate calibration and non-parametric methods have been combined to classify biological samples from profile signals obtained with an electronic nose. When significant differences in the concentration of one or more biomarkers were found with respect to the reference set, the sample is considered as a positive one and a new analysis was performed using a chromatographic method (HS-PTV-GC/MS) to confirm the result. The main advantage of the proposed HS-PTV-MS methodology is that no prior chromatographic separation and no sample manipulation are required, which allows an increase of the number of samples analyzed per hour and restricts the use of time-consuming techniques to only when necessary. Graphical abstract Schematic diagram of the developed methodology.

  14. The effect of surfactant on headspace single drop microextraction for the determination of some volatile aroma compounds in citronella grass and lemongrass leaves by gas chromatography

    Science.gov (United States)

    A rapid method for the determination of some volatile aromatic compounds (VACs), including citronellal, citronellol, neral, geranial, geraniol, and eugenol in citronella grass and lemongrass leaves, was developed using surfactant as a surface tension modifier while performing headspace single drop m...

  15. Tank 241-BY-105 Headspace Gas and Vapor Characterization Results for Samples Collected in May 1994 and July 1994. Revision 2

    International Nuclear Information System (INIS)

    Huckaby, J.L.; Bratzel, D.R.

    1995-09-01

    Significant changes have been made to all of the original vapor characterization reports. This report documents specific headspace gas and vapor characterization results for all vapor sampling events to date. In addition, changes have been made to the original vapor reports to qualify the data based on quality assurance issues associated with the performing laboratories

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

    Science.gov (United States)

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

    2016-01-01

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

  17. Variation in Scent Compounds of Oil-Bearing Rose (Rosa damascena Mill. Produced by Headspace Solid Phase Microextraction, Hydrodistillation and Solvent Extraction

    Directory of Open Access Journals (Sweden)

    Sabri Erbaş

    2016-03-01

    Full Text Available In this research, rose oil and rose water were hydro-distilled from the fresh oil-bearing rose flowers (Rosa damascena Mill. using Clevenger-type apparatus. Rose concretes were extracted from the fresh rose flowers by using non-polar solvents, e.g. diethyl ether, petroleum ether, cyclo-hexane, chloroform and n-hexane, and subsequently by evaporation of the solvents under vacuum. Absolutes were produced from the concretes with ethyl alcohol extraction at -20°C, leaving behind the wax and other paraffinic substances. Scent compounds of all these products detected by gas chromatography (GC-FID/GC-MS were compared with the natural scent compounds of fresh rose flower detected by using headspace solid phase microextraction (HS-SPME with carboxen/polydimethylsiloxane (CAR/PDMS fiber. A total of 46 compounds analysis were identified by HS-SPME-GC-MS in the fresh flower, and a total of 15 compounds were identified by GC-MS in the hydrodistilled rose oil. While main compounds in rose oil were geraniol (35.4%, citronellol (31.6%, and nerol (15.3%, major compound in fresh rose flower, rose water and residue water was phenylethyl alcohol (43.2, 35.6 and 98.2%, respectively. While the highest concrete yield (0.7% was obtained from diethyl ether extraction, the highest absolute yield (70.9% was obtained from the n-hexane concrete. The diethyl ether concrete gave the highest productivity of absolute, as 249.7 kg of fresh rose flowers was needed to produce 1 kg of absolute.

  18. Wireless electrochemical preparation of gradient nanoclusters consisting of copper(II), stearic acid and montmorillonite on a copper wire for headspace in-tube microextraction of chlorobenzenes.

    Science.gov (United States)

    Enteshari Najafabadi, Marzieh; Bagheri, Habib

    2017-12-26

    This work introduces a new gradient fiber coating for microextraction of chlorobenzenes. Nanoclusters of organoclay-Cu(II) on a copper wire were fabricated by wireless electrofunctionalization. The resultant gradient coatings are more robust, and thermally and mechanically stable. Wireless electrofunctionalization was carried out in a bipolar cell under a constant deposition potential and using an ethanolic electrolyte solution containing stearic acid and montmorillonite. Stearic acid acts as an inexpensive and green coating while montmorillonite acts as a modifier to impart thermal stability. The gradient morphology of the nanoclusters was investigated by scanning electron microscopy, thermogravimetric analysis and energy dispersive X-ray spectroscopy. The coated wire was placed in a hollow needle and used for headspace in-tube microextraction (HS-ITME) of chlorobenzenes (CBs). Effects of various parameters affecting synthesis and extraction were optimized. Following extraction, the needles were directly inserted into the GC injector, and the CBs (chlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3,4-tetrachlorobenzene) were quantified by GC-MS. The limits of detection under optimized conditions range from 0.5 to 10 ng.L -1 . The intra- and inter-day relative standard deviations (RSDs) (for n = 10, 5 respectively) using a single fiber are 6-10 and 10-15%, respectively. The fiber-to-fiber RSDs (for n = 3) is between 17 and 24%. The method was successfully applied to the extraction of CBs from real water samples, and relative recoveries are between 91 and 110%. Graphical abstract A gradient coating of organoclay-Cu nanoclusters was fabricated on a copper wire by wireless electrofunctionalization. The oxidation of copper takes place at the anodic pole (red) while dissolved oxygen in ethanol solution is reduced at the cathodic pole (blue).

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

    International Nuclear Information System (INIS)

    Zhang Zhuomin; Wang Qingtang; Li Gongke

    2012-01-01

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

  20. Orthogonal Design Study on Factors Affecting the Determination of Common Odors in Water Samples by Headspace Solid-Phase Microextraction Coupled to GC/MS

    Directory of Open Access Journals (Sweden)

    Shifu Peng

    2013-01-01

    Full Text Available Geosmin and 2-MIB are responsible for the majority of earthy and musty events related to the drinking water. These two odorants have extremely low odor threshold concentrations at ng L−1 level in the water, so a simple and sensitive method for the analysis of such trace levels was developed by headspace solid-phase microextraction coupled to gas chromatography/mass spectrometry. In this study, the orthogonal experiment design L32 (49 was applied to arrange and optimize experimental conditions. The optimum was the following: temperatures of extraction and desorption, 65°C and 260°C, respectively; times of extraction and desorption, 30 min and 5 min, respectively; ionic strength, 25% (w/v; rotate-speed, 600 rpm; solution pH, 5.0. Under the optimized conditions, limits of detection (S/N=3 were 0.04 and 0.13 ng L−1 for geosmin and 2-MIB, respectively. Calculated calibration curves gave high levels of linearity with a correlation coefficient value of 0.9999 for them. Finally, the proposed method was applied to water samples, which were previously analyzed and confirmed to be free of target analytes. Besides, the proposal method was applied to test environmental water samples. The RSDs were 2.75%~3.80% and 4.35%~7.6% for geosmin and 2-MIB, respectively, and the recoveries were 91%~107% and 91%~104% for geosmin and 2-MIB, respectively.

  1. Extension of a dynamic headspace multi-volatile method to milliliter injection volumes with full sample evaporation: Application to green tea.

    Science.gov (United States)

    Ochiai, Nobuo; Sasamoto, Kikuo; Tsunokawa, Jun; Hoffmann, Andreas; Okanoya, Kazunori; MacNamara, Kevin

    2015-11-20

    An extension of multi-volatile method (MVM) technology using the combination of a standard dynamic headspace (DHS) configuration, and a modified DHS configuration incorporating an additional vacuum module, was developed for milliliter injection volume of aqueous sample with full sample evaporation. A prior step involved investigation of water management by weighing of the water residue in the adsorbent trap. The extended MVM for 1 mL aqueous sample consists of five different DHS method parameter sets including choice of the replaceable adsorbent trap. An initial two DHS sampling sets at 25°C with the standard DHS configuration using a carbon-based adsorbent trap target very volatile solutes with high vapor pressure (>10 kPa) and volatile solutes with moderate vapor pressure (1-10 kPa). Subsequent three DHS sampling sets at 80°C with the modified DHS configuration using a Tenax TA trap target solutes with low vapor pressure (88%) for 17 test aroma compounds and moderate recoveries (44-71%) for 4 test compounds. The method showed good linearity (r(2)>0.9913) and high sensitivity (limit of detection: 0.1-0.5 ng mL(-1)) even with MS scan mode. The improved sensitivity of the method was demonstrated with analysis of a wide variety of aroma compounds in brewed green tea. Compared to the original 100 μL MVM procedure, this extension to 1 mL MVM allowed detection of nearly twice the number of aroma compounds, including 18 potent aroma compounds from top-note to base-note (e.g. 2,3-butanedione, coumarin, furaneol, guaiacol, cis-3-hexenol, linalool, maltol, methional, 3-methyl butanal, 2,3,5-trimethyl pyrazine, and vanillin). Sensitivity for 23 compounds improved by a factor of 3.4-15 under 1 mL MVM conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. 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

    Energy Technology Data Exchange (ETDEWEB)

    Varlet, V., E-mail: vincent.varlet@chuv.ch [Toxicology and Forensic Chemistry Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Smith, F. [Toxicology and Forensic Chemistry Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Froidmont, S. de; Dominguez, A.; Rinaldi, A. [Forensic Medicine Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Augsburger, M. [Toxicology and Forensic Chemistry Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland); Mangin, P.; Grabherr, S. [Forensic Medicine Unit, University Center of Legal Medicine Lausanne – Geneva, CH-1011 Lausanne (Switzerland)

    2013-06-19

    Graphical abstract: -- Highlights: •We developed a method for CO{sub 2} analysis in cardiac samples and quantification by {sup 13}CO{sub 2}. •This method was fully validated by accuracy profile. •We have applied this method to perform CO{sub 2} precise quantification for forensic applications. •Context of the death could be documented following CO{sub 2} concentrations. -- Abstract: A novel approach to measure carbon dioxide (CO{sub 2}) in gaseous samples, based on a precise and accurate quantification by {sup 13}CO{sub 2} 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 CO{sub 2}. The main drawback of the GC methods discussed in the literature for CO{sub 2} measurement is the lack of a specific internal standard necessary to perform quantification. CO{sub 2} 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 ({sup 13}CO{sub 2}) on the basis of the stoichiometric formation of CO{sub 2} by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH{sup 13}CO{sub 3}). This method allows a precise measurement of CO{sub 2} concentration and was validated on various human postmortem gas samples in order to study its efficiency.

  3. A novel sol-gel-based amino-functionalized fiber for headspace solid-phase microextraction of phenol and chlorophenols from environmental samples

    Energy Technology Data Exchange (ETDEWEB)

    Bagheri, Habib [Department of Chemistry, Sharif University of Technology, P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of)], E-mail: Bagheri@sharif.edu; Babanezhad, Esmaeil; Khalilian, Faezeh [Department of Chemistry, Sharif University of Technology, P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of)

    2008-05-26

    A novel amino-functionalized polymer was synthesized using 3-(trimethoxysilyl) propyl amine (TMSPA) as precursor and hydroxy-terminated polydimethylsiloxane (OH-PDMS) by sol-gel technology and coated on fused-silica fiber. The synthesis was designed in a way to impart polar moiety into the coating network. The scanning electron microscopy (SEM) images of this new coating showed the homogeneity and the porous surface structure of the film. The efficiency of new coating was investigated for headspace solid-phase microextraction (SPME) of some environmentally important chlorophenols from aqueous samples followed by gas chromatography-mass spectrometry (GC-MS) analysis. Effect of different parameters influencing the extraction efficiency such as extraction temperature, extraction time, ionic strength and pH was investigated and optimized. In order to improve the separation efficiency of phenolic compounds on chromatography column all the analytes were derivatized prior to extraction using acetic anhydride at alkaline condition. The detection limits of the method under optimized conditions were in the range of 0.02-0.05 ng mL{sup -1}. The relative standard deviations (R.S.D.) (n = 6) at a concentration level of 0.5 ng mL{sup -1} were obtained between 6.8 and 10%. The calibration curves of chlorophenols showed linearity in the range of 0.5-200 ng mL{sup -1}. The proposed method was successfully applied to the extraction from spiked tap water samples and relative recoveries were higher than 90% for all the analytes.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-05-21

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

  5. Novel polyamide-based nanofibers prepared by electrospinning technique for headspace solid-phase microextraction of phenol and chlorophenols from environmental samples

    Energy Technology Data Exchange (ETDEWEB)

    Bagheri, Habib, E-mail: bagheri@sharif.edu [Environmental and Bio-Analytical Laboratories, Department of Chemistry, Sharif University of Technology, Azadi Av., P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of); Aghakhani, Ali; Baghernejad, Masoud; Akbarinejad, Alireza [Environmental and Bio-Analytical Laboratories, Department of Chemistry, Sharif University of Technology, Azadi Av., P.O. Box 11365-9516, Tehran (Iran, Islamic Republic of)

    2012-02-24

    A novel solid phase microextraction (SPME) fiber was fabricated by electrospinning method in which a polymeric solution was converted to nanofibers using high voltages. A thin stainless steel wire was coated by the network of polymeric nanofibers. The polymeric nanofiber coating on the wire was mechanically stable due to the fine and continuous nanofibers formation around the wire with a three dimensional structure. Polyamide (nylon 6), due to its suitable characteristics was used to prepare the unbreakable SPME nanofiber. The scanning electron microscopy (SEM) images of this new coating showed a diameter range of 100-200 nm for polyamide nanofibers with a homogeneous and porous surface structure. The extraction efficiency of new coating was investigated for headspace solid-phase microextraction (HS-SPME) of some environmentally important chlorophenols from aqueous samples followed by gas chromatography-mass spectrometry (GC-MS) analysis. Effect of different parameters influencing the extraction efficiency including extraction temperature, extraction time, ionic strength and polyamide amount were investigated and optimized. In order to improve the chromatographic behavior of phenolic compounds, all the analytes were derivatized prior to the extraction process using basic acetic anhydride. The detection limits of the method under optimized conditions were in the range of 2-10 ng L{sup -1}. The relative standard deviations (RSD) (n = 3) at the concentration level of 1.7-6.7 ng mL{sup -1} were obtained between 1 and 7.4%. The calibration curves of chlorophenols showed linearity in the range of 27-1330 ng L{sup -1} for phenol and monochlorophenols and 7-1000 ng L{sup -1} for dichloro and trichlorophenols. Also, the proposed method was successfully applied to the extraction of phenol and chlorophenols from real water samples and relative recoveries were between 84 and 98% for all the selected analytes except for 2,4,6 tricholophenol which was between 72 and 74%.

  6. A salting out system for improving the efficiency of the headspace solid-phase microextraction of short and medium chain free fatty acids.

    Science.gov (United States)

    Fiorini, Dennis; Pacetti, Deborah; Gabbianelli, Rosita; Gabrielli, Serena; Ballini, Roberto

    2015-08-28

    Given the importance of short and medium chain free fatty acids (FFAs) in several fields, this study sought to improve the extraction efficiency of the solid-phase microextraction (SPME) of FFAs by evaluating salting out agents that appear promising for this application. The salts ammonium sulfate ((NH4)2SO4) and sodium dihydrogen phosphate (NaH2PO4) were tried on their own and in combination (3.7/1), in four different total amounts, as salting out agents in the headspace-SPME-gas chromatographic (HS-SPME-GC) analysis of the FFAs from acetic acid (C2) to decanoic acid (C10). Their performance in a model system of an aqueous standard mixture of FFAs at a pH of 3.5 was compared to that of the more commonly used sodium chloride (NaCl) and sodium sulfate (Na2SO4). All of the salts and salt systems evaluated, in proper amount, gave improved results compared to NaCl (saturated), which instead gave interesting results only for the least volatile FFAs C8 and C10. For C2-C6, the salt system that gave the best results compared to NaCl was (NH4)2SO4/NaH2PO4, in the highest of the four amounts evaluated, with factor increases between 1.2 and 4.1-fold, and NaH2PO4, between 1.0 and 4.3-fold. The SPME extraction efficiency given by the mixture (NH4)2SO4/NaH2PO4 was also assessed on biological and food samples, confirming that overall it performed better than NaCl. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Novel polyamide-based nanofibers prepared by electrospinning technique for headspace solid-phase microextraction of phenol and chlorophenols from environmental samples

    International Nuclear Information System (INIS)

    Bagheri, Habib; Aghakhani, Ali; Baghernejad, Masoud; Akbarinejad, Alireza

    2012-01-01

    A novel solid phase microextraction (SPME) fiber was fabricated by electrospinning method in which a polymeric solution was converted to nanofibers using high voltages. A thin stainless steel wire was coated by the network of polymeric nanofibers. The polymeric nanofiber coating on the wire was mechanically stable due to the fine and continuous nanofibers formation around the wire with a three dimensional structure. Polyamide (nylon 6), due to its suitable characteristics was used to prepare the unbreakable SPME nanofiber. The scanning electron microscopy (SEM) images of this new coating showed a diameter range of 100–200 nm for polyamide nanofibers with a homogeneous and porous surface structure. The extraction efficiency of new coating was investigated for headspace solid-phase microextraction (HS-SPME) of some environmentally important chlorophenols from aqueous samples followed by gas chromatography–mass spectrometry (GC–MS) analysis. Effect of different parameters influencing the extraction efficiency including extraction temperature, extraction time, ionic strength and polyamide amount were investigated and optimized. In order to improve the chromatographic behavior of phenolic compounds, all the analytes were derivatized prior to the extraction process using basic acetic anhydride. The detection limits of the method under optimized conditions were in the range of 2–10 ng L −1 . The relative standard deviations (RSD) (n = 3) at the concentration level of 1.7–6.7 ng mL −1 were obtained between 1 and 7.4%. The calibration curves of chlorophenols showed linearity in the range of 27–1330 ng L −1 for phenol and monochlorophenols and 7–1000 ng L −1 for dichloro and trichlorophenols. Also, the proposed method was successfully applied to the extraction of phenol and chlorophenols from real water samples and relative recoveries were between 84 and 98% for all the selected analytes except for 2,4,6 tricholophenol which was between 72 and 74%.

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

    Science.gov (United States)

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

    2012-02-01

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

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

    Science.gov (United States)

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

    2015-08-18

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

  10. Characterization of volatile substances in apples from Rosaceae family by headspace solid-phase microextraction followed by GC-qMS.

    Science.gov (United States)

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

    2009-06-01

    The volatile composition of different apple varieties of Malus domestica Borkh. species from different geographic regions at Madeira Islands, namely Ponta do Pargo (PP), Porto Santo (PS), and Santo da Serra (SS) was established by headspace solid-phase microextraction (HS-SPME) procedure followed by GC-MS (GC-qMS) analysis. Significant parameters affecting sorption process such as fiber coating, extraction temperature, extraction time, sample amount, dilution factor, ionic strength, and desorption time, were optimized and discussed. The SPME fiber coated with 50/30 microm divinylbenzene/carboxen/PDMS (DVB/CAR/PDMS) afforded highest extraction efficiency of volatile compounds, providing the best sensitivity for the target volatiles, particularly when the samples were extracted at 50 degrees C for 30 min with constant magnetic stirring. A qualitative and semi-quantitative analysis between the investigated apple species has been established. It was possible to identify about 100 of volatile compounds among pulp (46, 45, and 39), peel (64, 60, and 64), and entire fruit (65, 43, and 50) in PP, PS, and SS apples, respectively. Ethyl esters, terpenes, and higher alcohols were found to be the most representative volatiles. Alpha-farnesene, hexan-1-ol and hexyl 2-methylbutyrate were the compounds found in the volatile profile of studied apples with the largest GC area, representing, on average, 24.71, 14.06, and 10.80% of the total volatile fraction from PP, PS, and SS apples. In PP entire apple, the most abundant compounds identified were alpha-farnesene (30.49%), the unknown compound m/z (69, 101, 157) (21.82%) and hexyl acetate (6.57%). Regarding PS entire apple the major compounds were alpha-farnesene (16.87%), estragole (15.43%), hexan-1-ol (10.94), and E-2-hexenal (10.67). Alpha-farnesene (30.3%), hexan-1-ol (18.90%), 2-methylbutanoic acid (4.7%), and pentan-1-ol (4.6%) were also found as SS entire apple volatiles present in a higher relative content. Principal

  11. Tank vapor characterization project - headspace vapor characterization of Hanford Waste Tank 241-C-107: Second comparison study results from samples collected on 3/26/96

    International Nuclear Information System (INIS)

    Evans, J.C.; Pool, K.H.; Thomas, B.L.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of waste storage tank 241-C-107 (Tank C-107) at the Hanford Site in Washington State. The results described in this report is the second in a series comparing vapor sampling of the tank headspace using the Vapor Sampling System (VSS) and In Situ Vapor Sampling (ISVS) system without high efficiency particulate air (HEPA) prefiltration. The results include air concentrations of water (H 2 O) and ammonia (NH 3 ), permanent gases, total non-methane organic compounds (TO-12), and individual organic analytes collected in SUMMA trademark canisters and on triple sorbent traps (TSTs). Samples were collected by Westinghouse Hanford Company (WHC) and analyzed by Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volume measurements provided by WHC

  12. Tank vapor characterization project. Headspace vapor characterization of Hanford waste tank 241-BY-108: Second comparison study results from samples collected on 3/28/96

    International Nuclear Information System (INIS)

    Thomas, B.L.; Pool, K.H.; Evans, J.C.

    1997-01-01

    This report describes the analytical results of vapor samples taken from the headspace of waste storage tank 241-BY-108 (Tank BY-108) at the Hanford Site in Washington State. The results described in this report is the second in a series comparing vapor sampling of the tank headspace using the Vapor Sampling System (VSS) and In Situ Vapor Sampling (ISVS) system without high efficiency particulate air (HEPA) prefiltration. The results include air concentrations of water (H 2 O) and ammonia (NH 3 ), permanent gases, total non-methane organic compounds (TO-12), and individual organic analytes collected in SUMMA trademark canisters and on triple sorbent traps (TSTs). Samples were collected by Westinghouse Hanford Company (WHC) and analyzed by Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volume measurements provided by WHC

  13. Data on changes in red wine phenolic compounds, headspace aroma compounds and sensory profile after treatment of red wines with activated carbons with different physicochemical characteristics

    OpenAIRE

    Filipe-Ribeiro, Lu?s; Milheiro, Juliana; Matos, Carlos C.; Cosme, Fernanda; Nunes, Fernando M.

    2017-01-01

    Data in this article presents the changes on phenolic compounds, headspace aroma composition and sensory profile of a red wine spiked with 4-ethylphenol and 4-ethylguaiacol and treated with seven activated carbons with different physicochemical characteristics, namely surface area, micropore volume and mesopore volume (“Reduction of 4-ethylphenol and 4-ethylguaiacol in red wine by activated carbons with different physicochemical characteristics: impact on wine quality” Filipe-Ribeiro et al. (...

  14. Calibration-free sensor for pressure and H2O concentration in headspace of sterile vial using tunable diode laser absorption spectroscopy.

    Science.gov (United States)

    Cai, Tingdong; Gao, Guangzhen; Liu, Ying

    2013-11-10

    Tunable diode laser absorption measurements of pressure and H2O concentration in the headspace of vials using a distributed-feedback (DFB) diode laser near 1.4 μm are reported. A H2O line located near 7161.41 cm(-1) is selected based on its strong absorption strength and isolation from interference of neighboring transitions. Direct absorption spectra of H2O are obtained for the measurement path as well as the reference path by scanning the laser wavelength. The pressure and H2O vapor concentration in the headspace of a vial are inferred from a differential absorption signal, which is the difference between the measured and the referenced absorbance spectra. This sensor is calibration-free and no purge gas is needed. The demonstrated capability would enable measurements of pressure and H2O concentration in the headspace of vials within 2.21% and 2.86%, respectively. A precision of 1.02 Torr and 390 ppm is found for the pressure and H2O concentration, respectively. A set of measurements for commercial freeze-dried products are also performed to illustrate the usefulness of this sensor.

  15. Determination of methylmercury by electrothermal atomic absorption spectrometry using headspace single-drop microextraction with in situ hydride generation

    Energy Technology Data Exchange (ETDEWEB)

    Gil, Sandra [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Universidad de Vigo, Facultad de Ciencias (Quimica), As Lagoas-Marcosende s/n, 36200 Vigo (Spain); Fragueiro, Sandra [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Universidad de Vigo, Facultad de Ciencias (Quimica), As Lagoas-Marcosende s/n, 36200 Vigo (Spain); Lavilla, Isela [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Universidad de Vigo, Facultad de Ciencias (Quimica), As Lagoas-Marcosende s/n, 36200 Vigo (Spain); Bendicho, Carlos [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Universidad de Vigo, Facultad de Ciencias (Quimica), As Lagoas-Marcosende s/n, 36200 Vigo (Spain)]. E-mail: bendicho@uvigo.es

    2005-01-10

    A new method is proposed for preconcentration and matrix separation of methylmercury prior to its determination by electrothermal atomic absorption spectrometry (ETAAS). Generation of methylmercury hydride (MeHgH) from a 5-ml solution is carried out in a closed vial and trapped onto an aqueous single drop (3-{mu}l volume) containing Pd(II) or Pt(IV) (50 and 10 mg/l, respectively). The hydrogen evolved in the headspace (HS) after decomposition of sodium tetrahydroborate (III) injected for hydride generation caused the formation of finely dispersed Pd(0) or Pt(0) in the drop, which in turn, were responsible for the sequestration of MeHgH. A preconcentration factor of ca. 40 is achieved with both noble metals used as trapping agents. The limit of detection of methylmercury was 5 and 4 ng/ml (as Hg) with Pd(II) or Pt(IV) as trapping agents, and the precision expressed as relative standard deviation was about 7%. The preconcentration system was fully characterised through optimisation of the following variables: Pd(II) or Pt(IV) concentration in the drop, extraction time, pH of the medium, temperatures of both sample solution and drop, concentration of salt in the sample solution, sodium tetrahydroborate (III) concentration in the drop and stirring rate. The method has been successfully validated against two fish certified reference materials (CRM 464 tuna fish and CRM DORM-2 dogfish muscle) following selective extraction of methylmercury in 2 mol/l HCl medium.

  16. Microbes a Tool for the Remediation of Organotin Pollution Determined by Static Headspace Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Christopher Finnegan

    2018-03-01

    Full Text Available Tributyltin (TBT is one of the most toxic anthropogenic compounds introduced into the marine environment. Despite its global ban in 2008, TBT is still a problem of great concern due to its high affinity for particulate matter, providing a direct and potentially persistent route of entry into benthic sediments. Bioremediation strategies may constitute an alternative approach to conventional physicochemical methods, benefiting from the microorganism’s potential to metabolize anthropogenic compounds. In this work, a simple, precise and accurate static headspace gas chromatography method was developed to investigate the ability of TBT degrading microbes in sedimentary microcosms over a period of 120 days. The proposed method was validated for linearity, repeatability, accuracy, specificity, limit of detection and limit of quantification. The method was subsequently successfully applied for the detection and quantification of TBT and degradation compounds in sediment samples on day 0, 30, 60, 90 and 120 of the experiment employing the principles of green chemistry. On day 120 the concentration of TBT remaining in the microcosms ranged between 91.91 ng/g wet wt for the least effective microbial inoculant to 52.73 ng/g wet wt for the most effective microbial inoculant from a starting concentration of 100 ng/g wet wt.

  17. Determination of transformation products of unsymmetrical dimethylhydrazine in water using vacuum-assisted headspace solid-phase microextraction.

    Science.gov (United States)

    Orazbayeva, Dina; Kenessov, Bulat; Psillakis, Elefteria; Nassyrova, Dayana; Bektassov, Marat

    2018-06-22

    A new, sensitive and simple method based on vacuum-assisted headspace solid-phase microextraction (Vac-HSSPME) followed by gas chromatography-mass-spectrometry (GC-MS), is proposed for the quantification of rocket fuel unsymmetrical dimethylhydrazine (UDMH) transformation products in water samples. The target transformation products were: pyrazine, 1-methyl-1H-pyrazole, N-nitrosodimethylamine, N,N-dimethylformamide, 1-methyl-1Н-1,2,4-triazole, 1-methyl-imidazole and 1H-pyrazole. For these analytes and within shorter sampling times, Vac-HSSPME yielded detection limits (0.5-100 ng L -1 ) 3-10 times lower than those reported for regular HSSPME. Vac-HSSPME sampling for 30 min at 50 °C yielded the best combination of analyte responses and their standard deviations (24 h). Finally, multiple Vac-HSSME proved to be an efficient tool for controlling the matrix effect and quantifying UDMH transformation products. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Determination of methylmercury by electrothermal atomic absorption spectrometry using headspace single-drop microextraction with in situ hydride generation

    International Nuclear Information System (INIS)

    Gil, Sandra; Fragueiro, Sandra; Lavilla, Isela; Bendicho, Carlos

    2005-01-01

    A new method is proposed for preconcentration and matrix separation of methylmercury prior to its determination by electrothermal atomic absorption spectrometry (ETAAS). Generation of methylmercury hydride (MeHgH) from a 5-ml solution is carried out in a closed vial and trapped onto an aqueous single drop (3-μl volume) containing Pd(II) or Pt(IV) (50 and 10 mg/l, respectively). The hydrogen evolved in the headspace (HS) after decomposition of sodium tetrahydroborate (III) injected for hydride generation caused the formation of finely dispersed Pd(0) or Pt(0) in the drop, which in turn, were responsible for the sequestration of MeHgH. A preconcentration factor of ca. 40 is achieved with both noble metals used as trapping agents. The limit of detection of methylmercury was 5 and 4 ng/ml (as Hg) with Pd(II) or Pt(IV) as trapping agents, and the precision expressed as relative standard deviation was about 7%. The preconcentration system was fully characterised through optimisation of the following variables: Pd(II) or Pt(IV) concentration in the drop, extraction time, pH of the medium, temperatures of both sample solution and drop, concentration of salt in the sample solution, sodium tetrahydroborate (III) concentration in the drop and stirring rate. The method has been successfully validated against two fish certified reference materials (CRM 464 tuna fish and CRM DORM-2 dogfish muscle) following selective extraction of methylmercury in 2 mol/l HCl medium

  19. Forming and sustaining partnerships to provide integrated services for young people: an overview based on the headspace Geelong experience.

    Science.gov (United States)

    Callaly, Tom; von Treuer, Kathryn; van Hamond, Toni; Windle, Kelly

    2011-02-01

    To discuss critical considerations in the formation and maintenance of agency partnerships designed to provide integrated care for young people. Two years after its establishment, an evaluation of the headspace Barwon collaboration and a review of the health-care and management literature on agency collaboration were conducted. The principal findings together with the authors' experience working at establishing and maintaining the partnership are used to discuss critical issues in forming and maintaining inter-agency partnerships. Structural and process considerations are necessary but not sufficient for the successful formation and maintenance of inter-agency partnerships and integrated care provision. Specifically, organizational culture change and staff engagement is a significant challenge and planning for this is essential and often neglected. Although agreeing on common goals and objectives is an essential first step in forming partnerships designed to provide integrated care, goodwill is not enough, and the literature consistently shows that most collaborations fail to meet their objectives. Principles and lessons of organizational behaviour and management practices in the business sector can contribute a great deal to partnership planning. © 2011 Blackwell Publishing Asia Pty Ltd.

  20. Determination of chlorophenols in landfill leachate using headspace sampling with ionic liquid-coated solid-phase microextraction fibers combined with gas chromatography–mass spectrometry

    International Nuclear Information System (INIS)

    Ho, Tse-Tsung; Chen, Chung-Yu; Li Zuguang; Yang, Thomas Ching-Cherng; Lee, Maw-Rong

    2012-01-01

    Highlights: ► Ionic liquid (IL), ([C 4 MIM][PF 6 ]), was rapid synthesized by microwave radiation. ► Trace chlorophenols in landfill leachate were extract by SPME coated IL. ► The IL-coated SPME-GC/MS method is low-cost, solvent-free and sensitive. - Abstract: A new microextraction technique based on ionic liquid solid-phase microextraction (IL-SPME) was developed for determination of trace chlorophenols (CPs) in landfill leachate. The synthesized ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C 4 MIM][PF 6 ]), was coated onto the spent fiber of SPME for extraction of trace CPs. After extraction, the absorbed analytes were desorbed and quantified using gas chromatography–mass spectrometry (GC/MS). The term of the proposed method is as ionic liquid-coated of solid-phase microextraction combined with gas chromatography–mass spectrometry (IL-SPME-GC/MS). No carryover effect was found, and every laboratory-made ionic liquids-coated-fiber could be used for extraction at least eighty times without degradation of efficiency. The chlorophenols studied were 2,4-dichlorophenol (2,4-DP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), and pentachlorophenol (PCP). The best results of chlorophenols analysis were obtained with landfill leachate at pH 2, headspace extraction for 4 min, and thermal desorption with the gas chromatograph injector at 240 °C for 4 min. Linearity was observed from 0.1 to 1000 μg L −1 with relative standard deviations (RSD) less than 7% and recoveries were over 87%. The limit of detection (LOD) for pentachlorophenol was 0.008 μg L −1 . The proposed method was tested by analyzing landfill leachate from a sewage farm. The concentrations of chlorophenols were detected to range from 1.1 to 1.4 μg L −1 . The results demonstrate that the IL-SPME-GC/MS method is highly effective in analyzing trace chlorophenols in landfill leachate.

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

    International Nuclear Information System (INIS)

    Risticevic, Sanja; Carasek, Eduardo; Pawliszyn, Janusz

    2008-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Risticevic, Sanja [Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada); Carasek, Eduardo [Department of Chemistry, Federal University of Santa Catarina, Trindade, Florianopolis, 88040-900, Santa Catarina (Brazil); Pawliszyn, Janusz [Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada)], E-mail: janusz@uwaterloo.ca

    2008-06-09

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

  3. Determination of chlorophenols in landfill leachate using headspace sampling with ionic liquid-coated solid-phase microextraction fibers combined with gas chromatography-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Tse-Tsung; Chen, Chung-Yu [Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan (China); Li Zuguang [Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan (China); College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, Zhejiang (China); Yang, Thomas Ching-Cherng [Department of Chemistry, National Kaohsiung Normal University, Kaohsiung 82444, Taiwan (China); Lee, Maw-Rong, E-mail: mrlee@dragon.nchu.edu.tw [Department of Chemistry, National Chung Hsing University, Taichung 40227, Taiwan (China)

    2012-01-27

    Highlights: Black-Right-Pointing-Pointer Ionic liquid (IL), ([C{sub 4}MIM][PF{sub 6}]), was rapid synthesized by microwave radiation. Black-Right-Pointing-Pointer Trace chlorophenols in landfill leachate were extract by SPME coated IL. Black-Right-Pointing-Pointer The IL-coated SPME-GC/MS method is low-cost, solvent-free and sensitive. - Abstract: A new microextraction technique based on ionic liquid solid-phase microextraction (IL-SPME) was developed for determination of trace chlorophenols (CPs) in landfill leachate. The synthesized ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C{sub 4}MIM][PF{sub 6}]), was coated onto the spent fiber of SPME for extraction of trace CPs. After extraction, the absorbed analytes were desorbed and quantified using gas chromatography-mass spectrometry (GC/MS). The term of the proposed method is as ionic liquid-coated of solid-phase microextraction combined with gas chromatography-mass spectrometry (IL-SPME-GC/MS). No carryover effect was found, and every laboratory-made ionic liquids-coated-fiber could be used for extraction at least eighty times without degradation of efficiency. The chlorophenols studied were 2,4-dichlorophenol (2,4-DP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP), and pentachlorophenol (PCP). The best results of chlorophenols analysis were obtained with landfill leachate at pH 2, headspace extraction for 4 min, and thermal desorption with the gas chromatograph injector at 240 Degree-Sign C for 4 min. Linearity was observed from 0.1 to 1000 {mu}g L{sup -1} with relative standard deviations (RSD) less than 7% and recoveries were over 87%. The limit of detection (LOD) for pentachlorophenol was 0.008 {mu}g L{sup -1}. The proposed method was tested by analyzing landfill leachate from a sewage farm. The concentrations of chlorophenols were detected to range from 1.1 to 1.4 {mu}g L{sup -1}. The results demonstrate that the IL-SPME-GC/MS method is highly effective in

  4. The Use of Headspace Solid-Phase Microextraction (HS-SPME to Assess the Quality and Stability of Fruit Products: An Example Using Red Mombin Pulp (Spondias purpurea L.

    Directory of Open Access Journals (Sweden)

    Katieli Martins Todisco

    2014-10-01

    Full Text Available The present study aimed to evaluate the volatiles profile of red mombin (Spondias purpurea pulp and its powder produced by spray-drying (SD as an example to show utility of headspace solid-phase microextraction (HS-SPME in the analysis of parameters such as the quality and stability of fruit products. Volatiles profiles of the pulp were identified by gas chromatography-mass spectrometry (GC-MS, quantified by gas chromatography-flame ionization detector (GC-FID and compared to the profile of the powder stored at 0, 60 and 120 days in plastic (PP or laminated packages (LP. The results showed that the technique was able to identify 36 compounds in the red mombin pulp, 17 out of which have been described for the first time in this fruit, showing that red mombin fresh pulp appears to be unique in terms of volatiles composition. However, only 24 compounds were detected in the powder. This decrease is highly correlated (r2 = 0.99, at least for the majority of compounds, to the degree of volatility of compounds. Furthermore, the powder stored in PP or LP showed no statistical differences in the amounts of its components for a period of 120 days of storage. Finally, this work shows how HS-SPME analysis can be a valuable tool to assess the quality and stability of fruit products.

  5. Optimization and validation of liquid chromatography and headspace-gas chromatography based methods for the quantitative determination of capsaicinoids, salicylic acid, glycol monosalicylate, methyl salicylate, ethyl salicylate, camphor and l-menthol in a topical formulation.

    Science.gov (United States)

    Pauwels, Jochen; D'Autry, Ward; Van den Bossche, Larissa; Dewever, Cédric; Forier, Michel; Vandenwaeyenberg, Stephanie; Wolfs, Kris; Hoogmartens, Jos; Van Schepdael, Ann; Adams, Erwin

    2012-02-23

    Capsaicinoids, salicylic acid, methyl and ethyl salicylate, glycol monosalicylate, camphor and l-menthol are widely used in topical formulations to relieve local pain. For each separate compound or simple mixtures, quantitative analysis methods are reported. However, for a mixture containing all above mentioned active compounds, no assay methods were found. Due to the differing physicochemical characteristics, two methods were developed and optimized simultaneously. The non-volatile capsaicinoids, salicylic acid and glycol monosalicylate were analyzed with liquid chromatography following liquid-liquid extraction, whereas the volatile compounds were analyzed with static headspace-gas chromatography. For the latter method, liquid paraffin was selected as compatible dilution solvent. The optimized methods were validated in terms of specificity, linearity, accuracy and precision in a range of 80% to 120% of the expected concentrations. For both methods, peaks were well separated without interference of other compounds. Linear relationships were demonstrated with R² values higher than 0.996 for all compounds. Accuracy was assessed by performing replicate recovery experiments with spiked blank samples. Mean recovery values were all between 98% and 102%. Precision was checked at three levels: system repeatability, method precision and intermediate precision. Both methods were found to be acceptably precise at all three levels. Finally, the method was successfully applied to the analysis of some real samples (cutaneous sticks). Copyright © 2011 Elsevier B.V. All rights reserved.

  6. Generation of sub-part-per-billion gaseous volatile organic compounds at ambient temperature by headspace diffusion of aqueous standards through decoupling between ideal and nonideal Henry's law behavior.

    Science.gov (United States)

    Kim, Yong-Hyun; Kim, Ki-Hyun

    2013-05-21

    In the analysis of volatile organic compounds in air, the preparation of their gaseous standards at low (sub-ppb) concentration levels with high reliability is quite difficult. In this study, a simple dynamic headspace-based approach was evaluated as a means of generating vapor-phase volatile organic compounds from a liquid standard in an impinger at ambient temperature (25 °C). For a given sampling time, volatile organic compound vapor formed in the headspace was swept by bypassing the sweep gas through the impinger and collected four times in quick succession in separate sorbent tubes. In each experiment, a fresh liquid sample was used for each of the four sampling times (5, 10, 20, and 30 min) at a steady flow rate of 50 mL min(-1). The air-water partitioning at the most dynamic (earliest) sweeping stage was established initially in accord with ideal Henry's law, which was then followed by considerably reduced partitioning in a steady-state equilibrium (non-ideal Henry's law). The concentrations of gaseous volatile organic compounds, collected after the steady-state equilibrium, reached fairly constant values: for instance, the mole fraction of toluene measured at a sweeping interval of 10 and 30 min averaged 1.10 and 0.99 nmol mol(-1), respectively (after the initial 10 min sampling). In the second stage of our experiment, the effect of increasing the concentrations of liquid spiking standard was also examined by collecting sweep gas samples from two consecutive 10 min runs. The volatile organic compounds, collected in the first and second 10 min sweep gas samples, exhibited ideal and nonideal Henry's law behavior, respectively. From this observation, we established numerical relationships to predict the mole fraction (or mixing ratio) of each volatile organic compound in steady-state equilibrium in relation to the concentration of standard spiked into the system. This experimental approach can thus be used to produce sub-ppb levels of gaseous volatile organic

  7. Use of headspace gas chromatographic/FTIR for the monitoring of volatiles in commercial brand coffees

    Science.gov (United States)

    Compton, Senja V.; Compton, David A.

    1989-12-01

    Recently, the area of food analysis and product safety has become of major concern to consumers. Therefore, companies involved in the quality assurance of theirproducts have been encouraged to perform extensive analyses to guarantee safety and satisfaction. One of the largest consumer products in the beverage marketplace is coffee. Much emphasis has been placed upon the safety of the decaffeination processes used by various manufacturers; these involve extraction of the caffeine by a solvent system that may be aqueous or organic, and is sometimes,super-critical. Additionally, aroma (fragrance) of brewing coffee has been found to be of major concern to the individual by the marketing departments of the coffee companies. The heads ace analysis of coffees can be used to discover the species retained after the decaffeination of coffee, as well as to distinguish the volatile species released upon treatment of the coffee at boiling water temperatures.

  8. Determination of 2-Propenal Using Headspace Solid-Phase Microextraction Coupled to Gas Chromatography–Time-of-Flight Mass Spectrometry as a Marker for Authentication of Unrefined Sesame Oil

    Directory of Open Access Journals (Sweden)

    Ahmad Rois Mansur

    2017-01-01

    Full Text Available Ascertaining the authenticity of the unrefined sesame oil presents an ongoing challenge. Here, the determination of 2-propenal was performed by headspace solid-phase microextraction (HS-SPME under mild temperature coupled to gas chromatography with time-of-flight mass spectrometry, enabling the detection of adulteration of unrefined sesame oil with refined corn or soybean oil. Employing this coupled technique, 2-propenal was detected in all tested refined corn and soybean oils but not in any of the tested unrefined sesame oil samples. Using response surface methodology, the optimum extraction temperature, equilibrium time, and extraction time for the HS-SPME analysis of 2-propenal using carboxen/polydimethylsiloxane fiber were determined to be 55°C, 15 min, and 15 min, respectively, for refined corn oil and 55°C, 25 min, and 15 min, respectively, for refined soybean oil. Under these optimized conditions, the adulteration of unrefined sesame oil with refined corn or soybean oils (1–5% was successfully detected. The detection and quantification limits of 2-propenal were found to be in the range of 0.008–0.010 and 0.023–0.031 µg mL−1, respectively. The overall results demonstrate the potential of this novel method for the authentication of unrefined sesame oil.

  9. Comments on “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” by Varlet et al

    Energy Technology Data Exchange (ETDEWEB)

    Saffaj, T., E-mail: taoufiq.saffaj@usmba.ac.ma [Centre Universitaire Régional d’Interface, Université Sidi Mohamed Ben Abdellah, BP 2626, route d’Imouzzer, Fes Morocco (Morocco); Laboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, BP 2202, route d’Imouzzer, Fes Morocco (Morocco); Ihssane, B. [Laboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, BP 2202, route d’Imouzzer, Fes Morocco (Morocco)

    2014-01-31

    Graphical abstract: -- Highlights: •We comment on the validation results of the method for CO{sub 2} analysis in cardiac samples. •We demonstrate that the total error of the method exceeds the acceptance limits. •We show that the method is not valid according to the new SFSTP guideline. -- Abstract: Varlet et al. recently proposed a headspace-gas chromatography–mass spectrometry (HS-GC–MS) method applicable for the routine determination of CO{sub 2} in gaseous biologic matrices. This developed bioanalytical method was fully validated according to the SFSTP 1997 guidelines using the accuracy profile as a graphical decision-making tool.In this letter, we discuss the validity of HS-GC–MS method based on the newest SFSTP guideline. In particular, we demonstrate by the estimation of the β-expectation tolerance interval that the error total exceeds the acceptance limits (30%) for the second concentration level (0.5 μmol mL{sup −1} vial HS). Furthermore, we show through the risk profile that the probability to have future results inside the ±30% acceptance limits is smaller than 95%.

  10. Influence of harvest maturity and fruit logistics on pineapple (Ananas comosus [L.] Merr.) volatiles assessed by headspace solid phase microextraction and gas chromatography-mass spectrometry (HS-SPME-GC/MS).

    Science.gov (United States)

    Steingass, Christof B; Grauwet, Tara; Carle, Reinhold

    2014-05-01

    Profiling of volatiles from pineapple fruits was performed at four ripening stages using headspace solid-phase microextraction and gas chromatography-mass spectrometry (HS-SPME-GC/MS). In total, 142 volatiles were detected, of which 132 were identified. Multivariate data analysis was carried out to assess the effect of post-harvest storage on volatiles composition of green-ripe sea-freighted pineapple in comparison to air-freighted fruits harvested at full maturity. The latter fruits were characterised by volatiles described as potent odorants in pineapples, such as δ-octalactone, γ-lactones, 1-(E,Z)-3,5-undecatriene and 1,3,5,8-undecatetraene, as well as various methyl esters. In contrast, post-harvest storage of green-ripe sea-freighted fruits resulted in an increased formation of ethyl esters, acetates, acetoxy esters and alcohols, thus allowing the authentication of sea- and air-freighted pineapples, respectively. Particularly, compounds presumably derived from methyl-branched amino acid catabolism were identified in the fruits at later post-harvest stages. In addition, physicochemical traits were determined to characterise the fruit maturity stages. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. A novel headspace solid-phase microextraction method using in situ derivatization and a diethoxydiphenylsilane fibre for the gas chromatography-mass spectrometry determination of urinary hydroxy polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Mattarozzi, M; Musci, M; Careri, M; Mangia, A; Fustinoni, S; Campo, L; Bianchi, F

    2009-07-24

    An innovative and simple headspace solid-phase microextraction method using a novel diethoxydiphenylsilane fibre based on in situ derivatization with acetic anhydride was optimized and validated for the gas chromatography-mass spectrometry determination of some monohydroxy metabolites of polycyclic aromatic hydrocarbons, namely 1-hydroxynaphthalene, 2-hydroxynaphtalene, 9-hydroxyfluorene, 2-hydroxyfluorene and 1-hydroxypyrene at trace levels in human urine. Enzymatic hydrolysis was applied before derivatization, whereas extraction conditions, i.e. the effects of time and temperature of extraction and salt addition were investigated by experimental design. Regression models and desirability functions were applied to find the experimental conditions providing the highest global extraction response. These conditions were found in correspondence of an extraction temperature of 90 degrees C, an extraction time of 90 min and 25% NaCl added to urine samples. The capabilities of the developed method were proved obtaining limit of quantitations in the 0.1-2 microg/l range, thus allowing the bio-monitoring of these compounds in human urine. A good precision was observed both in terms of intra-batch and inter-batch repeatability with RSD always lower than 14%. Recoveries ranging from 98(+/-3) to 121(+/-1)% and extraction yields higher than 72% were also obtained. Finally, the analysis of urine specimens of coke-oven workers revealed analytes' concentrations in the 2.2-164 microg/l range, proving the exposure to PAHs of the involved workers.

  12. Analytical Method Development and Validation for the Quantification of Acetone and Isopropyl Alcohol in the Tartaric Acid Base Pellets of Dipyridamole Modified Release Capsules by Using Headspace Gas Chromatographic Technique

    Directory of Open Access Journals (Sweden)

    Sriram Valavala

    2018-01-01

    Full Text Available A simple, sensitive, accurate, robust headspace gas chromatographic method was developed for the quantitative determination of acetone and isopropyl alcohol in tartaric acid-based pellets of dipyridamole modified release capsules. The residual solvents acetone and isopropyl alcohol were used in the manufacturing process of the tartaric acid-based pellets of dipyridamole modified release capsules by considering the solubility of the dipyridamole and excipients in the different manufacturing stages. The method was developed and optimized by using fused silica DB-624 (30 m × 0.32 mm × 1.8 µm column with the flame ionization detector. The method validation was carried out with regard to the guidelines for validation of analytical procedures Q2 demanded by the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH. All the validation characteristics were meeting the acceptance criteria. Hence, the developed and validated method can be applied for the intended routine analysis.

  13. Analysis of volatile components from Melipona beecheii geopropolis from Southeast Mexico by headspace solid-phase microextraction.

    Science.gov (United States)

    Torres-González, Ahira; López-Rivera, Paulina; Duarte-Lisci, Georgina; López-Ramírez, Ángel; Correa-Benítez, Adriana; Rivero-Cruz, J Fausto

    2016-01-01

    A head space solid-phase microextraction method combined with gas chromatography-mass spectrometry was developed and optimised to extract and analyse volatile compounds of Melipona beecheii geopropolis. Seventy-three constituents were identified using this technique in the sample of geopropolis collected. The main compounds detected include β-fenchene (14.53-15.45%), styrene (8.72-9.98%), benzaldehyde (7.44-7.82%) and the most relevant volatile components presents at high level in the geopropolis were terpenoids (58.17%).

  14. Analysis of Illicit Liquor by Headspace Gas Chromatography-Mass Spectrometry (HS-GC-MS): A Preliminary Study.

    Science.gov (United States)

    Punia, Bhupinder Singh; Yadav, Praveen Kumar; Bumbrah, Gurvinder Singh; Sharma, Rakesh Mohan

    2017-01-01

    Illicit liquors are illegally manufactured to evade taxes and represent the majority of unrecorded liquors in developing countries. Because there are no standards, the composition of illicit liquors varies greatly from sample to sample. In the current study, we analyzed the volatile components of 27 different illicit liquors via samples collected from various locations in the northern region of India. Ethanol content varied drastically and methanol was not present in any of the samples. The components found can be categorized into different groups, namely alcohols, esters, acids, nitrogen-containing components, ketones, and aldehydes. Some components-such as 1-propanol; 1-pentanol; 1-butanol; d-limonene; phenylethyl alcohols; anethole; and decanoic, octanoic, and pentanoic acids-were frequently encountered.

  15. Sampling and Analysis of the Headspace Gas in 3013 Type Plutonium Storage Containers at Los Alamos National Laboratory

    International Nuclear Information System (INIS)

    Jackson, Jay M.; Berg, John M.; Hill, Dallas D.; Worl, Laura A.; Veirs, Douglas K.

    2012-01-01

    Department of Energy (DOE) sites have packaged approximately 5200 3013 containers to date. One of the requirements specified in DOESTD-3013, which specifies requirements for packaging plutonium bearing materials, is that the material be no greater than 0.5 weight percent moisture. The containers are robust, nested, welded vessels. A shelf life surveillance program was established to monitor these cans over their 50 year design life. In the event pressurization is detected by radiography, it will be necessary to obtain a head space gas sample from the pressurized container. This technique is also useful to study the head space gas in cans selected for random destructive evaluation. The atmosphere is sampled and the hydrogen to oxygen ratio is measured to determine the effects of radiolysis on the moisture in the container. A system capable of penetrating all layers of a 3013 container assembly and obtaining a viable sample of the enclosed gas and an estimate of internal pressure was designed.

  16. Identification of volatile organic compounds (VOCs) in different colour carrot (Daucus carota L.) cultivars using static headspace/gas chromatography/mass spectrometry

    OpenAIRE

    Zehra Güler; Fatih Karaca; Halit Yetisir

    2015-01-01

    Volatile organic compounds (VOCs) as well as sugar and acid contents affect carrot flavour. This study compared VOCs in 11 carrot cultivars. Gas chromatography/mass spectrometry using static headspace technique was applied to analyse the VOCs. The number of VOCs per sample ranged from 17 to 31. The primarily VOCs identified in raw carrots with the exception of “Yellow Stone” were terpenes, ranging from 65 to 95%. The monoterpenes with values ranging from 31 to 89% were higher than those (from...

  17. Microwave-assisted decomplexation and in-situ headspace in-syringe dynamic derivatization of dimethylamine borane with high performance liquid chromatography-fluorescence detection.

    Science.gov (United States)

    Muniraj, Sarangapani; Lee, Hua-Kwang; Hsiech, Chunming; Jen, Jen-Fon

    2018-02-16

    A rapid, sensitive, selective, and simple method for monitoring dimethylamine borane (DMAB) in aqueous sample is proposed by combining microwave-assisted de-complexation, headspace liquid phase in-situ derivatization extraction, and high-performance liquid chromatography-fluorescence detection for the determination of DMAB in samples. The present procedure involves de-complexation of DMAB using microwave irradiation, evolution of dimethylamine (DMA) to the headspace from an alkalized sample solution, and dynamic headspace liquid-phase derivatization extraction (Dy-HS-LPDE) of DMA with 9-fluorenylmethyl chloroformate in a syringe barrel. In addition to the optimal Dy-HS-LPDE and chromatographic parameters described in our previous study, the de-complexation of DMAB by thermal and microwave-assisted procedures and evolution of DMA into the headspace from an alkalized solution and modification of the Dy-HS-LPDE method are thoroughly investigated. The results indicate that complete de-complexation was obtained at 70 °C for 5 min, 30 °C for 10 min, or using microwave irradiation for 30 s at any applied power. It indicates that the DMAB complex easily undergoes de-complexation under microwave irradiation. The linearity range was 0.01-0.5 mg L -1 for DMAB and 0.0077-0.38 mg L -1 for DMA, with a coefficient of determination of 0.9995, and limit of detection of 3 μg L -1 (limit of quantitation of 10 μg L -1 ) for DMAB. The recoveries of DMAB are 95.3% (3.0% RSD) for waste water when spiked 0.05 mg L -1 and 93.5% (5.4% RSD) for the samples spiked with copper and nickel salts (5 mM each in the spiked waste sample). The whole analytical procedure can be completed within 25 min. The results confirm that the present method is a rapid, sensitive, selective, automated, low-cost and eco-friendly procedure to identify DMAB in samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Differentiation of Toxic Molds via Headspace SPME-GC/MS and Canine Detection

    Directory of Open Access Journals (Sweden)

    Kenneth G. Furton

    2007-08-01

    Full Text Available Indoor mold growth has recently become a concern in the legal world in regards to insurance litigation. Hazardous mold exposure to humans has been linked to many acute and chronic adverse health effects including death. As it grows, mold produces several types of primary and secondary metabolites, including microbial volatile organic compounds (MVOCs. Microbial volatile organic compound emission may be used as a preliminary indication of a mold infestation that is invisible to the unaided eye. The objective of the study is to identify the unique odor signatures of three species of molds, Aspergillus versicolor, Penicillium chrysogenum, and Stachybotrys chartarum by SPME-GC/MS analysis. Determining the compounds that are emitted by the selected species has made it possible to conduct validation studies of canine detection of these mold species through a series of field tests.

  19. Tank 241-TX-105 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-TX-105 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-TX-105 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  20. Tank 241-C-108 vapor sampling and analysis tank characterization report. Revision 1

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-C-108 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-C-108 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  1. Tank 241-BY-107 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-BY-107 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issuesclose quotes. Tank 241-BY-107 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolutionclose quotes

  2. Tank 241-BY-107 vapor sampling and analysis tank characterization report. Revision 1

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-BY-107 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-BY-107 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  3. Tank 241-BY-111 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-BY-111 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-BY-111 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  4. Tank 241-C-108 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-C-108 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in Program Plan for the Resolution of Tank Vapor Issues (Osborne and Huckaby 1994). Tank 241-C-108 was vapor sampled in accordance with Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution (Osborne et al., 1994)

  5. Tank 241-TX-118 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-TX-118 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-TX-118 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  6. Tank 241-BY-108 vapor sampling and analysis tank characterization report. Revision 1

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-BY-108 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in ''Program Plan for the Resolution of Tank Vapor Issues'' (Osborne and Huckaby 1994). Tank 241-BY-108 was vapor sampled in accordance with ''Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution (Osborne et al., 1994)

  7. Tank 241-BY-112 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-BY-112 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-BY-112 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  8. Tank 241-C-104 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-C-104 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-C-104 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  9. Tank 241-BY-103 vapor sampling and analysis tank characterization report

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-BY-103 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-BY-103 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  10. Tank 241-BY-106 vapor sampling and analysis tank characterization report. Revision 1

    International Nuclear Information System (INIS)

    Huckaby, J.L.

    1995-01-01

    Tank 241-BY-106 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in open-quotes Program Plan for the Resolution of Tank Vapor Issues.close quotes Tank 241-BY-106 was vapor sampled in accordance with open-quotes Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.close quotes

  11. Tank 241-U-107 vapor sampling and analysis tank characterization report

    Energy Technology Data Exchange (ETDEWEB)

    Huckaby, J.L.

    1995-05-31

    Tank 241-U-107 headspace gas and vapor samples were collected and analyzed to help determine the potential risks to tank farm workers due to fugitive emissions from the tank. The drivers and objectives of waste tank headspace sampling and analysis are discussed in {open_quotes}Program Plan for the Resolution of Tank Vapor Issues.{close_quotes} Tank 241-U-107 was vapor sampled in accordance with {open_quotes}Data Quality Objectives for Generic In-Tank Health and Safety Issue Resolution.{close_quotes}

  12. Headspace solid-phase microextraction for the determination of volatile organic sulphur and selenium compounds in beers, wines and spirits using gas chromatography and atomic emission detection.

    Science.gov (United States)

    Campillo, Natalia; Peñalver, Rosa; López-García, Ignacio; Hernández-Córdoba, Manuel

    2009-09-25

    A rapid and solvent-free method for the determination of eight volatile organic sulphur and two selenium compounds in different beverage samples using headspace solid-phase microextraction and gas chromatography with atomic emission detection has been developed. The bonded carboxen/polydimethylsiloxane fiber was the most suitable for preconcentrating the analytes from the headspace of the sample solution. Volumes of 20 mL of undiluted beer were used while, in the case of wines and spirits, sample:water ratios of 5:15 and 2:18, respectively, were used, in order to obtain the maximum sensitivity. Quantitation was carried out by using synthetic matrices of beer and wine, and a spiked sample for spirits, and using ethyl methyl sulphide and isopropyl disulphide as internal standards. Detection limits ranged from 8 ng L(-1) to 40 ng mL(-1), depending on the compound and the beverage sample analyzed, with a fiber time exposure of 20 min at ambient temperature. The optimized method was successfully applied to different samples, some of the studied compounds being detected at concentration levels in the 0.04-152 ng mL(-1) range.

  13. Quantification of 13 priority polycyclic aromatic hydrocarbons in human urine by headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Campo, Laura [Department of Occupational and Environmental Health, University of Milan and Fondazione IRCCS Ospedale Maggiore Policlinico, Mangiagalli e Regina Elena, Milan (Italy)], E-mail: laura.campo@unimi.it; Mercadante, Rosa; Rossella, Federica; Fustinoni, Silvia [Department of Occupational and Environmental Health, University of Milan and Fondazione IRCCS Ospedale Maggiore Policlinico, Mangiagalli e Regina Elena, Milan (Italy)

    2009-01-12

    Polycyclic aromatic hydrocarbons (PAHs) are common environmental pollutants in both living and working environments. The aim of this study was the development of a headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry (HS-SPME/GC-IDMS) method for the simultaneous quantification of 13 PAHs in urine samples. Different parameters affecting PAHs extraction by HS-SPME were considered and optimized: type/thickness of fiber coatings, extraction temperature/time, desorption temperature/time, ionic strength and sample agitation. The stability of spiked PAHs solutions and of real urine samples stored up to 90 days in containers of different materials was evaluated. In the optimized method, analytes were absorbed for 60 min at 80 deg. C in the sample headspace with a 100 {mu}m polydimethylsiloxane fiber. The method is very specific, with linear range from the limit of quantification to 8.67 x 10{sup 3} ng L{sup -1}, a within-run precision of <20% and a between-run precision of <20% for 2-, 3- and 4-ring compounds and of <30% for 5-ring compounds, trueness within 20% of the spiked concentration, and limit of quantification in the 2.28-2.28 x 10{sup 1} ng L{sup -1} range. An application of the proposed method using 15 urine samples from subjects exposed to PAHs at different environmental levels is shown.

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

    Science.gov (United States)

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

    2013-03-15

    A novel analytical approach combining solid-phase microextraction (SPME)/gas chromatography ion trap mass spectrometry (GC-IT-MS) was developed for the detection and quantification N,N-dimethyltryptamine (DMT), a powerful psychoactive indole alkaloid present in a variety of South American indigenous beverages, such as ayahuasca and vinho da jurema. These particular plant products, often used within a religious context, are increasingly consumed throughout the world following an expansion of religious groups and the availability of plant material over the Internet and high street shops. The method described in the present study included the use of SPME in headspace mode combined GC-IT-MS and included the optimization of the SPME procedure using multivariate techniques. The method was performed with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber in headspace mode (70 min at 60 °C) which resulted in good precision (RSDvinho da jurema samples, obtained from Brazilian religious groups, which revealed DMT concentration levels between 0.10 and 1.81 g L(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Degradation product emission from historic and modern books by headspace SPME/GC-MS: evaluation of lipid oxidation and cellulose hydrolysis.

    Science.gov (United States)

    Clark, Andrew J; Calvillo, Jesse L; Roosa, Mark S; Green, David B; Ganske, Jane A

    2011-04-01

    Volatile organic compounds emitted from a several decade series of bound periodicals (1859-1939) printed on ground wood paper, as well as historical books dating from the 1500s to early 1800s made from cotton/linen rag, were studied using an improved headspace SPME/GC-MS method. The headspace over the naturally aging books, stored upright in glass chambers, was monitored over a 24-h period, enabling the identification of a wide range of organic compounds emanating from the whole of the book. The detection of particular straight chain aldehydes, as well as characteristic alcohols, alkenes and ketones is correlated with oxidative degradation of the C(18) fatty acid constituency of paper. The relative importance of hydrolytic and oxidative chemistry involved in paper aging in books published between 1560 and 1939 was examined by comparing the relative abundances of furfural (FUR) a known cellulose hydrolysis product, and straight chain aldehydes (SCA) produced from the oxidation of fatty acids in paper. The relative abundance of furfural is shown to increase across the 379-year publication time span. A comparison of relative SCA peak areas across the series of books examined reveals that SCA emission is more important in the cotton/linen rag books than in the ground wood books.

  16. Full evaporation dynamic headspace in combination with selectable one-dimensional/two-dimensional gas chromatography-mass spectrometry for the determination of suspected fragrance allergens in cosmetic products.

    Science.gov (United States)

    Devos, Christophe; Ochiai, Nobuo; Sasamoto, Kikuo; Sandra, Pat; David, Frank

    2012-09-14

    Suspected fragrance allergens were determined in cosmetic products using a combination of full evaporation-dynamic headspace (FEDHS) with selectable one-dimensional/two-dimensional GC-MS. The full evaporation dynamic headspace approach allows the non-discriminating extraction and injection of both apolar and polar fragrance compounds, without contamination of the analytical system by high molecular weight non-volatile matrix compounds. The method can be applied to all classes of cosmetic samples, including water containing matrices such as shower gels or body creams. In combination with selectable (1)D/(2)D GC-MS, consisting of a dedicated heart-cutting GC-MS configuration using capillary flow technology (CFT) and low thermal mass GC (LTM-GC), a highly flexible and easy-to-use analytical solution is offered. Depending on the complexity of the perfume fraction, analyses can be performed in one-dimensional GC-MS mode or in heart-cutting two-dimensional GC-MS mode, without the need of hardware reconfiguration. The two-dimensional mode with independent temperature control of the first and second dimension column is especially useful to confirm the presence of detected allergen compounds when mass spectral deconvolution is not possible. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Photoassisted vapor generation in the presence of organic acids for ultrasensitive determination of Se by electrothermal-atomic absorption spectrometry following headspace single-drop microextraction

    International Nuclear Information System (INIS)

    Figueroa, Raul; Garcia, Monica; Lavilla, Isela; Bendicho, Carlos

    2005-01-01

    A method is described for the determination of selenium at the pg/mL level by electrothermal-atomic absorption spectrometry using in situ photogeneration of Se vapors, headspace sequestration onto an aqueous microdrop containing Pd(II) and subsequent injection in a graphite tube. Several organic acids (formic, oxalic, acetic, citric and ethylenediaminetetraacetic) have been tried for photoreduction of Se(IV) into volatile Se compounds under UV irradiation. Experimental variables such as UV irradiation time, organic acid concentration, Pd(II) concentration in the drop, sample and drop volumes, extraction time and pH were fully optimized. Low-molecular weight acids such as formic and acetic provided optimal photogeneration of volatile Se species at a 0.6 mol/L concentration. Citric and ethylenediaminetetraacetic acid allowed to use a concentration as low as 1 mmol/L, but extraction times were longer than for formic and acetic acids. Photogeneration of (CH 3 ) 2 Se from Se(IV) in the presence of acetic acid provided a detection limit of 20 pg/mL, a preconcentration factor of nearly 285 and a precision, expressed as relative standard deviation, of 4%. Analytical performance seemed to depend not only on the photogeneration efficiency obtained with each acid but also on the stability of the vapors in the headspace. The method showed a high freedom from interferences caused by saline matrices, but interferences were observed for transition metals at a relatively low concentration

  18. Coumarins as turn on/off fluorescent probes for detection of residual acetone in cosmetics following headspace single-drop microextraction.

    Science.gov (United States)

    Cabaleiro, N; de la Calle, I; Bendicho, C; Lavilla, I

    2014-11-01

    In this work, a new method based on headspace-single drop microextraction for the determination of residual acetone in cosmetics by microfluorospectrometry is proposed. Acetone causes fluorescence changes in a 2.5 µL-ethanolic drop (40% v/v) containing 3.10(-4) mol L(-1) 7-hydroxy-4-methylcoumarin ('turn off') or 6.10(-6) mol L(-1) 7-diethylamino-4-methylcoumarin ('turn on'). Polarity and ability to form hydrogen bonds of short chain alcohols (polar protic solvents) were crucial in order to observe these changes in the presence of acetone (polar aprotic solvent). Parameters related with the HS-SDME procedure were studied, namely headspace volume, composition, volume and temperature of drop, microextraction time, stirring rate, mass and temperature of sample, as well as the effect of potential interferents (alcohols and fragrances). The high volatility of acetone allows its extraction from an untreated cosmetic sample within 3 min. A detection limit of 0.26 µg g(-1) and repeatability, expressed as relative standard deviation, around 5% were reached. Accuracy of the proposed methodology was evaluated by means of recovery studies. The method was successfully used to analyze different cosmetics. Simplicity and high sample throughput can be highlighted. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Headspace Moisture Mapping and the Information That Can Be Gained about Freeze-Dried Materials and Processes.

    Science.gov (United States)

    Cook, Isobel A; Ward, Kevin R

    2011-01-01

    Regulatory authorities require proof that lyophilization (freeze drying) cycles have been developed logically and demonstrate uniformity. One measure of uniformity can be consistency of residual water content throughout a batch. In primary drying, heat transfer is effected by gaseous convection and conduction as well as the degree of shelf contact and evenness of heat applied; therefore residual water can be affected by container location, degree of container/tray/shelf contact, radiative heating, packing density, product formulation, and the cycle conditions themselves. In this study we have used frequency modulation spectroscopy (FMS) to create a map of headspace moisture (HSM) for 100% of vials within a number of freeze-dried batches. Karl Fischer (KF)/HSM correlations were investigated in parallel with the moisture mapping studies. A clear, linear relationship was observed between HSM and KF values for vials containing freeze-dried sucrose, implying a relatively straightforward interaction between water and the lyophilized cake for this material. Mannitol demonstrated a more complex correlation, with the interaction of different crystalline forms giving important information on the uniformity of the material produced. It was observed that annealing had a significant impact on the importance of heat transfer by conduction for vials in direct and non-direct contact with the shelf. Moisture mapping of all vials within the freeze dryer enabled further information to be obtained on the relationship of the formulation, process conditions, and equipment geometry on the intra-batch variability in HSM level. The ability of FMS to allow 100% inspection could mean that this method could play an important part in process validation and quality assurance. Lyophilization, also known as freeze drying, is a relatively old technique that has been used in its most basic form for thousands of years (e.g., preservation of fish and meat products). In its more advanced form it is

  20. Calculation note: project W-320 primary ventilation air flow requirements for mitigation of steady state flammable gas concentrations in the headspaces of tanks 241-C-106 and 241-AY-102

    International Nuclear Information System (INIS)

    Estey, S.D.

    1997-01-01

    This calculation note analyzes headspace concentrations of hydrogen dependent upon assumed ventilation flow rates provided for tanks 241-C-106 and 241-AY-102. The analyses are based on measured or estimated steady state hydrogen release rates. Tank 241-C-106 is analyzed prior to sluicing; tank 241-AY-102 is analyzed both prior to and after completion of sluicing. Specific analyses, using both best estimated and bounding hydrogen generation rates, include the minimum primary ventilation flow rates required in the tanks to ensure that the steady state hydrogen concentration in the respective tank headspace does not exceed 25% and 100% of the LFL. The headspace hydrogen concentration as a function of time as well as the time required to reach 25% and 100% of LFL upon complete loss of active ventilation, starting from the steady state hydrogen concentration based on a 200 CFM minimum flow rate in tank 241-C-106 and a 100 CFM minimum flow rate in tank241-AY-102. The headspace hydrogen concentration as a function of thee following partial loss of active ventilation (i.e., step changes to l60, l20, 80, and 40 CFM ventilation flow rates) in tank 241-C-106, staffing from a 200 CFM flow rate and the corresponding steady state hydrogen concentration based on the 200 CFM flow rate. The headspace hydrogen concentration as a function of the following partial loss of active ventilation i.e., step changes to 80, 60, 40, and 20 CFM ventilation flow rates) in tank 241-AY-102, starting from a 100 CFM flow rate and the corresponding steady state hydrogen concentration based on the 100 CFM flow rate

  1. Method development and optimization for the determination of benzene, toluene, ethylbenzene and xylenes in water at trace levels by static headspace extraction coupled to gas chromatography-barrier ionization discharge detection.

    Science.gov (United States)

    Pascale, Raffaella; Bianco, Giuliana; Calace, Stefania; Masi, Salvatore; Mancini, Ignazio M; Mazzone, Giuseppina; Caniani, Donatella

    2018-05-04

    Benzene, toluene, ethylbenzene, and xylenes, more commonly named BTEX, represent one of the most ubiquitous and hazardous groups of atmospheric pollutants. The goal of our research was the trace quantification of BTEX in water by using a new simple, low-cost, and accurate method, based on headspace (HS) extraction and gas chromatography (GC) coupled to barrier ionization discharge detector (BID). This water application dealt with simple matrices without protein, fat, or humic material that adsorb target analytes, thus the external standard calibration was suitable to quantify each compound. The validation steps included the study of linearity, detection and quantification limits, and accuracy. LODs and LOQs varied from 0.159 to 1.845 μg/L and from 0.202 to 2.452 μg/L, respectively. The recovery was between 0.74 ± 0.13 and 1.15 ± 0.09; relative standard deviations (% RDSs) were less than 12.81% (n = 5) and 14.84% (n = 10). Also, GC performance was evaluated in term of efficiency, peak tailing and resolution. Preliminary results from practical applications to analyses of real samples are presented. The results indicate that static HS coupled to GC-BID is a successful method for BTEX analysis in water samples at the μg/L levels, provided that hydrocarbons interference occur at similar concentration levels. GC-BID may become a routine reference method alongside the official analytical techniques for quality control purposes of contaminated waters. Moreover, the new method is amenable to automation by using commercial HS units. Copyright © 2018. Published by Elsevier B.V.

  2. Headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry for the determination of haloanisoles in sparkling (cava and cider) and non-sparkling (wine) alcoholic beverages.

    Science.gov (United States)

    Ruiz-Delgado, Ana; Arrebola-Liébanas, Francisco Javier; Romero-González, Roberto; López-Ruiz, Rosalía; Garrido Frenich, Antonia

    2016-10-01

    A highly sensitive analytical method was developed to determine 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,4,6-tribromoanisole (TBA) and 2,3,4,5,6-pentachloroanisole (PCA) in sparkling alcoholic beverages. The method was based on the use of headspace solid-phase microextraction (HS-SPME) using a polydimethylsiloxane (PDMS) fibre. It was coupled to gas chromatography-triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) for the detection and quantification of the target haloanisoles. The method was fully automated and no sample preparation was needed. The method was validated for alcoholic beverages. The influence of CO 2 on the extraction efficiency was also evaluated for the studied sparkling drinks (cava and cider). All the calibration curves showed good linearity (R 2  > 0.98) within the tested range (1-50 ng l -1 ). Recoveries were evaluated at three different levels (1, 5 and 50 ng l -1 ) and were always between 71% and 119%. Precision was expressed as relative standard deviation (RSD), and was evaluated as intra- and inter-day precisions, with values ≤ 22% in both cases. Limits of quantitation (LOQs) were ≤ 0.91 ng l -1 , which are below the sensory threshold levels for such compounds in humans. The validated method was applied to commercial samples, 10 cavas and 10 ciders, but it was also used for the analysis of nine red wines and four white wines, demonstrating the further applicability of the proposed method to non-sparkling beverages. TCA was detected in most samples at up to 0.45 ng l -1 .

  3. Determination of the Three Main Components of the Grapevine Moth Pest Pheromone in Grape-Related Samples by Headspace-Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    María del Carmen Alcudia-León

    2017-10-01

    Full Text Available The grapevine moth (Lobesia botrana is the most significant pest of viticulture. This article reports the development of an analytical method that allows the instrumental determination of the three main pheromone components of the pest ((E,Z-7,9-dodecadien-1-yl acetate, (E,Z-7,9-dodecadien-1-ol and (Z-9-dodecen-1-yl acetate in grape-related samples (must, table grape and wine grape. The combination of headspace, gas chromatography and mass spectrometry provides limits of detection in the range of 60–420 ng/Kg and precision, expressed as a relative standard deviation, better than 8.5%. This analytical approach is rapid and simple and opens a door to the study of the pest incidence on the final products.

  4. A novel method for the determination of adsorption partition coefficients of minor gases in a shale sample by headspace gas chromatography.

    Science.gov (United States)

    Zhang, Chun-Yun; Hu, Hui-Chao; Chai, Xin-Sheng; Pan, Lei; Xiao, Xian-Ming

    2013-10-04

    A novel method has been developed for the determination of adsorption partition coefficient (Kd) of minor gases in shale. The method uses samples of two different sizes (masses) of the same material, from which the partition coefficient of the gas can be determined from two independent headspace gas chromatographic (HS-GC) measurements. The equilibrium for the model gas (ethane) was achieved in 5h at 120°C. The method also involves establishing an equation based on the Kd at higher equilibrium temperature, from which the Kd at lower temperature can be calculated. Although the HS-GC method requires some time and effort, it is simpler and quicker than the isothermal adsorption method that is in widespread use today. As a result, the method is simple and practical and can be a valuable tool for shale gas-related research and applications. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Tank vapor characterization project. Headspace vapor characterization of Hanford waste Tank SX-101: Results from samples collected on 07/21/95

    International Nuclear Information System (INIS)

    Evans, J.C.; Clauss, T.W.; McVeety, B.D.; Pool, K.H.; Olsen, K.B.; Fruchter, J.S.; Silvers, K.L.

    1996-05-01

    Results described in this report were obtained to characterize the vapors present in the tank headspace and to support safety evaluations and tank-farm operations. They include air concentrations of inorganic and organic analytes and grouped compounds from samples. The vapor concentrations are based either on whole-volume samples or on sorbent traps exposed to sample flow. No immediate notifications were needed because analytical results indicated no specific analytes exceeded notification levels. Summary of results: NH3, 3.8 ppmv; NO2, 0.10 ppmv; NO, 0.13 ppm; H2O, 11.8 mg/L; CO2, 338 ppmv; CO, 3 ; methanol, 0.060 ppmv; acetone, 0.033 ppmv; trichlorofluoromethane, 0.023 ppmv; and acetone, 0.034 ppmv

  6. Headspace solid-phase microextraction (HS-SPME) and liquid-liquid extraction (LLE): comparison of the performance in classification of ecstasy tablets. Part 2.

    Science.gov (United States)

    Bonadio, Federica; Margot, Pierre; Delémont, Olivier; Esseiva, Pierre

    2008-11-20

    Headspace solid-phase microextraction (HS-SPME) is assessed as an alternative to liquid-liquid extraction (LLE) currently used for 3,4-methylenedioxymethampethamine (MDMA) profiling. Both methods were compared evaluating their performance in discriminating and classifying samples. For this purpose 62 different seizures were analysed using both extraction techniques followed by gas chromatography-mass spectroscopy (GC-MS). A previously validated method provided data for HS-SPME, whereas LLE data were collected applying a harmonized methodology developed and used in the European project CHAMP. After suitable pre-treatment, similarities between sample pairs were studied using the Pearson correlation. Both methods enable to distinguish between samples coming from the same pre-tabletting batches and samples coming from different pre-tabletting batches. This finding emphasizes the use of HS-SPME as an effective alternative to LLE, with additional advantages such as sample preparation and a solvent-free process.

  7. A novel multiple headspace extraction gas chromatographic method for measuring the diffusion coefficient of methanol in water and in olive oil.

    Science.gov (United States)

    Zhang, Chun-Yun; Chai, Xin-Sheng

    2015-03-13

    A novel method for the determination of the diffusion coefficient (D) of methanol in water and olive oil has been developed. Based on multiple headspace extraction gas chromatography (MHE-GC), the methanol released from the liquid sample of interest in a closed sample vial was determined in a stepwise fashion. A theoretical model was derived to establish the relationship between the diffusion coefficient and the GC signals from MHE-GC measurements. The results showed that the present method has an excellent precision (RSDwater and olive oil, when compared with data reported in the literature. The present method is simple and practical and can be a valuable tool for the determination of the diffusion coefficient of volatile analyte(s) into food simulants from food and beverage packaging material, both in research studies and in actual applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Determination of antioxidants in new and used lubricant oils by headspace-programmed temperature vaporization-gas chromatography-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Nogal Sanchez, Miguel del; Perez Pavon, Jose Luis; Garcia Pinto, Carmelo; Moreno Cordero, Bernardo [Universidad de Salamanca, Departamento de Quimica Analitica, Nutricion y Bromatologia, Salamanca (Spain); Glanzer, Paul [University of Vienna, Department of Analytical Chemistry, Vienna (Austria)

    2010-12-15

    A sensitive method is presented to determine antioxidants (2-, 3-, and 4-tert-butylphenol, 2,6-di-tert-butylphenol, 3-tert-butyl-4-hydroxyanisol, 2,6-di-tert-butyl-4-methylphenol, 1-naphthol, and diphenylamine) in new and used lubricant oil samples. Research was carried out on a GC device equipped with a headspace sampler, a programmed temperature vaporizer, and an MS detector unit. The proposed method does not require sample treatment prior to analyses, hence eliminating possible errors occurring in this step. Sample preparation is reduced when placing the oil sample (2.0 g) in the vial and adding propyl acetate (20 {mu}L). Solvent vent injection mode permits a pre-concentration of the compounds of interest in the liner filled with Tenax-TA {sup registered}, while venting other species present in the headspace. Thereby, both the life of the liner and the capillary column is prolonged, and unnecessary contamination of the detector unit is avoided. Calibration was performed by adding different concentrations of analytes to a new oil which did not contain any of the studied compounds. Limits of detection as low as 0.57 {mu}g/L (2-tert-butylphenol) with a precision lower or equal to 5.3% were achieved. Prediction of the antioxidants in new oil samples of different viscosities (5W40, 10W40, and 15W40) was accomplished with the previous calibration, and the results were highly satisfactory. To determine antioxidants in used engine oils, standard addition method was used due to the matrix effect. (orig.)

  9. GC-MS analysis of aroma of Medemia argun (mama-n-khanen or mama-n-xanin), an ancient Egyptian fruit palm.

    Science.gov (United States)

    Hamed, Arafa I; Leonardi, Michele; Stochmal, Anna; Oleszek, Wieslaw; Pistelli, Luisa

    2012-05-01

    The fruits of the edible and medicinal Egyptian palm, Medemia argun, were collected from Aswan in Egypt and the essential oil (EO) from fruits and headspace (HS) of the seeds and fleshy mesocarps were analyzed by GC and GC-MS. Results obtained by GC-MS analysis indicated a high variability in the oil and in the headspace from seeds and mesocarps. Sesquiterpene derivatives were the main group of volatiles in the EO from fruits and in the HS from seeds (45.0 and 64.0%, respectively), while oxygenated hydrocarbon derivatives were the main constituents in the HS obtained from fleshy mesocarps (96.5%). The different chemical composition of the headspace obtained from the seeds and mesocarps of M. argun can be correlated with the different roles that the different constituents play in the prevention of dehydration of the fruits in the desert region from where the plant was collected.

  10. Evaluation of noni (Morinda citrifolia volatile profile by dynamic headspace and gas chromatography-mass spectrometry Avaliação do perfil de voláteis em noni (Morinda citrifolia por headspace dinâmico e cromatografia gasosa-espectrometria de massas

    Directory of Open Access Journals (Sweden)

    Adriana Sousa

    2010-09-01

    Full Text Available Noni is a fruit that has interested the scientific community due to its medicinal and functional activities. Different products that contain noni are already in the market, but their consumption could be impaired by their distinctive unpleasant aroma and flavor. The aim of this work was to evaluate the noni pulp volatile profile by dynamic headspace and gas chromatography-mass spectrometry. Thirty seven volatile compounds were detected, mainly alcohols (63.3%, esters (26.9%, cetones (7.4%, and acids (1.2%.O noni é um fruto que tem interessado à comunidade científica por sua atividade funcional e medicinal. Já se encontram no mercado diferentes produtos que contêm noni em sua composição, mas seu consumo tem sido prejudicado por seu aroma e sabor desagradáveis. O objetivo deste trabalho foi o de avaliar o perfil de voláteis da polpa de noni pela técnica de headspace dinâmico e cromatografia gasosa-espectrometria de massas. Foram detectados 37 compostos voláteis, sendo os principais: alcoóis (63,3%, ésteres (26,9%, cetonas (7,4% e ácidos (1,2%.

  11. Determination of 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in soy sauce by headspace derivatization solid-phase microextraction combined with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Lee, Maw-Rong; Chiu, Tzu-Chun; Dou, Jianpeng

    2007-05-22

    This study proposes a method for identifying 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in aqueous matrices by using headspace on-fiber derivatization following solid-phase microextraction combined with gas chromatography-mass spectrometry. The optimized SPME experimental procedures for extracting 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in aqueous solutions involved a 85 microm polyacrylate-coated fiber at pH 6, a sodium chloride concentration of 0.36 g mL(-1), extraction at 50 degrees C for 15 min and desorption of analytes at 260 degrees C for 3 min. Headspace derivatization was conducted in a laboratory-made design with N-methyl-N-(trimethylsilyl)-trifluoroacetamide vapor following solid-phase microextraction by using 3 microL N-methyl-N-(trimethylsilyl)-trifluoroacetamide at an oil bath temperature of 230 degrees C for 40 s. This method had good repeatability (R.S.D.s or = 0.9972) for ultrapure water and soy sauce samples that were spiked with two analytes. Detection limits were obtained at the ng mL(-1). The result demonstrated that headspace on-fiber derivatization following solid-phase microextraction was a simple, fast and accurate technique for identifying trace 1,3-dichloro-2-propanol and 3-chloro-1,2-propandiol in soy sauce.

  12. Determination of residual volatile organic compounds migrated from polystyrene food packaging into food simulant by headspace solid phase micro extraction-gas chromatography

    International Nuclear Information System (INIS)

    Mohd Marsin Sanagi; Ling, Susie Lu; Zalilah Nasir; Wan Aini Wan Ibrahim; Abu Naim, Ahmedy

    2008-01-01

    The residual styrene and other volatile organic compounds (VOCs) present in the polystyrene food packaging are of concern as these compounds have the potential to migrate into the food in contact. This work describes a method for quantitative determination of VOCs, namely styrene, toluene, ethyl benzene, iso-propylbenzene and n-propylbenzene that have migrated from polystyrene food packaging into food stimulant by gas chromatography-flame ionization detection (GC-FID). Headspace solid phase micro extraction (HS-SPME) technique was applied for migration test using water as food stimulant. The effects of extraction variables including sample volume, eluotropic strength, extraction temperature, extraction time, desorption time, sample agitation, and salt addition on the amounts of the extracted analyses were studied to obtain the optimal HS-SPME conditions. The optimized method was applied to test the VOCs migrated from polystyrene bowls and cups at storage temperatures ranging from 24 to 80 degree Celsius for 30 min. Styrene and ethyl benzene were found to migrate from the samples into the food stimulant. The migration of analyze was found to be strongly dependent upon the storage temperature. The HS-SPME is useful as an alternative method to determine the migration of VOCs from food packaging material into food stimulant. (author)

  13. 32-Week Holding-Time Study of SUMMA Polished Canisters and Triple Sorbent Traps Used To Sample Organic Constituents in Radioactive Waste Tank Vapor Headspace

    International Nuclear Information System (INIS)

    Evans, John C.; Huckaby, James L.; Mitroshkov, Alexandre V.; Julya, Janet L.; Hayes, James C.; Edwards, Jeffrey A.; Sasaki, Leela M.

    1997-01-01

    Two sampling methods[SUMMA polished canisters and triple sorbent traps (TSTs)] were compared for long-term storage of trace organic vapor samples collected from the headspaces of high-level radioactive waste tanks at the U.S. Department of Energy's Hanford Site in Washington State. Because safety, quality assurance, radiological controls, the long-term stability of the sampling media during storage needed to be addressed. Samples were analyzed with a gas chromatograph/mass spectrometer (GC/MS) using cryogenic reconcentration or thermal desorption sample introduction techniques. SUMMA canister samples were also analyzed for total non-methane organic compounds (TNMOC) by GC/flame ionization detector (FID) using EPA Compendium Method TO-12 . To verify the long-term stability of the sampling media, multiple samples were collected in parallel from a typical passively ventilated radioactive waste tank known to contain moderately high concentrations of both polar and nonpolar organic compounds. Analyses for organic analytes and TNMOC were conducted at increasing intervals over a 32-week period to determine whether any systematic degradation of sample integrity occurred. Analytes collected in the SUMMA polished canisters generally showed good stability over the full 32 weeks with recoveries at the 80% level or better for all compounds studied. The TST data showed some loss (50-80% recovery) for a few high-volatility compounds even in the refrigerated samples; losses for unrefrigerated samples were far more pronounced with recoveries as low as 20% observed in a few cases

  14. Speciation and determination of inorganic mercury and methylmercury by headspace single drop microextraction and electrothermal atomic absorption spectrometry in water and fish

    Energy Technology Data Exchange (ETDEWEB)

    Sarica, Deniz Yurtsever [Scientific and Technological Research Council of Turkey, Ankara Test and Analysis Laboratory, TUeBITAK/ATAL, Besevler, Ankara (Turkey); Tuerker, Ali Rehber [Science Faculty, Department of Chemistry, Gazi University, Ankara (Turkey)

    2012-05-15

    In this study, headspace single drop microextraction (HS-SDME) method in combination with electrothermal atomic absorption spectrometry (ETAAS) method was developed and validated for the speciation and determination of inorganic mercury (iHg) and methylmercury (MeHg). MeHg and iHg species were reduced to volatile methylmercury hydride (CH{sub 3}HgH) and elemental mercury, respectively, in the presence of NaBH{sub 4} and trapped onto a drop of acceptor phase in the tip of a microsyringe. Thiourea and ammonium pyrrolydinedithiocarbamate (APDC) were tested as the acceptor phase. The experimental parameters of the method such as microextraction time, temperature, NaBH{sub 4} concentration, acceptor phase concentration, and pH of the medium were investigated to obtain distinctive conditions for mercury species. Possible interference effects have also been investigated. In order to validation of the method, analytical figures of merits such as accuracy, precision, limit of detection (LOD), limit of quantitation (LOQ), and linear working range have been evaluated. Accuracy of the method has been verified by analyzing certified reference materials (BCR 453 Tuna fish) and spiked samples. The proposed method was applied for the speciation and determination of mercury species in water and fish samples. Mercury species (MeHg and iHg) have been determined in the real samples with a relative error less than 10%. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    Science.gov (United States)

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

    2016-09-10

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

  16. Quantification of 2-acetyl-1-pyrroline in rice by stable isotope dilution assay through headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Maraval, Isabelle [UMR Qualisud, CIRAD, 73 Rue J. F. Breton, 34398 Montpellier Cedex 5 (France); UMR Qualisud, Universite Montpellier 2, place E. Bataillon, 34095 Montpellier Cedex 5 (France); Sen, Kemal [Department of Food Engineering, Faculty of Agriculture, University of Cukurova, 01330 Adana (Turkey); Agrebi, Abdelhamid; Menut, Chantal; Morere, Alain [UMR 5247, Institut des Biomolecules Max Mousseron (IBMM), CNRS, Universites Montpellier 2 et 1, Ecole Nationale Superieure de Chimie de Montpellier, 8 Rue de l' Ecole Normale, 34296 Montpellier Cedex 5 (France); Boulanger, Renaud [UMR Qualisud, CIRAD, 73 Rue J. F. Breton, 34398 Montpellier Cedex 5 (France); Gay, Frederic [CIRAD, DORAS Centre, Research and Development Building, Kasetsart University, Bangkok 10900 (Thailand); Mestres, Christian [UMR Qualisud, CIRAD, 73 Rue J. F. Breton, 34398 Montpellier Cedex 5 (France); Gunata, Ziya, E-mail: zgunata@univ-montp2.fr [UMR Qualisud, Universite Montpellier 2, place E. Bataillon, 34095 Montpellier Cedex 5 (France)

    2010-08-24

    A new and convenient synthesis of 2-acetyl-1-pyrroline (2AP), a potent flavor compound in rice, and its ring-deuterated analog, 2-acetyl-1-d{sub 2}-pyrroline (2AP-d{sub 2}), was reported. A stable isotope dilution assay (SIDA), involving headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-positive chemical ionization-ion trap-tandem mass spectrometry (GC-PCI-IT-MS-MS), was developed for 2AP quantification. A divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was used for HS-SPME procedure and parameters affecting analytes recovery, such as extraction time and temperature, pH and salt, were studied. The repeatability of the method (n = 10) expressed as relative standard deviation (RSD) was 11.6%. A good linearity was observed from 5.9 to 779 ng of 2AP (r{sup 2} = 0.9989). Limits of detection (LOD) and quantification (LOQ) for 2AP were 0.1 and 0.4 ng g{sup -1} of rice, respectively. The recovery of spiked 2AP from rice matrix was almost complete. The developed method was applied to the quantification of 2AP in aerial parts and grains of scented and non-scented rice cultivars.

  17. A selective and sensitive optical sensor for dissolved ammonia detection via agglomeration of fluorescent Ag nanoclusters and temperature gradient headspace single drop microextraction.

    Science.gov (United States)

    Dong, Jiang Xue; Gao, Zhong Feng; Zhang, Ying; Li, Bang Lin; Li, Nian Bing; Luo, Hong Qun

    2017-05-15

    In this paper, a simple sensor platform is presented for highly selective and sensitive detection of dissolved ammonia in aqueous solutions without pretreatment based on temperature gradient headspace single drop microextraction (HS-SDME) technique, and fluorescence and UV-vis spectrophotometry are utilized with the Ag nanoclusters (Ag NCs) functioned by citrate and glutathione as the probe. The sensing mechanism is based on the volatility of ammonia gas and the active response of Ag NCs to pH change caused by the introduction of ammonia. High pH can make the Ag NCs agglomerate and lead to the obvious decrease of fluorescence intensity and absorbance of Ag NCs solution. Moreover, the presented method exhibits a remarkably high selectivity toward dissolved ammonia over most of inorganic ions and amino acid, and shows a good linear range of 10-350μM (0.14-4.9mgNL -1 ) with a low detection limit of 336nM (4.70μgNL -1 ) at a signal-to-noise ratio of 3. In addition, the practical applications of the sensor have been successfully demonstrated by detecting dissolved ammonia in real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Hydrogen sulfide measurement by headspace-gas chromatography-mass spectrometry (HS-GC-MS): application to gaseous samples and gas dissolved in muscle.

    Science.gov (United States)

    Varlet, Vincent; Giuliani, Nicole; Palmiere, Cristian; Maujean, Géraldine; Augsburger, Marc

    2015-01-01

    The aim of our study was to present a new headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable to the routine determination of hydrogen sulfide (H(2)S) concentrations in biological and gaseous samples. The primary analytical drawback of the GC/MS methods for H(2)S measurement discussed in the literature was the absence of a specific H(2)S internal standard required to perform quantification. Although a deuterated hydrogen sulfide (D(2)S) standard is currently available, this standard is not often used because this standard is expensive and is only available in the gas phase. As an alternative approach, D(2)S can be generated in situ by reacting deuterated chloride with sodium sulfide; however, this technique can lead to low recovery yield and potential isotopic fractionation. Therefore, N(2)O was chosen for use as an internal standard. This method allows precise measurements of H(2)S concentrations in biological and gaseous samples. Therefore, a full validation using accuracy profile based on the β-expectation tolerance interval is presented. Finally, this method was applied to quantify H(2)S in an actual case of H(2)S fatal intoxication. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  19. Multivariate optimization of a headspace solid-phase microextraction method followed by gas chromatography with mass spectrometry for the determination of terpenes in Nicotiana langsdorffii.

    Science.gov (United States)

    Ardini, Francisco; Carro, Marina Di; Abelmoschi, Maria Luisa; Grotti, Marco; Magi, Emanuele

    2014-07-01

    A simple and sensitive procedure based on headspace solid-phase microextraction and gas chromatography with mass spectrometry was developed for the determination of five terpenes (α-pinene, limonene, linalool, α-terpineol, and geraniol) in the leaves of Nicotiana langsdorffii. The microextraction conditions (extraction temperature, equilibration time, and extraction time) were optimized by means of a Doehlert design. The experimental design showed that, for α-pinene and limonene, a low temperature and a long extraction time were needed for optimal extraction, while linalool, α-terpineol, and geraniol required a high temperature and a long extraction time. The chosen compromise conditions were temperature 60°C, equilibration time 15 min and extraction time 50 min. The main analytical figures of the optimized method were evaluated; LODs ranged from 0.07 ng/g (α-pinene) to 8.0 ng/g (geraniol), while intraday and interday repeatability were in the range 10-17% and 9-13%, respectively. Finally, the procedure was applied to in vitro wild-type and transgenic specimens of N. langsdorffii subjected to abiotic stresses (chemical and heat stress). With the exception of geraniol (75-374 ng/g), low concentration levels of terpenes were measured (ng/g level or lower); some interesting variations in terpene concentration induced by abiotic stress were observed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Identification of volatile organic compounds (VOCs in different colour carrot (Daucus carota L. cultivars using static headspace/gas chromatography/mass spectrometry

    Directory of Open Access Journals (Sweden)

    Zehra Güler

    2015-12-01

    Full Text Available Volatile organic compounds (VOCs as well as sugar and acid contents affect carrot flavour. This study compared VOCs in 11 carrot cultivars. Gas chromatography/mass spectrometry using static headspace technique was applied to analyse the VOCs. The number of VOCs per sample ranged from 17 to 31. The primarily VOCs identified in raw carrots with the exception of “Yellow Stone” were terpenes, ranging from 65 to 95%. The monoterpenes with values ranging from 31 to 89% were higher than those (from 2 to 15% of sesquiterpenes. Monoterpene α-terpinolene (with ranging from 23 to 63% and (--α-pinene (26%, and alcohol ethanol (35% was the main VOC in extracts from the nine carrot cultivars, “Purple” and “Yellow Stone”, respectively. As a result, among 16 identified monoterpenes, 7 monoterpenes (--α-pinene, (--β-pinene, β-myrcene, d-limonene, γ-terpinene, α-terpinolene and p-cymene constituted more than 60% of total VOCs identified in carrots including “Atomic Red”, “Nantes”, “Cosmic Purple”, “Red Samurai”, “Eregli Black”, “White Satin”, “Parmex” and “Baby Carrot”. Thus, these cultivars may advise to carrot breeders due to the beneficial effects of terpenes, especially monoterpenes on health.

  1. Non-Destructive Assessment of Aroma Volatiles from a Climacteric Near-Isogenic Line of Melon Obtained by Headspace Stir-Bar Sorptive Extraction

    Directory of Open Access Journals (Sweden)

    Juan Pablo Fernández-Trujillo

    2013-08-01

    Full Text Available A climacteric aromatic near-isogenic line (NIL of melon (Cucumis melo L. SC3-5-1 contained an introgression of the non-climacteric Korean cultivar “Shongwan Charmi” accession PI 161375 (SC in the genetic background of the non-climacteric cultivar “Piel de Sapo” (PS. The aroma production was monitored during ripening at 21 °C in intact fruit using headspace sorptive bar extraction (HSSE. Bars were composed of polydimethylsiloxane (PDMS and aromas were desorbed and analyzed by gas-chromatography mass-spectrometry. The aromatic profile was composed of 70 aromatic compounds plus 21 alkanes with a predominance of esters, particularly acetate (2-methylbutyl acetate, 2-methylpropyl acetate, hexyl acetate, and phenylmethyl acetate. Some compounds were severely affected by postharvest time. The acetate esters (3-methylbutyl acetate, butan-2-yl acetate and phenylmethyl acetate decreased with ripening and sulfur-derived compounds (S-methyl butanethioate and S-methyl 3-methylbutanethioate increased gradually with ripening. A few compounds increased at the senescence phase (propyl ethanoate. Other compounds such as hexadecanoic acid showed a marked decrease after harvest, some decreasing from a relative maximum at harvest (2-methylpropyl hexanoate; n-hexanoic acid; nonanoic acid.

  2. Ethanol concentration in 56 refillable electronic cigarettes liquid formulations determined by headspace gas chromatography with flame ionization detector (HS-GC-FID).

    Science.gov (United States)

    Poklis, Justin L; Wolf, Carl E; Peace, Michelle R

    2017-10-01

    Personal battery-powered vaporizers or electronic cigarettes were developed as an alternative to traditional cigarettes. The modern electronic cigarettes were patented in 2004 by Hon Lik in China. In May 2016, the US Food and Drug Administration (FDA) imposed regulatory statutes on e-cigarettes and their liquid formulations (e-liquids); prior to that, they were unregulated. E-liquids are typically composed of propylene glycol and/or glycerin, flavouring component(s), and active ingredient(s), such as nicotine. Fifty-six commercially available e-liquids, purchased from various sources, contained a variety of flavours and active ingredients. A headspace gas chromatography with flame ionization detector (HS-GC-FID) method was used to analyze these e-liquids for volatiles content. Only one of the e-liquids listed ethanol as a component. The chromatographic separation of volatiles was performed on a Restek BAC-1 column. A linear calibration was generated for ethanol with limits of detection and quantification (LOD/LOQ) of 0.05 mg/mL. Ethanol concentrations in the 56 e-liquids ranged from none detected to 206 mg/mL. The ethanol determined in these products may have been used in flavourants or a solvent; the reason for inclusion cannot be fully ascertained. The implications of vaporizing ethanol as an e-liquid component are unknown. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  3. The influence of headspace and dissolved oxygen level on growth and haemolytic BL enterotoxin production of a psychrotolerant Bacillus weihenstephanensis isolate on potato based ready-to-eat food products.

    Science.gov (United States)

    Samapundo, S; Everaert, H; Wandutu, J N; Rajkovic, A; Uyttendaele, M; Devlieghere, F

    2011-04-01

    The major objective of this study was to determine the influence of the initial headspace and dissolved O(2) level and vacuum packaging on growth and diarrhoeal enterotoxin production by Bacillus weihenstephanensis on potato based ready-to-eat food products. In general, the lower the initial headspace or dissolved O(2) level the slower the maximum growth rate (μ(max), log(10) CFU g(-1) d(-1)), the longer the lag phase duration (λ, d) and the smaller the maximum population density (N(max), log(10) CFU g(-1)) became. The slowest μ(max), the longest λ and the smallest N(max) were generally found for growth under vacuum packaging. This implies shorter shelf-lives will occur at higher initial headspace or dissolved O(2) levels as the growth of B. weihenstephanensis to the infective dose of 10(5) CFU g(-1) in such atmospheres takes a shorter time. Significant consumption of dissolved O(2) only occurred when growth shifted from the lag to the exponential phase and growth generally transitioned from the exponential to the stationary phase when the dissolved O(2) levels fell below ca. 75 ppb. Diarrhoeal enterotoxin production (determined via detection of the L2 component of haemolytic BL) was similar for growth under initial headspace O(2) levels of 1-20.9%, and was only reduced when growth took place under vacuum packaging. The reduction in L2 production when growth took place under vacuum was most probably related to the low final cell densities observed under this condition. Both growth and L2 production were inhibited over a 32-day incubation period at 7 °C by 40% CO(2) irrespective of the headspace or dissolved O(2) levels. The results illustrate the importance of residual O(2) and CO(2) on the shelf-stability and safety of modified atmosphere packaged potato based ready-to-eat food products with regards to B. weihenstephanensis. Copyright © 2010 Elsevier Ltd. All rights reserved.

  4. Screening of transformation products in soils contaminated with unsymmetrical dimethylhydrazine using headspace SPME and GC-MS

    NARCIS (Netherlands)

    Kenessov, B.N.; Koziel, J.A.; Grotenhuis, J.T.C.; Carlsen, L.

    2010-01-01

    The paper describes a novel SPME-based approach for sampling and analysis of transformation products of highly reactive and toxic unsymmetrical dimethylhydrazine (UDMH) which is used as a fuel in many Russian, European, Indian, and Chinese heavy cargo carrier rockets. The effects of several

  5. Determination of volatile polycyclic aromatic hydrocarbons in waters using headspace solid-phase microextraction with a benzyl-functionalized crosslinked polymeric ionic liquid coating.

    Science.gov (United States)

    Merdivan, Melek; Pino, Verónica; Anderson, Jared L

    2017-08-01

    A benzyl-functionalized crosslinked polymeric ionic liquid (PIL), produced through the co-polymerization of the 1-vinylbenzyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (VBHDIM-NTf 2 ) ionic liquid (IL) monomer and 1,12-di(3-vinylbenzylimidazolium)dodecane bis[(trifluoromethyl)sulfonyl]imide ((DVBIM) 2 C 12- 2NTf 2 ) IL crosslinker, was successfully used as a sorbent coating in headspace solid-phase microextraction (SPME) coupled to gas chromatography (GC) with flame-ionization detection (FID) to determine seven volatile polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Optimum extraction conditions for the PAHs when using the novel sorbent include an extraction temperature of 50°C, an ionic strength content adjusted with 30% (w/v) NaCl in the aqueous sample, and an extraction time of 60 min. The extraction performance of the crosslinked PIL fiber was compared to the SPME commercial coating polydimethylsiloxane fiber. The calibration ranges of the studied PAHs were linear in the range of 0.02-20 µg L -1 for the crosslinked PIL fiber. The accuracy of the proposed method was demonstrated by examining the spiked recoveries of seven PAHs which produced values ranging from 67.2% to 130% (for river- and seawater samples), and precision values lower than 9.4% for a spiked level of 1 µg L -1 , and detection limits between 0.01 and 0.04 µg L -1 , which supports the sensitivity of the method using GC-FID.

  6. Simple determination of hydrazine in waste water by headspace solid-phase micro extraction and gas chromatography-tandem mass spectrometry after derivatization with trifluoro pentanedione.

    Science.gov (United States)

    Oh, Jin-Aa; Shin, Ho-Sang

    2017-01-15

    A headspace solid-phase micro extraction (HS-SPME) and gas chromatography-tandem mass spectrometric (GC-MS/MS) method is described to detect hydrazine after derivatization with 1,1,1-trifluoro-2,4-pentanedione (1,1,1-TFPD) to 3-methyl-5-(trifluoromethyl) pyrazole in industrial waste water. The following optimal HS-SPME conditions were used: 85 μm-carboxen-polydimethylsiloxane fibre, 100 mg L -1 TFPD, saturated NaCl, an extraction/derivatization temperature of 80 °C, a heating time of 40 min, and a pH of 9.5. Under the established conditions, the detection and quantification limits were 0.002 μg L -1 and 0.007 μg L -1  by using 5 mL of waste water and the intra- and inter-day relative standard deviations were less than 10.2% at concentrations of 0.02 and 0.1 μg L -1 . The calibration curve showed good linearity, with r 2  = 0.998; the accuracy was in the range of 98.0-103%; and the precision of the assay was less than 10.2% in industrial waste water. Hydrazine was detected over a concentration range of 0.011-0.074 μg L -1 in 5 of 20 waste water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2018-04-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-15

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

  9. Headspace solid phase microextraction--GC/C-IRMS for delta13CVPDB measurements of mono-aromatic hydrocarbons using EA-IRMS calibration.

    Science.gov (United States)

    Ebongué, Véronique Woule; Geypens, Benny; Berglund, Michael; Taylor, Philip

    2009-03-01

    This work aims at comparing the delta(13)C(VPDB) of mono-aromatic hydrocarbons benzene, toluene, ethylbenzene and xylene isomers (BTEX) measured by elemental analyser (EA)-isotope ratio mass spectrometer (IRMS) with the delta(13)C(VPDB) measured on the same compounds by headspace solid phase microextraction - GC/C-IRMS (hSPME - GC/C-IRMS) with the final goal of using these compounds as internal standards on the latter system. The EA-IRMS measurements were done using calcium and lithium carbonate isotopic reference materials: NBS19 and L-SVEC for establishing the delta(13)C(VPDB) scale. The EA-IRMS measurements with helium dilution of a set of five reference materials (USGS40, USGS41, IAEA-CH-6, IAEA-CH-3 and IAEA-601) show systematic bias of 1 per thousand relative to their assigned values. This bias due to the dilution mechanism in the used ConfloII interface device could not be avoided. As the selected hydrocarbons: BTEX could not be analysed by EA-IRMS without helium dilution, their delta(13)C(VPDB) must be corrected from this observed bias using an external calibration. The CO(2) gas calibrated using EA-IRMS without helium dilution, was used as an in-house reference for the delta(13)C(VPDB) measurements of the BTEX by the hSPME - GC/C-IRMS system. The comparison made between the delta(13)C(VPDB) measured on the same BTEX compounds by EA-IRMS (with external calibration) and by hSPME - GC/C-IRMS techniques showed good agreement.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  11. Evaluation of peroxidative stress of cancer cells in vitro by real-time quantification of volatile aldehydes in culture headspace

    Czech Academy of Sciences Publication Activity Database

    Shestivska, Violetta; Rutter, A. V.; Sule-Suso, J.; Smith, D.; Španěl, Patrik

    2017-01-01

    Roč. 31, č. 16 (2017), s. 1344-1352 ISSN 0951-4198 R&D Projects: GA ČR(CZ) GP14-15771P Institutional support: RVO:61388955 Keywords : ion flow tube * active oxygen forms * trace gas-analysis * sift-ms * mass-spectrometry Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 1.998, year: 2016

  12. Evaluation of peroxidative stress of cancer cells in vitro by real-time quantification of volatile aldehydes in culture headspace

    Czech Academy of Sciences Publication Activity Database

    Shestivska, Violetta; Rutter, A. V.; Sule-Suso, J.; Smith, D.; Španěl, Patrik

    2017-01-01

    Roč. 31, č. 16 (2017), s. 1344-1352 ISSN 0951-4198 R&D Projects: GA ČR(CZ) GP14-15771P Institutional support: RVO:61388955 Keywords : ion flow tube * active oxygen forms * trace gas- analysis * sift-ms * mass-spectrometry Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 1.998, year: 2016

  13. Combining information from headspace mass spectrometry and visible spectroscopy in the classification of the Ligurian olive oils

    Energy Technology Data Exchange (ETDEWEB)

    Casale, Monica [Dipartimento di Chimica e Tecnologie Farmaceutiche ed Alimentari, Universita di Genova, Via Brigata Salerno (ponte), I-16147 Genova (Italy)]. E-mail: monica@dictfa.unige.it; Armanino, Carla [Dipartimento di Chimica e Tecnologie Farmaceutiche ed Alimentari, Universita di Genova, Via Brigata Salerno (ponte), I-16147 Genova (Italy); Casolino, Chiara [Dipartimento di Chimica e Tecnologie Farmaceutiche ed Alimentari, Universita di Genova, Via Brigata Salerno (ponte), I-16147 Genova (Italy); Forina, Michele [Dipartimento di Chimica e Tecnologie Farmaceutiche ed Alimentari, Universita di Genova, Via Brigata Salerno (ponte), I-16147 Genova (Italy)

    2007-04-18

    An electronic nose and an UV-Vis spectrophotometer, in combination with multivariate analysis, have been used to verify the geographical origin of extra virgin olive oils. Forty-six oil samples from three different areas of Liguria were included in this analysis. Initially, the data obtained from the two instruments were analysed separately. Then, the potential of the synergy between these two technologies for testing food authenticity and quality was investigated. Application of Linear Discriminant Analysis, after feature selection, was sufficient to differentiate the three geographical denominations of Liguria ('Riviera dei Fiori', 'Riviera del Ponente Savonese' and 'Riviera di Levante'), obtaining 100% success in classification and close to 100% in prediction. The models built using SIMCA as a class-modelling tool, were not so effective, but confirmed that the results improve using the synergy between different analytical techniques. This paper shows that objective instrumental data related to two important organoleptic features such as oil colour and aroma, supply complementary information.

  14. Principles of qualitative analysis in the chromatographic context.

    Science.gov (United States)

    Valcárcel, M; Cárdenas, S; Simonet, B M; Carrillo-Carrión, C

    2007-07-27

    This article presents the state of the art of qualitative analysis in the framework of the chromatographic analysis. After establishing the differences between two main classes of qualitative analysis (analyte identification and sample classification/qualification) the particularities of instrumental qualitative analysis are commented on. Qualitative chromatographic analysis for sample classification/qualification through the so-called chromatographic fingerprint (for complex samples) or the volatiles profile (through the direct coupling headspace-mass spectrometry using the chromatograph as interface) is discussed. Next, more technical exposition of the qualitative chromatographic information is presented supported by a variety of representative examples.

  15. Compostos voláteis dos frutos de maracujá (Passiflora edulis forma Flavicarpa e de cajá (Spondias mombin L. obtidos pela técnica de headspace dinâmico Volatile compounds in passion fruit (Passiflora edulis forma Flavicarpa and yellow mombin (Spondias mombin L. fruits obtained by dynamic headspace technique

    Directory of Open Access Journals (Sweden)

    Nerendra Narain

    2004-06-01

    Full Text Available Entre as inúmeras frutas tropicais e subtropicais produzidas no Brasil, duas que se destacam do ponto de vista do aroma da polpa são maracujá amarelo (Passiflora edulis forma Flavicarpa e cajá (Spondias mombin L.. Os voláteis da polpa destas frutas foram capturados pela técnica de headspace dinâmico e analisados no sistema de cromatografia gasosa de alta resolução e espectrometria de massa. Foram identificados 48 e 33 compostos voláteis na polpa de maracujá e cajá, respectivamente. Os compostos voláteis predominantes na polpa de maracujá pertenceram às classes de ésteres (59,24%, aldeídos (15,27%, cetonas (11,70% e álcoois (6,56%, enquanto na polpa de cajá as principais classes de compostos foram de ésteres (48,76%, álcoois (21,69%, aldeídos (11,61% e cetonas (4,19%. Outros compostos aromáticos característicos foram para maracujá: beta-ionona e linalol e para cajá: gama-octalactona e ácidos butírico e hexanóico.Among the numerous tropical and sub-tropical fruits produced in Brazil, two that attain relatively greater importance from the point of view of aroma of their pulp are yellow passion fruit (Passiflora edulis forma Flavicarpa and yellow mombin (Spondias mombin L.. The volatile components in the pulp of these fruits were captured by dynamic headspace technique and were analyzed in a system of high-resolution gas chromatography and mass spectrometry. Forty-eight and thirty-one volatile compounds were identified in passion fruit and yellow mombin fruit pulp, respectively. The predominant volatile compounds in passion fruit pulp belonged to the classes of esters (59.24%, aldehydes (15.27%, ketones (11.70% and alcohols (6.56% while in the yellow mombin pulp, the principal classes of compounds were esters (48.76%, alcohols (21.69%. aldehydes (11.61% and ketones (4.19%. The other characteristic aroma compounds for passion fruit were beta-ionone and linalool and for yellow mombin were gamma-octalactone, butanoic and

  16. Volatiles and primary metabolites profiling in two Hibiscus sabdariffa (roselle) cultivars via headspace SPME-GC-MS and chemometrics.

    Science.gov (United States)

    Farag, Mohamed A; Rasheed, Dalia M; Kamal, Islam M

    2015-12-01

    Hibiscus sabdariffa (roselle) is a plant of considerable commercial importance worldwide as functional food due to its organic acids, mucilage, anthocyanins, macro and micro-nutrients content. Although Hibiscus flowers are emerging as very competitive targets for phytochemical studies, very little is known about their volatile composition and or aroma, such knowledge can be suspected to be relevant for understanding its olfactory and taste properties. To provide insight into Hibiscus flower aroma composition and for its future use in food and or pharmaceutical industry, volatile constituents from 2 cultivars grown in Egypt, viz. Aswan and Sudan-1 were profiled using solid-phase microextraction (SPME) coupled to GCMS. A total of 104 volatiles were identified with sugar and fatty acid derived volatiles amounting for the major volatile classes. To reveal for cultivar effect on volatile composition in an untargeted manner, multivariate data analysis was applied. Orthogonal projection to latent structures-discriminant analysis (OPLS-DA) revealed for 1-octen-3-ol versus furfural/acetic acid enrichment in Aswan and Sudan-1 cvs., respectively. Primary metabolites contributing to roselle taste and nutritional value viz. sugars and organic acids were profiled using GC-MS after silylation. The impact of probiotic bacteria on roselle infusion aroma profile was further assessed and revealed for the increase in furfural production with Lactobacillus plantarum inoculation and without affecting its anthocyanin content. This study provides the most complete map for volatiles, sugars and organic acids distribution in two Hibiscus flower cultivars and its fermented product. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Headspace-Sampling Paper-Based Analytical Device for Colorimetric/Surface-Enhanced Raman Scattering Dual Sensing of Sulfur Dioxide in Wine.

    Science.gov (United States)

    Li, Dan; Duan, Huazhen; Ma, Yadan; Deng, Wei

    2018-05-01

    This study demonstrates a novel strategy for colorimetric/surface-enhanced Raman scattering (SERS) dual-mode sensing of sulfur dioxide (SO 2 ) by coupling headspace sampling (HS) with paper-based analytical device (PAD). The smart and multifunctional PAD is fabricated with a vacuum filtration method in which 4-mercaptopyridine (Mpy)-modified gold nanorods (GNRs)-reduced graphene oxide (rGO) hybrids (rGO/MPy-GNRs), anhydrous methanol, and starch-iodine complex are immobilized into cellulose-based filter papers. The resultant PAD exhibits a deep-blue color with a strong absorption peak at 600 nm due to the formation of an intermolecular charge-transfer complex between starch and iodine. However, the addition of SO 2 induces the Karl Fischer reaction, resulting in the decrease of color and increase of SERS signals. Therefore, the PAD can be used not only as a naked-eye indicator of SO 2 changed from blue to colorless but also as a highly sensitive SERS substrates because of the SO 2 -triggered conversion of Mpy to pyridine methyl sulfate on the GNRs. A distinguishable change in the color was observed at a SO 2 concentration of 5 μM by the naked eye, and a detection limit as low as 1.45 μM was obtained by virtue of UV-vis spectroscopy. The PAD-based SERS method is effective over a wide range of concentrations (1 μM to 2000 μM) for SO 2 , and the detection limit for SO 2 is found to be 1 μM. The HS-PAD based colorimetric/SERS method is applied for the determination of SO 2 in wine, and the detection results match well with those obtained from the traditional Monier-Williams method. This study not only offers a new method for on-site monitoring of SO 2 but also provides a new strategy for designing of paper-based sensing platform for a wide range of field-test applications.

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

    International Nuclear Information System (INIS)

    Cervera, M.I.; Beltran, J.; Lopez, F.J.; Hernandez, F.

    2011-01-01

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

  19. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC-qMSD for evaluation the chemical profile in alcoholic beverages

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, F.; Caldeira, M. [Centro de Quimica da Madeira, Departamento de Quimica, Universidade da Madeira, Campus Universitario da Penteada, 9000-390 Funchal (Portugal); Camara, J.S. [Centro de Quimica da Madeira, Departamento de Quimica, Universidade da Madeira, Campus Universitario da Penteada, 9000-390 Funchal (Portugal)], E-mail: jsc@uma.pt

    2008-02-18

    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC-qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 {mu}m); polyacrylate (PA, 85 {mu}m); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 {mu}m); carboxen{sup TM}/polydimethylsiloxane (CAR/PDMS, 75 {mu}m) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 {mu}m) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC-qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-10-17

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

  1. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC-qMSD for evaluation the chemical profile in alcoholic beverages

    International Nuclear Information System (INIS)

    Rodrigues, F.; Caldeira, M.; Camara, J.S.

    2008-01-01

    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC-qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 μm); polyacrylate (PA, 85 μm); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm); carboxen TM /polydimethylsiloxane (CAR/PDMS, 75 μm) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 μm) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC-qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl decanoate (58

  2. Determination of the analytical performance of a headspace capillary gas chromatographic technique and karl Fischer coulometric titration by system calibration using oil samples containing known amounts of moisture.

    Science.gov (United States)

    Jalbert, J; Gilbert, R; Tétreault, P

    1999-08-01

    Over the past few years, concerns have been raised in the literature about the accuracy of the Karl Fischer (KF) method for assessing moisture in transformer mineral oils. To better understand this issue, the performance of a static headspace capillary gas chromatographic (HS-CGC) technique was compared to that of KF coulometric titration by analyzing moisture in samples containing known amounts of water and various samples obtained from the National Institute of Standards and Technology (NIST). Two modes of adding samples into the KF vessel were used:  direct injection and indirect injection via an azeotropic distillation of the moisture with toluene. Under the conditions used for direct injection, the oil matrix was totally dissolved in the anolyte, which allowed the moisture to be titrated in a single-phase solution rather than in a suspension. The results have shown that when HS-CGC and combined azeotropic distillation/KF titration are calibrated with moisture-in-oil standards, a linear relation is observed over 0-60 ppm H(2)O with a correlation coefficient better than 0.9994 (95% confidence), with the regression line crossing through zero. A similar relation can also be observed when calibration is achieved by direct KF addition of standards prepared with octanol-1, but in this case an intercept of 4-5 ppm is noted. The amount of moisture determined by curve interpolation in NIST reference materials by the three calibrated systems ranges from 13.0 to 14.8 ppm for RM 8506 and 42.5 to 46.4 ppm for RM 8507, and in any case, the results were as high as those reported in the literature with volumetric KF titration. However, titration of various dehydrated oil and solvent samples showed that direct KF titration is affected by a small bias when samples contain very little moisture. The source of error after correction for the large sample volume used for the determination (8 mL) is about 6 ppm for Voltesso naphthenic oil and 4 ppm for toluene, revealing a matrix

  3. Comparative Analyses of the Volatile Components of Citrus Aurantium L. Flowers Using Ultrasonic-Assisted Headspace SPME and Hydrodistillation Combined with GC-MS and Evaluation of their Antimicrobial Activities

    Directory of Open Access Journals (Sweden)

    Akram Rahimi

    2014-12-01

    Full Text Available The volatile components of Citrus aurantium L. flowers were characterized by GC-MS with two different extraction techniques, hydrodistillation (HD and ultrasonic-assisted headspace solid phase microextraction (UA-HS-SPME. In the SPME method, the volatile components of the samples, irradiated by ultrasonic radiation, were collected on a polydimethyl siloxane (PDMS commercial fiber as well as some manually prepared nanoporous fibers from the samples headspace. To reach the better results, the extraction conditions were carefully optimized for the PDMS fiber. Under the optimized conditions (i.e. sonication time 15 min, extraction time 30 min and extraction temperature 55 ºC, 54 compounds were identified by the UA-HS-SPME-GC/MS method. The essential oil components of Citrus aurantium L. flower samples from two different regions of Iran and new and old samples from the same region were compared to one another. The major components identified for the samples with both the SPME and HD methods were linalool, linalyl acetate, limonene, β-myrcene, geranyl acetate, and neryl acetate, respectively. However, a substantial variation in the percentages of the components was identified for different samples and different extraction methods. The antimicrobial activities of the oil were also examined against six standard bacteria. There was some activity against Enterococcus fecalis, Escherichia coli, and Bacillus cereus, indicating important biological activities of the oil.

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

    Science.gov (United States)

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

    2014-11-19

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

  5. Selected Ion Flow Tube Mass Spectrometry Analysis of Volatile Metabolites in Urine Headspace for the Profiling of Gastro-Esophageal Cancer

    Czech Academy of Sciences Publication Activity Database

    Huang, J.; Kumar, S.; Abbassi-Ghadi, N.; Španěl, Patrik; Smith, D.

    2013-01-01

    Roč. 85, č. 6 (2013), s. 3409-3416 ISSN 0003-2700 Institutional support: RVO:61388955 Keywords : SOLID-PHASE MICROEXTRACTION * SIFT-MS * ORGANIC-COMPOUNDS Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 5.825, year: 2013

  6. Analysis of Formaldehyde in the Headspace of Urine from Bladder and Prostate Cancer Patients Using Selected Ion Flow Tube Mass Spectrometry

    Czech Academy of Sciences Publication Activity Database

    Španěl, Patrik; Smith, D.; Holland, T. A.; Singary, W. A.; Elder, J. B.

    1999-01-01

    Roč. 13, - (1999), s. 1354-1359 ISSN 0951-4198 R&D Projects: GA ČR GA203/97/P130 Grant - others:North Staffs Research Institute(GB) SIFT Project; Royal Society London(GB) Joint Project Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.437, year: 1999

  7. (E-2-Nonenal determination in brazilian beers using headspace solid-phase microextraction and gas chromatographic coupled mass spectrometry (HS-SPME-GC-MS Determinação de (E-2-nonenal em cervejas brasileiras utilizando microextração em fase sólida do headspace e cromatografia gasosa acoplada a espectrometria de massas

    Directory of Open Access Journals (Sweden)

    Rodrigo Scherer

    2010-05-01

    Full Text Available (E-2-nonenal is considered an important off-flavor of beer, related to the flavor of beer staling. In this study, a new method for determination of (E-2-nonenal in beer using headspace solid-phase microextraction and gas chromatographic coupled mass spectrometry (HS-SPME-GC-MS was developed and applied in Brazilian beer samples. The extractions were carried out in CAR-PDMS (carboxen-polydimethylsiloxane fiber and the best results were found with 15 minutes of equilibrium and 90 minutes of extraction at 50 °C. The method was linear in the range from 0.02 to 4.0 μg.L-1 with correlation coefficient of 0.9994. The limits of detection and quantification were 0.01 and 0.02 μg.L-1, respectively. 96.5% of recovery and 4% precision (RSD were obtained in the fortification of beer samples with 2.0 μg.L-1 of (E-2-nonenal. The developed method proved to be simple, efficient and highly sensitive to the determination of this analyte being easily applied in the quality control of the brewery. (E-2-nonenal was found in all beer samples analyzed with levels between 0.17 and 0.42 μg.L-1.O (E-2-nonenal é considerado um importante off-flavor da cerveja, sendo relacionado ao sabor de cerveja envelhecida. Neste estudo, um novo método para determinação de (E-2-nonenal em cerveja usando microextração em fase sólida do headspace e cromatografia a gás acoplada à espectrometria de massa (HS-SPME-GC-MS foi desenvolvido e aplicado em amostras de cerveja brasileira. As extrações foram realizadas utilizando a fibra CAR/PDMS (carboxen/polidimetilsiloxano, com 15 minutos de tempo de equilíbrio e 90 minutos de exposição da fibra a 50 °C. O método foi linear na faixa de 0,02 e 4,0 μg.L-1, com coeficiente de correlação de 0,9994. Os limites de detecção e quantificação foram 0,01 e 0,02 μg.L-1, respectivamente. Foram obtidos 96,5% de recuperação e 4% de variação entre replicatas de amostras de cerveja fortificadas com 2,0 μg.L-1 de (E-2-nonenal. O m

  8. Análise de pesticidas organoclorados em água usando a microextração em fase sólida por headspace com cromatografia gasosa e espectrometria de massas

    Directory of Open Access Journals (Sweden)

    Crislaine Batista Prates

    2011-01-01

    Full Text Available A method based on headspace - solid phase microextraction coupled with gas chromatography - mass spectrometry was validated for the quantitative determination of 18 organochlorine pesticides in water. For the extraction conditioning some parameters as the best type of coating fiber, time and temperature of extraction, pH and ionic strength were evaluated. The method HS-SPME/GC-MS/MS showed linear coefficient above 0.9948. The repeatability of the measurements were lower than 7.6%. Relative recoveries were between 88 and 110%. Limits of detection from 0.5 x 10-3 to 1.0 mg L-1 were obtained. A total of 31 samples were analyzed and 16 presented from 1 to 5 pesticides.

  9. Determination of N-vinyl-2-pyrrolidone and N-methyl-2-pyrrolidone in drugs using polypyrrole-based headspace solid-phase microextraction and gas chromatography-nitrogen-phosphorous detection.

    Science.gov (United States)

    Mehdinia, Ali; Ghassempour, Alireza; Rafati, Hasan; Heydari, Rouhollah

    2007-03-21

    A headspace solid-phase microextraction and gas chromatography-nitrogen-phosphorous detection (HS-SPME-GC-NPD) method using polypyrrole (PPy) fibers has been introduced to determine two derivatives of pyrrolidone; N-vinyl-2-pyrrolidone (NVP) and N-methyl-2-pyrrolidone (NMP). Two types of PPy fibers, prepared using organic and aqueous media, were compared in terms of extraction efficiency and thermal stability. It was found that PPy film prepared using organic medium (i.e. acetonitrile) had higher extraction efficiency and more thermal stability compared to the film prepared in aqueous medium. To enhance the sensitivity of HS-SPME, the effects of pH, ionic strength, extraction time, extraction temperature and the headspace volume on the extraction efficiency were optimized. Using the results of this research, high sensitivity and selectivity had been achieved due to the combination of the high extraction efficiency of PPy film prepared in organic medium and the high sensitivity and selectivity of nitrogen-phosphorous detection. Linear range of the analytes was found to be between 1.0 and 1000 microg L(-1) with regression coefficients (R(2)) of 0.998 and 0.997 for NVP and NMP, consequently. Limits of detection (LODs) were 0.074 and 0.081 microg L(-1) for NVP and NMP, respectively. Relative standard deviation (R.S.D.) for five replications of analyses was found to be less than 6.0%. In real samples the mean recoveries were 94.81% and 94.15% for NVP and NMP, respectively. The results demonstrated the suitability of the HS-SPME technique for analyzing NVP and NMP in two different pharmaceutical matrices. In addition, the method was used for simultaneous detection of NVP, 2-pyrrolidone (2-Pyr), gamma-butyrolactone (GBL) and ethanolamine (EA) compounds.

  10. A molybdenum disulfide/reduced graphene oxide fiber coating coupled with gas chromatography-mass spectrometry for the saponification-headspace solid-phase microextraction of polychlorinated biphenyls in food.

    Science.gov (United States)

    Lv, Fangying; Gan, Ning; Cao, Yuting; Zhou, You; Zuo, Rongjie; Dong, Youren

    2017-11-24

    In this work, the molybdenum disulfide/reduced graphene oxide (MoS 2 /RGO) composite material was synthesized as a fiber coating to extract seven indicator polychlorinated biphenyls (PCBs; PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB180) present in food via a saponification-headspace solid-phase microextraction assay (saponification-HS-SPME). The MoS 2 /RGO coating was prepared and deposited on a stainless steel wire with the help of a silicone sealant and used as an SPME fiber. The alkali solution dissolved the fat and helped in releasing the PCBs present in milk to the headspace for extraction under 100°C. Following desorption in the inlet, the targets were quantified by gas chromatography-mass spectrometry. The effects of sorbent dosage, extraction time, added salts, and stirring rate on the extraction efficiency were investigated. The new coating was able to adsorb a higher amount of analytes, which was about 1.1-2.9 times in comparison with the commercially available SPME fiber (coated with divinylbenzene/carboxen/polydimethylsiloxane). It also showed the highest adsorption capability toward PCBs, which was 1.5-2.7 times that of the prepared RGO modified fiber. Moreover, MoS 2 also showed a strong affinity toward PCBs in a manner similar to its affinity for graphene. The developed method is simple and environmentally friendly as it does not require any organic solvents. Furthermore, it exhibits good sensitivity with detection limits less than 0.1ngmL -1 , linearity (0.25-100ngmL -1 ), and reproducibility (relative standard deviation below 10% for n=3). The novel SPME fibers are inexpensive, reusable, and can be easily prepared and manipulated. In addition, the saponification-HS-SPME assay was also found to be suitable for screening persistent organic pollutants in dairy products. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. A sol-gel based solid phase microextraction fiber for the analysis of aliphatic alcohols in apple juices.

    Science.gov (United States)

    Farhadi, Khalil; Maleki, Ramin; Tahmasebi, Raheleh

    2010-01-01

    A new fiber based on titania-chitin sol-gel coated on a silver wire for the headspace solid phase microextraction of aliphatic alcohols from apple juice samples was developed. The influences of fiber coating composition and microextraction conditions (extraction temperature, extraction time, and ionic strength of the sample matrix) on the fiber performance were investigated. Also, the influence of temperature and time on desorption of analytes from fiber were studied. Under the optimized conditions, a porous fiber with a high extraction capacity and good thermal stability (up to 250 degrees C) was obtained. The proposed headspace solid-phase microextraction-GC method was successfully used for the analysis of aliphatic alcohols in apple juice and concentrate samples. The recovery values were from 92.8 to 98.6%. The RSD (n=5) for all analytes were below 7.8%.

  12. Comparison of Three Methods for Extraction of Volatile Lipid Oxidation Products from Food Matrices for GC–MS Analysis

    DEFF Research Database (Denmark)

    Thomsen, Birgitte Raagaard; Yesiltas, Betül; Sørensen, Ann-Dorit Moltke

    2016-01-01

    The aim of this study was to compare three different collection methods; purge and trap, solid phase micro extraction and automated dynamic headspace/thermal desorption, all followed by GC–MS analysis used for the measurements of concentrations of volatile oxidation products in three different food...... of the calibration curves depending on the collection method. However, some challenges were observed for solid phase micro extraction and automated dynamic headspace/thermal desorption, namely, competition problems and overestimation of concentration by calibration curves, respectively. Based on the results, we...... suggest mainly to apply solid phase micro extraction on simple matrices and to be cautious with more complex matrices such as enriched milk and highly oxidized oils. Thereby, the study confirmed some challenges observed by other authors regarding competition problems on the fiber when using solid phase...

  13. Determinação de metil-etil-cetona em amostras de urina com amostragem por micro extração em fase sólida (MEFS em headspace associada à cromatografia gasosa com detector de ionização de chama (CG-DIC Determination of methyl ethyl ketone in urine samples by headspace solid phase micro extraction (SPME sampling associated to gas chromatography with flame-ionization detectoR (GC-FID

    Directory of Open Access Journals (Sweden)

    Marina Venzon Antunes

    2008-01-01

    Full Text Available Methyl ethyl ketone (MEK is a solvent commonly used in chemical, paint and shoe industry. The aim of this study was to develop and validate a method for urinary quantification of MEK, employing headspace solid phase micro extraction sampling (SPME coupled to gas chromatography with flame ionization detection (GC-FID. The calibration curve (y=4.6851x-0.0011 presented good linearity with r²=0.9993. Accuracy (94-109%, intra-assay precision (4.07-5.91% and inter-assay precision (3.03-5.62% were acceptable. The quantification limit was 0.19 mg/L. This low cost method can be used routinely in the biological monitoring of occupational exposure to MEK, according to the requirements of the Brazilian legislation.

  14. Volatile flavor analysis and sensory evaluation of custard desserts varying in type and concentration of carboxymethyl cellulose.

    Science.gov (United States)

    van Ruth, Saskia M; de Witte, Leontien; Uriarte, Amaya Rey

    2004-12-29

    The influence of type and concentration of carboxymethyl cellulose (CMC) on flavor and textural properties of custard desserts was examined. A synthetic strawberry flavor mixture was used to flavor the custards; it comprised 15 volatile flavor compounds. The viscosity of the custards was determined using rheometric measurements. Static headspace gas chromatography and in-nose proton transfer reaction-mass spectrometry analyses were conducted to determine the custards' volatile flavor properties. Perceived odor, flavor, and textural properties were assessed in sensory analysis experiments using magnitude estimation against a fixed modulus. Both type and concentration of CMC altered the viscosity of the custards. Softer custards had higher static headspace flavor concentrations. On the contrary, firmer custards demonstrated higher in-nose flavor concentrations. In sensory analysis, firmer custards showed higher thickness and lower sweetness intensities than their low-viscosity counterparts. The thickness perception corresponded to the viscosity of the custards. Removal of sucrose from the custards affected sweetness intensity only and not the intensity of other attributes. Therefore, the influence of the viscosity of the custards on the release of sweet-tasting components is held responsible for the effect on perceived sweetness intensity. Odor intensities were generally higher for the low-viscosity custard, whereas fruity flavor intensities were higher for the firmer custards. Odor intensities correlated with static headspace concentrations and flavor intensities related reasonably well with in-nose concentrations. Opening and closing of the nasal cavity is regarded as an important factor determining the discrepancy between static and in-nose measurements.

  15. Resonance enhanced laser mass spectrometry for process- and environmental-analysis: Applications and perspectives

    International Nuclear Information System (INIS)

    Zimmermann, Ralf; Dorfner, Ralph; Kettrup, Antonius; Heger, Hans Joerg; Boesl, Ulrich

    1998-01-01

    Laser induced Resonance-Enhanced Multi-Photon Ionization Time-Of-Flight Mass Spectrometry (REMPI TOFMS) is a highly selective as well as sensitive analytical technique, well suited for species selective, on-line monitoring of trace-substances. In this contribution some analytical applications of a mobile REMPI-TOFMS are presented. This includes REMPI-TOMS on-line analysis of coffee roasting gas and waste incineration flue gas as well as headspace measurements of pulp processing lye or rapid analysis of polycyclic aromatic hydrocarbons from soil samples via thermal desorption

  16. Liquid-liquid extraction/headspace/gas chromatographic/mass spectrometric determination of benzene, toluene, ethylbenzene, (o-, m- and p-)xylene and styrene in olive oil using surfactant-coated carbon nanotubes as extractant.

    Science.gov (United States)

    Carrillo-Carrión, Carolina; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel

    2007-11-09

    BTEX-S compounds are widely distributed in the environment and can be present in different foodstuffs, including olive oil. Taking into account the risks of the exposure to these compounds, analytical methods for their determination in different matrices are mandatory. In this paper, the use of surfactant-coated multiwalled carbon nanotubes as additive in liquid-liquid extraction is applied for the determination of single-ring aromatic compounds in olive oil samples. After sample treatment, the aqueous extracts are subsequently analyzed by headspace/gas chromatography/mass spectrometry allowing the determination of BTEX-S within ca. 15 min. Each stage of the proposed LLE/HS/GC/MS configuration involves a selectivity enhancement avoiding the interference of other compounds of the sample matrix. Limits of detection were in the range 0.25 ng mL(-1) (obtained for ethylbenzene) and 0.43 ng mL(-1) (for benzene). The repeatability of the proposed method expressed as RSD varied between 1.9% (styrene) and 3.3% (benzene) (n=11).

  17. Acetone, butanone, pentanone, hexanone and heptanone in the headspace of aqueous solution and urine studied by selected ion flow tube mass spectrometry

    Czech Academy of Sciences Publication Activity Database

    Wang, T.; Pysanenko, A.; Španěl, Patrik; Smith, D.

    2009-01-01

    Roč. 23, č. 8 (2009), s. 1097-1104 ISSN 0951-4198 Institutional research plan: CEZ:AV0Z40400503 Keywords : trace gras-analysis * breath analysis * exhaled breath Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.695, year: 2009

  18. Quantification of selected volatile organic compounds in human urine by gas chromatography selective reagent ionization time of flight mass spectrometry (GC-SRI-TOF-MS) coupled with head-space solid-phase microextraction (HS-SPME).

    Science.gov (United States)

    Mochalski, Paweł; Unterkofler, Karl

    2016-08-07

    Selective reagent ionization time of flight mass spectrometry with NO(+) as the reagent ion (SRI-TOF-MS(NO(+))) in conjunction with gas chromatography (GC) and head-space solid-phase microextraction (HS-SPME) was used to determine selected volatile organic compounds in human urine. A total of 16 volatiles exhibiting high incidence rates were quantified in the urine of 19 healthy volunteers. Amongst them there were ten ketones (acetone, 2-butanone, 3-methyl-2-butanone, 2-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, and 4-heptanone), three volatile sulphur compounds (dimethyl sulfide, allyl methyl sulfide, and methyl propyl sulfide), and three heterocyclic compounds (furan, 2-methylfuran, 3-methylfuran). The concentrations of the species under study varied between 0.55 nmol L(-1) (0.05 nmol mmol(-1)creatinine) for allyl methyl sulfide and 11.6 μmol L(-1) (1.54 μmol mmol(-1)creatinine) for acetone considering medians. Limits of detection (LODs) ranged from 0.08 nmol L(-1) for allyl methyl sulfide to 1.0 nmol L(-1) for acetone and furan (with RSDs ranging from 5 to 9%). The presented experimental setup assists both real-time and GC analyses of volatile organic compounds, which can be performed consecutively using the same analytical system. Such an approach supports the novel concept of hybrid volatolomics, an approach which combines VOC profiles obtained from two or more body fluids to improve and complement the chemical information on the physiological status of an individual.

  19. Determination of Ignitable Liquids in Fire Debris: Direct Analysis by Electronic Nose

    Directory of Open Access Journals (Sweden)

    Marta Ferreiro-González

    2016-05-01

    Full Text Available Arsonists usually use an accelerant in order to start or accelerate a fire. The most widely used analytical method to determine the presence of such accelerants consists of a pre-concentration step of the ignitable liquid residues followed by chromatographic analysis. A rapid analytical method based on headspace-mass spectrometry electronic nose (E-Nose has been developed for the analysis of Ignitable Liquid Residues (ILRs. The working conditions for the E-Nose analytical procedure were optimized by studying different fire debris samples. The optimized experimental variables were related to headspace generation, specifically, incubation temperature and incubation time. The optimal conditions were 115 °C and 10 min for these two parameters. Chemometric tools such as hierarchical cluster analysis (HCA and linear discriminant analysis (LDA were applied to the MS data (45–200 m/z to establish the most suitable spectroscopic signals for the discrimination of several ignitable liquids. The optimized method was applied to a set of fire debris samples. In order to simulate post-burn samples several ignitable liquids (gasoline, diesel, citronella, kerosene, paraffin were used to ignite different substrates (wood, cotton, cork, paper and paperboard. A full discrimination was obtained on using discriminant analysis. This method reported here can be considered as a green technique for fire debris analyses.

  20. Determination of Ignitable Liquids in Fire Debris: Direct Analysis by Electronic Nose

    Science.gov (United States)

    Ferreiro-González, Marta; Barbero, Gerardo F.; Palma, Miguel; Ayuso, Jesús; Álvarez, José A.; Barroso, Carmelo G.

    2016-01-01

    Arsonists usually use an accelerant in order to start or accelerate a fire. The most widely used analytical method to determine the presence of such accelerants consists of a pre-concentration step of the ignitable liquid residues followed by chromatographic analysis. A rapid analytical method based on headspace-mass spectrometry electronic nose (E-Nose) has been developed for the analysis of Ignitable Liquid Residues (ILRs). The working conditions for the E-Nose analytical procedure were optimized by studying different fire debris samples. The optimized experimental variables were related to headspace generation, specifically, incubation temperature and incubation time. The optimal conditions were 115 °C and 10 min for these two parameters. Chemometric tools such as hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA) were applied to the MS data (45–200 m/z) to establish the most suitable spectroscopic signals for the discrimination of several ignitable liquids. The optimized method was applied to a set of fire debris samples. In order to simulate post-burn samples several ignitable liquids (gasoline, diesel, citronella, kerosene, paraffin) were used to ignite different substrates (wood, cotton, cork, paper and paperboard). A full discrimination was obtained on using discriminant analysis. This method reported here can be considered as a green technique for fire debris analyses. PMID:27187407

  1. Multivariate study of parameters in the determination of pesticide residues in apple by headspace solid phase microextraction coupled to gas chromatography-mass spectrometry using experimental factorial design.

    Science.gov (United States)

    Abdulra'uf, Lukman Bola; Tan, Guan Huat

    2013-12-15

    Solid-phase microextraction (SPME) is a solvent-less sample preparation method which combines sample preparation, isolation, concentration and enrichment into one step. In this study, multivariate strategy was used to determine the significance of the factors affecting the solid phase microextraction of pesticide residues (fenobucarb, diazinon, chlorothalonil and chlorpyrifos) using a randomised factorial design. The interactions and effects of temperature, time and salt addition on the efficiency of the extraction of the pesticide residues were evaluated using 2(3) factorial designs. The analytes were extracted with 100 μm PDMS fibres according to the factorial design matrix and desorbed into a gas chromatography-mass spectrometry detector. The developed method was applied for the analysis of apple samples and the limits of detection were between 0.01 and 0.2 μg kg(-)(1), which were lower than the MRLs for apples. The relative standard deviations (RSD) were between 0.1% and 13.37% with average recovery of 80-105%. The linearity ranges from 0.5-50 μg kg(-)(1) with correlation coefficient greater than 0.99. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Vacuum-assisted headspace-solid phase microextraction for determining volatile free fatty acids and phenols. Investigations on the effect of pressure on competitive adsorption phenomena in a multicomponent system.

    Science.gov (United States)

    Trujillo-Rodríguez, María J; Pino, Verónica; Psillakis, Elefteria; Anderson, Jared L; Ayala, Juan H; Yiantzi, Evangelia; Afonso, Ana M

    2017-04-15

    This work proposes a new vacuum headspace solid-phase microextraction (Vac-HSSPME) method combined to gas chromatography-flame ionization detection for the determination of free fatty acids (FFAs) and phenols. All target analytes of the multicomponent solution were volatiles but their low Henry's Law constants rendered them amenable to Vac-HSSPME. The ability of a new and easy to construct Vac-HSSPME sampler to maintain low-pressure conditions for extended sampling times was concurrently demonstrated. Vac-HSSPME and regular HSSPME methods were independently optimized and the results were compared at all times. The performances of four commercial SPME fibers and two polymeric ionic liquid (PIL)-based SPME fibers were evaluated and the best overall results were obtained with the adsorbent-type CAR/PDMS fiber. For the concentrations used here, competitive displacement became more intense for the smaller and more volatile analytes of the multi-component solution when lowering the sampling pressure. The extraction time profiles showed that Vac-HSSPME had a dramatic positive effect on extraction kinetics. The local maxima of adsorbed analytes recorded with Vac-HSSPME occurred faster, but were always lower than that with regular HSSPME due to the faster analyte-loading from the multicomponent solution. Increasing the sampling temperature during Vac-HSSPME reduced the extraction efficiency of smaller analytes due to the enhancement in water molecule collisions with the fiber. This effect was not recorded for the larger phenolic compounds. Based on the optimum values selected, Vac-HSSPME required a shorter extraction time and milder sampling conditions than regular HSSPME: 20 min and 35 °C for Vac-HSSPME versus 40 min and 45 °C for regular HSSPME. The performance of the optimized Vac-HSSPME and regular HSSPME procedures were assessed and Vac-HSSPME method proved to be more sensitive, with lower limits of detection (from 0.14 to 13 μg L -1 ), and better intra

  3. Fatty acid composition and its association with chemical and sensory analysis of boar taint.

    Science.gov (United States)

    Liu, Xiaoye; Trautmann, Johanna; Wigger, Ruth; Zhou, Guanghong; Mörlein, Daniel

    2017-09-15

    A certain level of disagreement between the chemical analysis of androstenone and skatole and the human perception of boar taint has been found in many studies. Here we analyze whether the fatty acid composition can explain such inconsistency between sensory evaluation and chemical analysis of boar taint compounds. Therefore, back fat samples (n=143) were selected according to their sensory evaluation by a 10-person sensory panel, and the chemical analysis (stable isotope dilution analysis with headspace solid-phase microextraction and gas chromatography-mass spectrometry) of androstenone and skatole. Subsequently a quantification of fatty acids using gas chromatography-flame ionization detection was conducted. The correlation analyses revealed that several fatty acids are significantly correlated with androstenone, skatole, and the sensory rating. However, multivariate analyses (principal component analysis) revealed no explanation of the fatty acid composition with respect to the (dis-)agreement between sensory and chemical analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Differentiation of closely related fungi by electronic nose analysis

    DEFF Research Database (Denmark)

    Karlshøj, Kristian; Nielsen, Per Væggemose; Larsen, Thomas Ostenfeld

    2007-01-01

    the electronic nose potentially responded to, volatile metabolites were collected, by diffusive sampling overnight onto tubes containing Tenax TA, between the 7th and 8th day of Incubation.Volatiles were analyzed by gas chromatography coupled to mass spectrometry and the results indicated that mail alcohols...... as well as the noacheese ociated P. expansum have been investigated by electronic nose, GC-MS, and LGMS analysis. The isolates were inoculated on yeast extract sucroseagar in 20-mL headspace flasks and electronicnose analysis was performed daily for a-74period. To assess which volatile metabolites...... by high pressure liquid chromatography, coupled-to a diode array detector and a time of flight mass spectrometer. Several mycotoxins were detected in samples from the specles P.nordicum, P.roqueforti, P.paneum, P.carneum, and P.expansum. Differentiation of closely related mycotoxin producing fungi...

  5. Alternative fuels in fire debris analysis: biodiesel basics.

    Science.gov (United States)

    Stauffer, Eric; Byron, Doug

    2007-03-01

    Alternative fuels are becoming more prominent on the market today and, soon, fire debris analysts will start seeing them in liquid samples or in fire debris samples. Biodiesel fuel is one of the most common alternative fuels and is now readily available in many parts of the United States and around the world. This article introduces biodiesel to fire debris analysts. Biodiesel fuel is manufactured from vegetable oils and/or animal oils/fats. It is composed of fatty acid methyl esters (FAMEs) and is sold pure or as a blend with diesel fuel. When present in fire debris samples, it is recommended to extract the debris using passive headspace concentration on activated charcoal, possibly followed by a solvent extraction. The gas chromatographic analysis of the extract is first carried out with the same program as for regular ignitable liquid residues, and second with a program adapted to the analysis of FAMEs.

  6. Estimating the measurement uncertainty in forensic blood alcohol analysis.

    Science.gov (United States)

    Gullberg, Rod G

    2012-04-01

    For many reasons, forensic toxicologists are being asked to determine and report their measurement uncertainty in blood alcohol analysis. While understood conceptually, the elements and computations involved in determining measurement uncertainty are generally foreign to most forensic toxicologists. Several established and well-documented methods are available to determine and report the uncertainty in blood alcohol measurement. A straightforward bottom-up approach is presented that includes: (1) specifying the measurand, (2) identifying the major components of uncertainty, (3) quantifying the components, (4) statistically combining the components and (5) reporting the results. A hypothetical example is presented that employs reasonable estimates for forensic blood alcohol analysis assuming headspace gas chromatography. These computations are easily employed in spreadsheet programs as well. Determining and reporting measurement uncertainty is an important element in establishing fitness-for-purpose. Indeed, the demand for such computations and information from the forensic toxicologist will continue to increase.

  7. Analysis

    DEFF Research Database (Denmark)

    Mathiesen, Brian Vad; Liu, Wen; Zhang, Xiliang

    2014-01-01

    three major technological changes: energy savings on the demand side, efficiency improvements in energy production, and the replacement of fossil fuels by various sources of renewable energy. Consequently, the analysis of these systems must include strategies for integrating renewable sources...

  8. Analysis of low-molecular weight radiolysis products in extracts of gamma-irradiated polymers by gas chromatography and high-performance liquid chromatography

    International Nuclear Information System (INIS)

    Buchalla, Rainer; Begley, Timothy H.; Morehouse, Kim M.

    2002-01-01

    Estimating exposure to radiolysis products of polymers is an important part of the regulatory evaluation of packaging materials for use in food irradiation. However, as Koni Grob recently put it, the comprehensive analysis of migrants is a challenge. This paper discusses some of the analytical difficulties and presents results obtained with extracts of irradiated polystyrene and polyamide-6. The results indicate that headspace or thermal desorption techniques may, in some instances, lead to an overestimation of radiolysis product concentrations. It is concluded that validated analytical methods and a better understanding of the underlying radiation chemistry would greatly facilitate the safety assessment of irradiated packaging materials

  9. Comparative analysis of different methods of extraction of present hydrocarbons in industrial residual waters

    International Nuclear Information System (INIS)

    Santa, Judith Rocio; Serrano, Martin; Stashenko, Elena

    2002-01-01

    A comparison among four extraction techniques such as: liquid - liquid (LLE) continuous and for lots, solid phase extraction (SPE), solid phase micro extraction (SPME) and static headspace (S-HS) was carried out. The main purpose of this research was to determine the highest recovery efficiencies and how reproducible the tests are while varying parameters such as time, extraction technique, type of solvents and others. Chromatographic parameters were optimized in order to carry out the analyses. Hydrocarbon's quantification of residual waters was achieved by using a high-resolution gas chromatography with a gas flame ionization detector (HRGC-FID). Validation of the method was carried out by analyzing real samples taken in different sampling places of the residual waters treatment plant of Ecopetrol - Barrancabermeja. The use of extraction methods that require big solvent quantities and long time for analysis are losing validity day by day. Techniques such as the HS-SPME and static HS are offered as alternatives for quantifying hydrocarbons. They show total lack of solvents, high sensibility, selectivity and the techniques are reproducible. Solid phase micro extraction (SPME) and static headspace (static HS) techniques were chosen as the extraction techniques to validate the method in real samples. Both techniques showed similar results for the determination of total hydrocarbons (in the gasoline range)

  10. Plutonium-238 Decision Analysis

    International Nuclear Information System (INIS)

    Brown, Mike; Lechel, David J.; Leigh, C.D.

    1999-01-01

    Five transuranic (TRU) waste sites in the Department of Energy (DOE) complex, collectively, have more than 2,100 cubic meters of Plutonium-238 (Pu-238) TRU waste that exceed the wattage restrictions of the Transuranic Package Transporter-II (TRUPACT-11). The Waste Isolation Pilot Plant (WIPP) is being developed by the DOE as a repository for TRU waste. With the Waste Isolation Pilot Plant (WIPP) opening in 1999, these sites are faced with a need to develop waste management practices that will enable the transportation of Pu-238 TRU waste to WIPP for disposal. This paper describes a decision analysis that provided a logical framework for addressing the Pu-238 TRU waste issue. The insights that can be gained by performing a formalized decision analysis are multifold. First and foremost, the very process. of formulating a decision tree forces the decision maker into structured, logical thinking where alternatives can be evaluated one against the other using a uniform set of criteria. In the process of developing the decision tree for transportation of Pu-238 TRU waste, several alternatives were eliminated and the logical order for decision making was discovered. Moreover, the key areas of uncertainty for proposed alternatives were identified and quantified. The decision analysis showed that the DOE can employ a combination approach where they will (1) use headspace gas analyses to show that a fraction of the Pu-238 TRU waste drums are no longer generating hydrogen gas and can be shipped to WIPP ''as-is'', (2) use drums and bags with advanced filter systems to repackage Pu-238 TRU waste drums that are still generating hydrogen, and (3) add hydrogen getter materials to the inner containment vessel of the TRUPACT-11to relieve the build-up of hydrogen gas during transportation of the Pu-238 TRU waste drums

  11. Analysis of aroma compounds of pitaya fruit wine

    Science.gov (United States)

    Gong, Xiao; Ma, Lina; Li, Liuji; Yuan, Yuan; Peng, Shaodan; Lin, Mao

    2017-12-01

    In order to analyze the volatile components in red pitaya fruit wine, the study using headspace solid phase microextractionand gas chromatography-mass spectrometry technology of pitaya fruit juice and wine aroma composition analysis comparison. Results showed that 55 volatile components were detected in red pitaya fruit wine, including 12 kinds of alcohol (18.16%), 18 kinds of esters (66.17%), 7 kinds of acids (5.94%), 11 kinds of alkanes (4.32%), one kind of aldehyde (0.09%), 2 kinds of olefins (0.09%) and 3 kinds of other volatile substances (0.23%). Relative contents among them bigger have 11 species, such as decanoic acid, ethyl ester (22.92%), respectively, diisoamylene (20.75%), octanoic acid, ethyl ester (17.73%), etc. The red pitaya fruit wine contained a lot of aroma components, which offer the products special aroma like brandy, rose and fruit.

  12. Rapid direct analysis to discriminate geographic origin of extra virgin olive oils by flash gas chromatography electronic nose and chemometrics.

    Science.gov (United States)

    Melucci, Dora; Bendini, Alessandra; Tesini, Federica; Barbieri, Sara; Zappi, Alessandro; Vichi, Stefania; Conte, Lanfranco; Gallina Toschi, Tullia

    2016-08-01

    At present, the geographical origin of extra virgin olive oils can be ensured by documented traceability, although chemical analysis may add information that is useful for possible confirmation. This preliminary study investigated the effectiveness of flash gas chromatography electronic nose and multivariate data analysis to perform rapid screening of commercial extra virgin olive oils characterized by a different geographical origin declared in the label. A comparison with solid phase micro extraction coupled to gas chromatography mass spectrometry was also performed. The new method is suitable to verify the geographic origin of extra virgin olive oils based on principal components analysis and discriminant analysis applied to the volatile profile of the headspace as a fingerprint. The selected variables were suitable in discriminating between "100% Italian" and "non-100% Italian" oils. Partial least squares discriminant analysis also allowed prediction of the degree of membership of unknown samples to the classes examined. Copyright © 2016. Published by Elsevier Ltd.

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

    Science.gov (United States)

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

    2017-05-05

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

  14. Ambient analysis of trace compounds in gaseous media by SIFT-MS.

    Science.gov (United States)

    Smith, David; Spaněl, Patrik

    2011-05-21

    The topic of ambient gas analysis has been rapidly developed in the last few years with the evolution of the exciting new techniques such as DESI, DART and EESI. The essential feature of all is that analysis of trace gases can be accomplished either in the gas phase or those released from surfaces, crucially avoiding sample collection or modification. In this regard, selected ion flow tube mass spectrometry, SIFT-MS, also performs ambient analyses both accurately and rapidly. In this focused review we describe the underlying ion chemistry underpinning SIFT-MS through a discourse on the reactions of different classes of organic and inorganic molecules with H(3)O(+), NO(+) and O(2)(+)˙ studied using the SIFT technique. Rate coefficients and ion products of these reactions facilitate absolute SIFT-MS analyses and can also be useful for the interpretation of data obtained by the other ambient analysis methods mentioned above. The essential physics and flow dynamics of SIFT-MS are described that, together with the reaction kinetics, allow SIFT-MS to perform absolute ambient analyses of trace compounds in humid atmospheric air, exhaled breath and the headspace of aqueous liquids. Several areas of research that, through pilot experiments, are seen to benefit from ambient gas analysis using SIFT-MS are briefly reviewed. Special attention is given to exhaled breath and urine headspace analysis directed towards clinical diagnosis and therapeutic monitoring, and some other areas researched using SIFT-MS are summarised. Finally, extensions to current areas of application and indications of other directions in which SIFT-MS can be exploited for ambient analysis are alluded to.

  15. Volatile Organic Compound (VOC) Analysis For Disease Detection: Proof Of Principle For Field Studies Detecting Paratuberculosis And Brucellosis

    Science.gov (United States)

    Knobloch, Henri; Köhler, Heike; Nicola, Commander; Reinhold, Petra; Turner, Claire; Chambers, Mark

    2009-05-01

    A proof of concept investigation was performed to demonstrate that two independent infectious diseases of cattle result in different patterns of volatile organic compounds (VOC) in the headspace of serum samples detectable using an electronic nose (e-nose). A total of 117 sera from cattle naturally infected with Mycobacterium avium subsp. paratuberculosis (paraTB, n = 43) or Brucella sp. (n = 26) and sera from corresponding control animals (n = 48) were randomly and analysed blind to infection status using a ST214 e-nose (Scensive Ltd, Leeds, UK). Samples were collected under non-standardised conditions on different farms from the UK (brucellosis) and Germany (paraTB). The e-nose could differentiate the sera from brucellosis infected, paraTB infected and healthy animals at the population level, but the technology used was not suitable for determination of the disease status of individual animals. Nevertheless, the data indicate that there are differences in the sensor responses depending on the disease status, and therefore, it shows the potential of VOC analysis from serum headspace samples for disease detection.

  16. Characterisation of volatile profile and sensory analysis of fresh-cut "Radicchio di Chioggia" stored in air or modified atmosphere.

    Science.gov (United States)

    Cozzolino, Rosaria; Martignetti, Antonella; Pellicano, Mario Paolo; Stocchero, Matteo; Cefola, Maria; Pace, Bernardo; De Giulio, Beatrice

    2016-02-01

    The volatile profile of two hybrids of "Radicchio di Chioggia", Corelli and Botticelli, stored in air or passive modified atmosphere (MAP) during 12 days of cold storage, was monitored by solid phase micro-extraction (SPME) GC-MS. Botticelli samples were also subjected to sensory analysis. Totally, 61 volatile organic compounds (VOCs) were identified in the headspace of radicchio samples. Principal component analysis (PCA) showed that fresh product possessed a metabolic content similar to that of the MAP samples after 5 and 8 days of storage. Projection to latent structures by partial least squares (PLS) regression analysis showed the volatiles content of the samples varied depending only on the packaging conditions. Specifically, 12 metabolites describing the time evolution and explaining the effects of the different storage conditions were highlighted. Finally, a PCA analysis revealed that VOCs profile significantly correlated with sensory attributes. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Estimation of perimortal percent carboxy-heme in nonstandard postmortem specimens using analysis of carbon monoxide by GC/MS and iron by flame atomic absorption spectrophotometry.

    Science.gov (United States)

    Middleberg, R A; Easterling, D E; Zelonis, S F; Rieders, F; Rieders, M F

    1993-01-01

    In decomposed, formalin-fixed, embalmed, exhumed, and some fire-dried cases in which normal blood is unavailable, the usual methods for determination of carboxyhemoglobin saturation frequently fail. To address these specimens, a method utilizing both gas chromatography/mass spectrometric (GC/MS) determination of carbon monoxide (CO) and flame atomic absorption spectrophotometry (FAAS) determination of iron (Fe), in the same specimen, was developed. The method is reported here, along with its application to seven pertinent forsensic death investigations. The CO analytical methodology involves acid liberation of the gas from the specimen aliquot in a headspace vial. After heating and equilibrating, a sample of the headspace vapor is injected into the GC/MS system with a gastight syringe. Quantitation is achieved by standard addition comparison utilizing the ideal gas law equation. Iron is quantified by FAAS analysis of the same aliquot used for the CO determination, following nitric acid digestion. The concentration is determined by comparison to a standard curve. A formula for determining the minimum percent carboxy-heme saturation was derived by using the ratio of the amount of CO to the amount of Fe in the aliquot analyzed. Tissue types analyzed include spleen, liver, muscle, dried blood, and unspecified decomposed tissue.

  18. Preparation and characterization of sodium dodecyl sulfate doped polypyrrole solid phase micro extraction fiber and its application to endocrine disruptor pesticide analysis.

    Science.gov (United States)

    Korba, Korcan; Pelit, Levent; Pelit, Füsun Okçu; Ozdokur, K Volkan; Ertaş, Hasan; Eroğlu, Ahmet E; Ertaş, F Nil

    2013-06-15

    A robust in house solid-phase micro extraction (SPME) surface has been developed for the headspace (HS)-SPME determination of endocrine disruptor pesticides, namely, Chlorpyrifos, Penconazole, Procymidone, Bromopropylate and Lambda-Cyhalothrin in wine sample by using sodium dodecylsulfate doped polypyrrole SPME fiber. Pyrrole monomer was electrochemically polymerized on a stainless steel wire in laboratory conditions in virtue of diminishing the cost and enhancing the analyte retention on its surface to exert better selectivity and hence the developed polymerized surface could offer to analyst to exploit it as a fiber in headspace SPME analysis. The parameters, mainly, adsorption temperature and time, desorption temperature, stirring rate and salt amount were optimized to be as 70°C and 45min, 200°C, 600rpm and 10gL(-1), respectively. Limit of detection was estimated in the range of 0.073-1.659ngmL(-1) for the pesticides studied. The developed method was applied in to red wine sample with acceptable recovery values (92-107%) which were obtained for these selected pesticides. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Improving the knowledge on Piper betle: targeted metabolite analysis and effect on acetylcholinesterase.

    Science.gov (United States)

    Valentão, Patrícia; Gonçalves, Rui F; Belo, Cristóvão; de Pinho, Paula Guedes; Andrade, Paula B; Ferreres, Federico

    2010-10-01

    Piper betle is a species growing in South East Asia, where its leaves are economically and medicinally important. To screen the highest possible number of volatile and semivolatile components, the leaves were subjected to headspace solid-phase microextraction, hydrodistillation and Soxhlet extraction, prior to analysis by GC/MS. Fifty compounds (identified by comparison with standard compounds or tentatively by National Institute of Standards and Technology database) were determined, 23 being described for the first time in this matrix. An aqueous extract was also analysed, in which only seven compounds were characterized. The organic acids' composition of this extract was determined by HPLC/UV and eight compounds are reported for the first time in P. betle. This extract also displayed acetylcholinesterase inhibitory capacity.

  20. Analysis and optimization of a synthetic milkweed floral attractant for mosquitoes.

    Science.gov (United States)

    Otienoburu, Philip E; Ebrahimi, Babak; Phelan, P Larry; Foster, Woodbridge A

    2012-07-01

    A pentane extract of flowers of common milkweed, Asclepias syriaca (Asclepiadaceae), elicited significant orientation from both male and female Culex pipiens in a dual-port flight olfactometer. Analysis of the extract by gas chromatography-mass spectrometry revealed six major constituents in order of relative abundance: benzaldehyde, (E)-β-ocimene, phenylacetaldehyde, benzyl alcohol, nonanal, and (E)-2-nonenal. Although not all were collected from the headspace profile of live flowers, a synthetic blend of these six compounds, when presented to mosquitoes in the same levels and proportions that occur in the extract, elicited a response comparable to the extract. Subtractive behavioral bioassays demonstrated that a three-component blend consisting of benzaldehyde, phenylacetaldehyde, and (E)-2-nonenal was as attractive as the full blend. These findings suggest the potential use of synthetic floral-odor blends for monitoring or control of both male and female disease-vectoring mosquitoes.

  1. Application of chemometric analysis based on physicochemical and chromatographic data for the differentiation origin of plant protection products containing chlorpyrifos.

    Science.gov (United States)

    Miszczyk, Marek; Płonka, Marlena; Bober, Katarzyna; Dołowy, Małgorzata; Pyka, Alina; Pszczolińska, Klaudia

    2015-01-01

    The aim of this study was to investigate the similarities and dissimilarities between the pesticide samples in form of emulsifiable concentrates (EC) formulation containing chlorpyrifos as active ingredient coming from different sources (i.e., shops and wholesales) and also belonging to various series. The results obtained by the Headspace Gas Chromatography-Mass Spectrometry method and also some selected physicochemical properties of examined pesticides including pH, density, stability, active ingredient and water content in pesticides tested were compared using two chemometric methods. Applicability of simple cluster analysis and also principal component analysis of obtained data in differentiation of examined plant protection products coming from different sources was confirmed. It would be advantageous in the routine control of originality and also in the detection of counterfeit pesticides, respectively, among commercially available pesticides containing chlorpyrifos as an active ingredient.

  2. Characterizing the Smell of Marijuana by Odor Impact of Volatile Compounds: An Application of Simultaneous Chemical and Sensory Analysis.

    Directory of Open Access Journals (Sweden)

    Somchai Rice

    Full Text Available Recent U.S. legislation permitting recreational use of marijuana in certain states brings the use of marijuana odor as probable cause for search and seizure to the forefront of forensic science, once again. This study showed the use of solid-phase microextraction with multidimensional gas chromatography--mass spectrometry and simultaneous human olfaction to characterize the total aroma of marijuana. The application of odor activity analysis offers an explanation as to why high volatile chemical concentration does not equate to most potent odor impact of a certain compound. This suggests that more attention should be focused on highly odorous compounds typically present in low concentrations, such as nonanal, decanol, o-cymene, benzaldehyde, which have more potent odor impact than previously reported marijuana headspace volatiles.

  3. Analysis of seven salad rocket (Eruca sativa) accessions: The relationships between sensory attributes and volatile and non-volatile compounds.

    Science.gov (United States)

    Bell, Luke; Methven, Lisa; Signore, Angelo; Oruna-Concha, Maria Jose; Wagstaff, Carol

    2017-03-01

    Sensory and chemical analyses were performed on accessions of rocket (Eruca sativa) to determine phytochemical influences on sensory attributes. A trained panel was used to evaluate leaves, and chemical data were obtained for polyatomic ions, amino acids, sugars and organic acids. These chemical data (and data of glucosinolates, flavonols and headspace volatiles previously reported) were used in Principal Component Analysis (PCA) to determine variables statistically important to sensory traits. Significant differences were observed between samples for polyatomic ion and amino acid concentrations. PCA revealed strong, positive correlations between glucosinolates, isothiocyanates and sulfur compounds with bitterness, mustard, peppery, warming and initial heat mouthfeel traits. The ratio between glucosinolates and sugars inferred reduced perception of bitter aftereffects. We highlight the diversity of E. sativa accessions from a sensory and phytochemical standpoint, and the potential for breeders to create varieties that are nutritionally and sensorially superior to existing ones. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

  4. Application of acetone acetals as water scavengers and derivatization agents prior to the gas chromatographic analysis of polar residual solvents in aqueous samples.

    Science.gov (United States)

    van Boxtel, Niels; Wolfs, Kris; Van Schepdael, Ann; Adams, Erwin

    2015-12-18

    The sensitivity of gas chromatography (GC) combined with the full evaporation technique (FET) for the analysis of aqueous samples is limited due to the maximum tolerable sample volume in a headspace vial. Using an acetone acetal as water scavenger prior to FET-GC analysis proved to be a useful and versatile tool for the analysis of high boiling analytes in aqueous samples. 2,2-Dimethoxypropane (DMP) was used in this case resulting in methanol and acetone as reaction products with water. These solvents are relatively volatile and were easily removed by evaporation enabling sample enrichment leading to 10-fold improvement in sensitivity compared to the standard 10μL FET sample volumes for a selection of typical high boiling polar residual solvents in water. This could be improved even further if more sample is used. The method was applied for the determination of residual NMP in an aqueous solution of a cefotaxime analogue and proved to be considerably better than conventional static headspace (sHS) and the standard FET approach. The methodology was also applied to determine trace amounts of ethylene glycol (EG) in aqueous samples like contact lens fluids, where scavenging of the water would avoid laborious extraction prior to derivatization. During this experiment it was revealed that DMP reacts quantitatively with EG to form 2,2-dimethyl-1,3-dioxolane (2,2-DD) under the proposed reaction conditions. The relatively high volatility (bp 93°C) of 2,2-DD makes it possible to perform analysis of EG using the sHS methodology making additional derivatization reactions superfluous. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Volatile-Compound Fingerprinting by Headspace-Gas-Chromatography Ion-Mobility Spectrometry (HS-GC-IMS) as a Benchtop Alternative to 1H NMR Profiling for Assessment of the Authenticity of Honey.

    Science.gov (United States)

    Gerhardt, Natalie; Birkenmeier, Markus; Schwolow, Sebastian; Rohn, Sascha; Weller, Philipp

    2018-02-06

    This work describes a simple approach for the untargeted profiling of volatile compounds for the authentication of the botanical origins of honey based on resolution-optimized HS-GC-IMS combined with optimized chemometric techniques, namely PCA, LDA, and kNN. A direct comparison of the PCA-LDA models between the HS-GC-IMS and 1 H NMR data demonstrated that HS-GC-IMS profiling could be used as a complementary tool to NMR-based profiling of honey samples. Whereas NMR profiling still requires comparatively precise sample preparation, pH adjustment in particular, HS-GC-IMS fingerprinting may be considered an alternative approach for a truly fully automatable, cost-efficient, and in particular highly sensitive method. It was demonstrated that all tested honey samples could be distinguished on the basis of their botanical origins. Loading plots revealed the volatile compounds responsible for the differences among the monofloral honeys. The HS-GC-IMS-based PCA-LDA model was composed of two linear functions of discrimination and 10 selected PCs that discriminated canola, acacia, and honeydew honeys with a predictive accuracy of 98.6%. Application of the LDA model to an external test set of 10 authentic honeys clearly proved the high predictive ability of the model by correctly classifying them into three variety groups with 100% correct classifications. The constructed model presents a simple and efficient method of analysis and may serve as a basis for the authentication of other food types.

  6. Validation of an analytical method for nitrous oxide (N2O) laughing gas by headspace gas chromatography coupled to mass spectrometry (HS-GC-MS): forensic application to a lethal intoxication.

    Science.gov (United States)

    Giuliani, N; Beyer, J; Augsburger, M; Varlet, V

    2015-03-01

    Drug abuse is a widespread problem affecting both teenagers and adults. Nitrous oxide is becoming increasingly popular as an inhalation drug, causing harmful neurological and hematological effects. Some gas chromatography-mass spectrometry (GC-MS) methods for nitrous oxide measurement have been previously described. The main drawbacks of these methods include a lack of sensitivity for forensic applications; including an inability to quantitatively determine the concentration of gas present. The following study provides a validated method using HS-GC-MS which incorporates hydrogen sulfide as a suitable internal standard allowing the quantification of nitrous oxide. Upon analysis, sample and internal standard have similar retention times and are eluted quickly from the molecular sieve 5Å PLOT capillary column and the Porabond Q column therefore providing rapid data collection whilst preserving well defined peaks. After validation, the method has been applied to a real case of N2O intoxication indicating concentrations in a mono-intoxication. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. A new method for the determination of short-chain fatty acids from the aliphatic series in wines by headspace solid-phase microextraction-gas chromatography-ion trap mass spectrometry.

    Science.gov (United States)

    Olivero, Sergio J Pérez; Trujillo, Juan P Pérez

    2011-06-24

    A new analytical method for the determination of nine short-chain fatty acids (acetic, propionic, isobutyric, butyric, isovaleric, 2-methylbutyric, hexanoic, octanoic and decanoic acids) in wines using the automated HS/SPME-GC-ITMS technique was developed and optimised. Five different SPME fibers were tested and the influence of different factors such as temperature and time of extraction, temperature and time of desorption, pH, strength ionic, tannins, anthocyans, SO(2), sugar and ethanol content were studied and optimised using model solutions. Some analytes showed matrix effect so a study of recoveries was performed. The proposed HS/SPME-GC-ITMS method, that covers the concentration range of the different analytes in wines, showed wide linear ranges, values of repeatability and reproducibility lower than 4.0% of RSD and detection limits between 3 and 257 μgL(-1), lower than the olfactory thresholds. The optimised method is a suitable technique for the quantitative analysis of short-chain fatty acids from the aliphatic series in real samples of white, rose and red wines. Copyright © 2011 Elsevier B.V. All rights reserved.

  8. Tank 241-AZ-101 and tank 241-AZ-102, airlift circulator operation vapor sampling and analysis plan

    International Nuclear Information System (INIS)

    TEMPLETON, A.M.

    1999-01-01

    This sampling and analysis plan (SAP) identifies characterization objectives pertaining to sample collection, laboratory analytical evaluation, and reporting requirements for vapor samples obtained during the operation of the tank 241-AZ-101 and 241-AZ-102 airlift circulators (ALCs). The purpose of the ALC operation is to support portions of the operational test procedure (OTP) for Project W-030 (OTP-W030-001) and to perform functional test in support of Project W-151. Project W-030 is the 241-A-702 ventilation upgrade project (241-AZ-702) and Project W-151 is the 241-AZ-101 Mixer Pump Test. The functional tests will check the operability of the tank 241-AZ-101 ALCs. Process Memo's No.2E98-082 and No.2E99-001 (LMHC 1999a, LMHC 1999b) direct the operation of the ALCs and the Industrial Hygiene monitoring respectively. A series of tests will be conducted in which the ALCs in tanks 241-AZ-101 and 241-AZ-102 will be operated at different air flow rates. Vapor samples will be obtained to determine constituents that may be present in the tank headspace during ALC operation at tanks 241-AZ-101 and 241-AZ-102 as the waste is disturbed. During the testing, vapor samples will be obtained from the headspace of tanks 241-AZ-101 and 241-AZ-102 via the unused port on the standard hydrogen monitoring system (SHMS). Results will be used to provide the waste feed delivery program with environmental air permitting data for tank waste disturbing activities. Because of radiological concerns, the samples will be filtered for particulates. It is recognized that this may remove some organic compounds

  9. Application of novel activated carbon fiber solid-phase, microextraction to the analysis of chlorinated hydrocarbons in water by gas chromatography-mass spectrometry

    International Nuclear Information System (INIS)

    Sun Tonghua; Jia Jinping; Fang Nenghu; Wang Yalin

    2005-01-01

    This paper presents a study on the performance of activated carbon fiber (ACF) used as extraction fiber for solid-phase microextraction (SPME) and its application for analysis of chlorinated hydrocarbons in water. By means of evaluating scanning electron microscope (SEM) images, specific surface area, pore volume, pore distribution, and properties of adsorption and desorption, the optimal active concentration of phosphoric acid has been determined. Coupled with gas chromatograph-mass spectrometry (GC-MS), ACF-SPME is suitable for determination chlorinated hydrocarbons in water with headspace. Experimental parameters such as adsorption and desorption conditions were studied. The optimized method has an acceptable linearity, good precision, with R.S.D. values <10% for each compound. Compared with commercial fibers, ACF has many advantages such as better resistance to organic solvents, better endurance to high temperature and longer lifetime

  10. Determination of Methyl tert-Butyl Ether and tert-Butyl Alcohol in Water by Solid-Phase Microextraction/Head Space Analysis in Comparison to EPA Method 5030/8260B

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Keun-Chan; Stringfellow, William T.

    2003-10-02

    Methyl tert-butyl ether (MTBE) is now one of the most common groundwater contaminants in the United States. Groundwater contaminated with MTBE is also likely to be contaminated with tert-butyl alcohol (TBA), because TBA is a component of commercial grade MTBE, TBA can also be used as a fuel oxygenate, and TBA is a biodegradation product of MTBE. In California, MTBE is subject to reporting at concentrations greater than 3 {micro}g/L. TBA is classified as a ''contaminant of current interest'' and has a drinking water action level of 12 {micro}g/L. In this paper, we describe the development and optimization of a simple, automated solid phase microextraction (SPME) method for the analysis of MTBE and TBA in water and demonstrate the applicability of this method for monitoring MTBE and TBA contamination in groundwater, drinking water, and surface water. In this method, the headspace (HS) of a water sample is extracted with a carboxen/polydimethylsiloxane SPME fiber, the MTBE and TBA are desorbed into a gas chromatograph (GC), and detected using mass spectrometry (MS). The method is optimized for the routine analysis of MTBE and TBA with a level of quantitation of 0.3 {micro}g/L and 4 {micro}g/L, respectively, in water. MTBE quantitation was linear for over two orders of concentration (0.3 {micro}g/L -80 {micro}g/L). TBA was found to be linear within the range of 4 {micro}g/L-7,900 {micro}g/L. The lower level of detection for MTBE is 0.03 {micro}g/L using this method. This SPME method using headspace extraction was found to be advantageous over SPME methods requiring immersion of the fiber into the water samples, because it prolonged the life of the fiber by up to 400 sample analyses. This is the first time headspace extraction SPME has been shown to be applicable to the measurement of both MTBE and TBA at concentrations below regulatory action levels. This method was compared with the certified EPA Method 5030/8260B (purge-and-trap/GC/MS) using split

  11. Special Analysis: Disposal Plan for Pit 38 at Technical Area 54, Area G

    Energy Technology Data Exchange (ETDEWEB)

    French, Sean B. [Los Alamos National Laboratory; Shuman, Rob [URS Coporation

    2012-06-26

    been made to utilize the remaining disposal capacity within MDA G to the greatest extent possible. One approach for doing this has been to dispose of low-activity waste from cleanup operations at LANL in the headspace of selected disposal pits. Waste acceptance criteria (WAC) for the material placed in the headspace of pits 15, 37, and 38 have been developed (LANL, 2010) and the impacts of placing waste in the headspace of these units has been evaluated (LANL, 2012a). The efforts to maximize disposal efficiency have taken on renewed importance because of the disposal demands placed on MDA G by the large volumes of waste that are being generated at LANL by cleanup efforts. For example, large quantities of waste were recently generated by the retrieval of waste formerly disposed of at TA-21, MDA B. A portion of this material has been disposed of in the headspace of pit 38 in compliance with the WAC developed for that disposal strategy; a large amount of waste has also been sent to off-site facilities for disposal. Nevertheless, large quantities of MDA B waste remain that require disposal. An extension of pit 38 was proposed to provide the disposal capacity that will be needed to dispose of institutional waste and MDA B waste through 2013. A special analysis was prepared to evaluate the impacts of the pit extension (LANL, 2012b). The analysis concluded that the disposal unit could be extended with modest increases in the exposures projected for the Area G performance assessment and composite analysis, as long as limits were placed on the radionuclide concentrations in the waste that is placed in the headspace of the pit. Based, in part, on the results of the special analysis, the extension of pit 38 was approved and excavation of the additional disposal capacity was started in May 2012. The special analysis presented here uses performance modeling to identify a disposal plan for the placement of waste in pit 38. The modeling uses a refined design of the disposal unit and

  12. Special Analysis: Disposal Plan for Pit 38 at Technical Area 54, Area G

    International Nuclear Information System (INIS)

    French, Sean B.; Shuman, Rob

    2012-01-01

    have been made to utilize the remaining disposal capacity within MDA G to the greatest extent possible. One approach for doing this has been to dispose of low-activity waste from cleanup operations at LANL in the headspace of selected disposal pits. Waste acceptance criteria (WAC) for the material placed in the headspace of pits 15, 37, and 38 have been developed (LANL, 2010) and the impacts of placing waste in the headspace of these units has been evaluated (LANL, 2012a). The efforts to maximize disposal efficiency have taken on renewed importance because of the disposal demands placed on MDA G by the large volumes of waste that are being generated at LANL by cleanup efforts. For example, large quantities of waste were recently generated by the retrieval of waste formerly disposed of at TA-21, MDA B. A portion of this material has been disposed of in the headspace of pit 38 in compliance with the WAC developed for that disposal strategy; a large amount of waste has also been sent to off-site facilities for disposal. Nevertheless, large quantities of MDA B waste remain that require disposal. An extension of pit 38 was proposed to provide the disposal capacity that will be needed to dispose of institutional waste and MDA B waste through 2013. A special analysis was prepared to evaluate the impacts of the pit extension (LANL, 2012b). The analysis concluded that the disposal unit could be extended with modest increases in the exposures projected for the Area G performance assessment and composite analysis, as long as limits were placed on the radionuclide concentrations in the waste that is placed in the headspace of the pit. Based, in part, on the results of the special analysis, the extension of pit 38 was approved and excavation of the additional disposal capacity was started in May 2012. The special analysis presented here uses performance modeling to identify a disposal plan for the placement of waste in pit 38. The modeling uses a refined design of the disposal unit

  13. Detection of mastitis pathogens by analysis of volatile bacterial metabolites.

    Science.gov (United States)

    Hettinga, K A; van Valenberg, H J F; Lam, T J G M; van Hooijdonk, A C M

    2008-10-01

    The ability to detect mastitis pathogens based on their volatile metabolites was studied. Milk samples from cows with clinical mastitis, caused by Staphylococcus aureus, coagulase-negative staphylococci, Streptococcus uberis, Streptococcus dysgalactiae, and Escherichia coli were collected. In addition, samples from cows without clinical mastitis and with low somatic cell count (SCC) were collected for comparison. All mastitis samples were examined by using classical microbiological methods, followed by headspace analysis for volatile metabolites. Milk from culture-negative samples contained a lower number and amount of volatile components compared with cows with clinical mastitis. Because of variability between samples within a group, comparisons between pathogens were not sufficient for classification of the samples by univariate statistics. Therefore, an artificial neural network was trained to classify the pathogen in the milk samples based on the bacterial metabolites. The trained network differentiated milk from uninfected and infected quarters very well. When comparing pathogens, Staph. aureus produced a very different pattern of volatile metabolites compared with the other samples. Samples with coagulase-negative staphylococci and E. coli had enough dissimilarity with the other pathogens, making it possible to separate these 2 pathogens from each other and from the other samples. The 2 streptococcus species did not show significant differences between each other but could be identified as a different group from the other pathogens. Five groups can thus be identified based on the volatile bacterial metabolites: Staph. aureus, coagulase-negative staphylococci, streptococci (Strep. uberis and Strep. dysgalactiae as one group), E. coli, and uninfected quarters.

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

    African Journals Online (AJOL)

    Pharmacotherapy Group, Faculty of Pharmacy, University of Benin, Benin City, 300001 Nigeria. All rights ... to the Compositae family. The plant .... different temperatures, balance periods, and ... No conflict of interest associated with this work.

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

    African Journals Online (AJOL)

    Tropical Journal of Pharmaceutical Research May 2015; 14(5): 891-898. ISSN: 1596-5996 ... with the potential to analyze volatile compounds in raw and processed FCP. .... hydrocarbons, furans and oxazoles were formed during the ..... vol. 1. Beijing: China Medical Science and Technology. Press; pp 29-30. 11. Zhu CY ...

  16. All rights reserved Development of Headspace Solid-Phase ...

    African Journals Online (AJOL)

    ADOWIE PERE

    1 Department of Chemistry, Faculty of Science, University of Malaya, Pantai ... mixture of organic solvents was optimized using design of experiment (DOE) with simplex ... food pose a potential health risk to animal and human ... The GC oven temperature program was .... sample pH also helps to transform the analytes into.

  17. A comparison of sorptive extraction techniques coupled to a new quantitative, sensitive, high throughput GC-MS/MS method for methoxypyrazine analysis in wine.

    Science.gov (United States)

    Hjelmeland, Anna K; Wylie, Philip L; Ebeler, Susan E

    2016-02-01

    Methoxypyrazines are volatile compounds found in plants, microbes, and insects that have potent vegetal and earthy aromas. With sensory detection thresholds in the low ng L(-1) range, modest concentrations of these compounds can profoundly impact the aroma quality of foods and beverages, and high levels can lead to consumer rejection. The wine industry routinely analyzes the most prevalent methoxypyrazine, 2-isobutyl-3-methoxypyrazine (IBMP), to aid in harvest decisions, since concentrations decrease during berry ripening. In addition to IBMP, three other methoxypyrazines IPMP (2-isopropyl-3-methoxypyrazine), SBMP (2-sec-butyl-3-methoxypyrazine), and EMP (2-ethyl-3-methoxypyrazine) have been identified in grapes and/or wine and can impact aroma quality. Despite their routine analysis in the wine industry (mostly IBMP), accurate methoxypyrazine quantitation is hindered by two major challenges: sensitivity and resolution. With extremely low sensory detection thresholds (~8-15 ng L(-1) in wine for IBMP), highly sensitive analytical methods to quantify methoxypyrazines at trace levels are necessary. Here we were able to achieve resolution of IBMP as well as IPMP, EMP, and SBMP from co-eluting compounds using one-dimensional chromatography coupled to positive chemical ionization tandem mass spectrometry. Three extraction techniques HS-SPME (headspace-solid phase microextraction), SBSE (stirbar sorptive extraction), and HSSE (headspace sorptive extraction) were validated and compared. A 30 min extraction time was used for HS-SPME and SBSE extraction techniques, while 120 min was necessary to achieve sufficient sensitivity for HSSE extractions. All extraction methods have limits of quantitation (LOQ) at or below 1 ng L(-1) for all four methoxypyrazines analyzed, i.e., LOQ's at or below reported sensory detection limits in wine. The method is high throughput, with resolution of all compounds possible with a relatively rapid 27 min GC oven program. Copyright © 2015

  18. Detection of colorectal cancer (CRC) by urinary volatile organic compound analysis.

    Science.gov (United States)

    Arasaradnam, Ramesh P; McFarlane, Michael J; Ryan-Fisher, Courtenay; Westenbrink, Erik; Hodges, Phoebe; Hodges, Paula; Thomas, Matthew G; Chambers, Samantha; O'Connell, Nicola; Bailey, Catherine; Harmston, Christopher; Nwokolo, Chuka U; Bardhan, Karna D; Covington, James A

    2014-01-01

    Colorectal cancer (CRC) is a leading cause of cancer related death in Europe and the USA. There is no universally accepted effective non-invasive screening test for CRC. Guaiac based faecal occult blood (gFOB) testing has largely been superseded by Faecal Immunochemical testing (FIT), but sensitivity still remains poor. The uptake of population based FOBt testing in the UK is also low at around 50%. The detection of volatile organic compounds (VOCs) signature(s) for many cancer subtypes is receiving increasing interest using a variety of gas phase analytical instruments. One such example is FAIMS (Field Asymmetric Ion Mobility Spectrometer). FAIMS is able to identify Inflammatory Bowel disease (IBD) patients by analysing shifts in VOCs patterns in both urine and faeces. This study extends this concept to determine whether CRC patients can be identified through non-invasive analysis of urine, using FAIMS. 133 patients were recruited; 83 CRC patients and 50 healthy controls. Urine was collected at the time of CRC diagnosis and headspace analysis undertaken using a FAIMS instrument (Owlstone, Lonestar, UK). Data was processed using Fisher Discriminant Analysis (FDA) after feature extraction from the raw data. FAIMS analyses demonstrated that the VOC profiles of CRC patients were tightly clustered and could be distinguished from healthy controls. Sensitivity and specificity for CRC detection with FAIMS were 88% and 60% respectively. This study suggests that VOC signatures emanating from urine can be detected in patients with CRC using ion mobility spectroscopy technology (FAIMS) with potential as a novel screening tool.

  19. Analysis of organic micropollutants in drinking water using SPME and GC-MS

    International Nuclear Information System (INIS)

    Guidotti, M.; Ravaioli, G.

    1999-01-01

    In this work the purpose was to develop accurate and reproducible methods for the qualitative and quantitative analysis of pesticides/herbicides, phthalates, chlorinated solvents, trihalomethanes, polycyclic aromatic hydrocarbons (PAHs) and chlorophenols in drinking waters, using solid-phase micro extraction and GC-MS techniques. The SPME developed by J. Pawliszyn and co-workers, consists of an fused silica fibre, coated with an appropriate absorbent phase, hosted inside the needle of a holder that looks like a GC-syringe; the needle pierces the septum of a sealed vial and the fibre is lowered, by depressing the plunger of the holder, into the liquid (or in the headspace, if that is the case) that contains the analytes of interest. After a set period of time, necessary to reach the partitioning equilibrium, the fibre is retracted inside the needle, the needle is inserted into the GC injector port and the fibre pushed in the heated injector. Here the compounds of interest (that have adsorbed onto the fibre) are thermally desorbed and analysed by GC-MS. After three minutes the fibre is extracted and is ready for a new analysis. The SPME technique has already found many applications in food and environmental analysis. Many of the analytes investigated in this research are listed Italian legislation as possible pollutants of drinking waters and their presence and concentrations require monitoring. The list of compounds included in this work is reported in Table 1

  20. Factorial analysis of the trihalomethanes formation in water disinfection using chlorine

    International Nuclear Information System (INIS)

    Rodrigues, Pedro M.S.M.; Esteves da Silva, Joaquim C.G.; Antunes, Maria Cristina G.

    2007-01-01

    The factors that affect trihalomethane (THM) (chloroform, bromodichloromethane, chlorodibromomethane and bromoform) formation from the chlorination of aqueous solutions of hydrophobic fulvic acids (FA) were investigated in a prototype laboratorial simulation using factorial analysis. This strategy involved a fractional factorial design (16 plus 5 center experiments) of five factors (fulvic acids concentration, chlorine dose, temperature, pH and bromide concentration) and a Box Behnken design (12 plus 3 center experiments) for the detailed analysis of three factors (FA concentration, chlorine dose and temperature). The concentration of THM was determined by headspace analysis by GC-ECD. The most significant factors that affect the four THM productions were the following: chloroform-FA concentration and temperature; bromodichloromethane-FA concentration and chlorine dose; chlorodibromomethane-chlorine dose; and, bromoform-chlorine dose and bromide concentration. Moreover, linear models were obtained for the four THM concentrations in the disinfection solution as function of the FA concentration, chlorine dose and temperature, and it was observed that the complexity of the models (number of significant factors and interactions) increased with increasing bromine atoms in the THM. Also, this study shows that reducing the FA concentration the relative amount of bromated THM increases

  1. Characterization of the volatile components in green tea by IRAE-HS-SPME/GC-MS combined with multivariate analysis.

    Science.gov (United States)

    Yang, Yan-Qin; Yin, Hong-Xu; Yuan, Hai-Bo; Jiang, Yong-Wen; Dong, Chun-Wang; Deng, Yu-Liang

    2018-01-01

    In the present work, a novel infrared-assisted extraction coupled to headspace solid-phase microextraction (IRAE-HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS) was developed for rapid determination of the volatile components in green tea. The extraction parameters such as fiber type, sample amount, infrared power, extraction time, and infrared lamp distance were optimized by orthogonal experimental design. Under optimum conditions, a total of 82 volatile compounds in 21 green tea samples from different geographical origins were identified. Compared with classical water-bath heating, the proposed technique has remarkable advantages of considerably reducing the analytical time and high efficiency. In addition, an effective classification of green teas based on their volatile profiles was achieved by partial least square-discriminant analysis (PLS-DA) and hierarchical clustering analysis (HCA). Furthermore, the application of a dual criterion based on the variable importance in the projection (VIP) values of the PLS-DA models and on the category from one-way univariate analysis (ANOVA) allowed the identification of 12 potential volatile markers, which were considered to make the most important contribution to the discrimination of the samples. The results suggest that IRAE-HS-SPME/GC-MS technique combined with multivariate analysis offers a valuable tool to assess geographical traceability of different tea varieties.

  2. Characterization of the volatile components in green tea by IRAE-HS-SPME/GC-MS combined with multivariate analysis.

    Directory of Open Access Journals (Sweden)

    Yan-Qin Yang

    Full Text Available In the present work, a novel infrared-assisted extraction coupled to headspace solid-phase microextraction (IRAE-HS-SPME followed by gas chromatography-mass spectrometry (GC-MS was developed for rapid determination of the volatile components in green tea. The extraction parameters such as fiber type, sample amount, infrared power, extraction time, and infrared lamp distance were optimized by orthogonal experimental design. Under optimum conditions, a total of 82 volatile compounds in 21 green tea samples from different geographical origins were identified. Compared with classical water-bath heating, the proposed technique has remarkable advantages of considerably reducing the analytical time and high efficiency. In addition, an effective classification of green teas based on their volatile profiles was achieved by partial least square-discriminant analysis (PLS-DA and hierarchical clustering analysis (HCA. Furthermore, the application of a dual criterion based on the variable importance in the projection (VIP values of the PLS-DA models and on the category from one-way univariate analysis (ANOVA allowed the identification of 12 potential volatile markers, which were considered to make the most important contribution to the discrimination of the samples. The results suggest that IRAE-HS-SPME/GC-MS technique combined with multivariate analysis offers a valuable tool to assess geographical traceability of different tea varieties.

  3. Detection of Low Molecular Weight Adulterants in Beverages by Direct Analysis in Real Time Mass Spectrometry.

    Science.gov (United States)

    Sisco, Edward; Dake, Jeffrey

    2016-04-14

    Direct Analysis in Real Time Mass Spectrometry (DART-MS) has been used to detect the presence of non-narcotic adulterants in beverages. The non-narcotic adulterants that were examined in this work incorporated a number low molecular weight alcohols, acetone, ammonium hydroxide, and sodium hypochlorite. Analysis of the adulterants was completed by pipetting 1 µL deposits onto glass microcapillaries along with an appropriate dopant species followed by introduction into the DART gas stream. It was found that detection of these compounds in the complex matrices of common beverages (soda, energy drinks, etc.) was simplified through the use of a dopant species to allow for adduct formation with the desired compound(s) of interest. Other parameters that were investigated included DART gas stream temperature, in source collision induced dissociation, ion polarity, and DART needle voltage. Sensitivities of the technique were found to range from 0.001 % volume fraction to 0.1 % volume fraction, comparable to traditional analyses completed using headspace gas chromatography mass spectrometry (HS-GC/MS). Once a method was established using aqueous solutions, , fifteen beverages were spiked with each of the nine adulterants, to simulate real world detection, and in nearly all cases the adulterant could be detected either in pure form, or complexed with the added dopant species. This technique provides a rapid way to directly analyze beverages believed to be contaminated with non-narcotic adulterants at sensitivities similar to or exceeding those of traditional confirmatory analyses.

  4. The GC/MS Analysis of Volatile Components Extracted by Different Methods from Exocarpium Citri Grandis

    Directory of Open Access Journals (Sweden)

    Zhisheng Xie

    2013-01-01

    Full Text Available Volatile components from Exocarpium Citri Grandis (ECG were, respectively, extracted by three methods, that is, steam distillation (SD, headspace solid-phase microextraction (HS-SPME, and solvent extraction (SE. A total of 81 compounds were identified by gas chromatography-mass spectrometry including 77 (SD, 56 (HS-SPME, and 48 (SE compounds, respectively. Despite of the extraction method, terpenes (39.98~57.81% were the main volatile components of ECG, mainly germacrene-D, limonene, 2,6,8,10,14-hexadecapentaene, 2,6,11,15-tetramethyl-, (E,E,E-, and trans-caryophyllene. Comparison was made among the three methods in terms of extraction profile and property. SD relatively gave an entire profile of volatile in ECG by long-time extraction; SE enabled the analysis of low volatility and high molecular weight compounds but lost some volatiles components; HS-SPME generated satisfactory extraction efficiency and gave similar results to those of SD at analytical level when consuming less sample amount, shorter extraction time, and simpler procedure. Although SD and SE were treated as traditionally preparative extractive techniques for volatiles in both small batches and large scale, HS-SPME coupled with GC/MS could be useful and appropriative for the rapid extraction and qualitative analysis of volatile components from medicinal plants at analytical level.

  5. Analysis of honeybush tea (Cyclopia spp.) volatiles by comprehensive two-dimensional gas chromatography using a single-stage thermal modulator.

    Science.gov (United States)

    Ntlhokwe, Gaalebalwe; Tredoux, Andreas G J; Górecki, Tadeusz; Edwards, Matthew; Vestner, Jochen; Muller, Magdalena; Erasmus, Lené; Joubert, Elizabeth; Christel Cronje, J; de Villiers, André

    2017-07-01

    The applicability of comprehensive two-dimensional gas chromatography (GC×GC) using a single-stage thermal modulator was explored for the analysis of honeybush tea (Cyclopia spp.) volatile compounds. Headspace solid phase micro-extraction (HS-SPME) was used in combination with GC×GC separation on a non-polar × polar column set with flame ionisation (FID) detection for the analysis of fermented Cyclopia maculata, Cyclopia subternata and Cyclopia genistoides tea infusions of a single harvest season. Method optimisation entailed evaluation of the effects of several experimental parameters on the performance of the modulator, the choice of columns in both dimensions, as well as the HS-SPME extraction fibre. Eighty-four volatile compounds were identified by co-injection of reference standards. Principal component analysis (PCA) showed clear differentiation between the species based on their volatile profiles. Due to the highly reproducible separations obtained using the single-stage thermal modulator, multivariate data analysis was simplified. The results demonstrate both the complexity of honeybush volatile profiles and the potential of GC×GC separation in combination with suitable data analysis techniques for the investigation of the relationship between sensory properties and volatile composition of these products. The developed method therefore offers a fast and inexpensive methodology for the profiling of honeybush tea volatiles. Graphical abstract Surface plot obtained for the GC×GC-FID analysis of honeybush tea volatiles.

  6. Formation of chloroform in spruce forest soil - results from laboratory incubation studies

    DEFF Research Database (Denmark)

    Haselmann, K.F.; Laturnus, F.; Svensmark, B.

    2000-01-01

    The release of chloroform, 1,1,1-trichloroethane, tetrachloromethane, trichloroethene and tetrachloroethene from an organic rich spruce forest soil was studied in laboratory incubation experiments by dynamic headspace analysis, thermodesorption and gas chromatography. Performance parameters...... are presented for the dynamic headspace system. For spruce forest soil, the results showed a significant increase in chloroform concentration in the headspace under aerobic conditions over a period of seven days, whereas the concentration of the other compounds remained fairly constant. A biogenic formation...

  7. Characterisation of the volatile profile of coconut water from five varieties using an optimised HS-SPME-GC analysis.

    Science.gov (United States)

    Prades, Alexia; Assa, Rebecca Rachel Ablan; Dornier, Manuel; Pain, Jean-Pierre; Boulanger, Renaud

    2012-09-01

    Coconut (Cocos nucifera L.) water is a refreshing tropical drink whose international market has recently been growing. However, little is yet known about its physicochemical composition, particularly its aroma. This study set out to characterise the volatile profile of water from five coconut varieties. Aroma compounds were characterised by headspace solid phase microextraction gas chromatography (HS-SPME-GC) analysis. An experimental design was established to optimise SPME conditions, leading to an equilibration time of 10 min followed by an extraction time of 60 min at 50 °C. Accordingly, immature coconut water from WAT (West African Tall), PB121 (MYD × WAT Hybrid), MYD (Malayan Yellow Dwarf), EGD (Equatorial Guinea Green Dwarf) and THD (Thailand Aromatic Green Dwarf) palms was analysed and described. Ketones were mainly present in the Tall and Hybrid varieties, whereas aldehydes were most abundant in the Dwarf palms. Tall coconut water was characterised by a high lactone content. THD exhibited a high ethyl octanoate level. The cluster analysis of the volatile fraction from the five coconut cultivars was found to be related to their genetic classification. The volatile compounds of immature coconut water from five varieties were characterised for the first time. Volatile profile analysis could be a useful tool for the selection of Dwarf coconut varieties, which are mainly consumed as a beverage. Copyright © 2012 Society of Chemical Industry.

  8. Aroma analysis and quality control of food using highly sensitive analytical methods

    International Nuclear Information System (INIS)

    Mayr, D.

    2003-02-01

    This thesis deals with the development of quality control methods for food based on headspace measurements by Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) and with aroma analysis of food using PTR-MS and Gas Chromatography-Olfactometry (GC-O). An objective method was developed for the determination of a herb extract's quality; this quality was checked by a sensory analysis until now. The concentrations of the volatile organic compounds (VOCs) in the headspace of 81 different batches were measured by PTR-MS. Based on the sensory judgment of the customer, characteristic differences in the emissions of 'good' and 'bad' quality samples were identified and a method for the quality control of this herb extract was developed. This novel method enables the producing company to check and ensure that they are only selling high-quality products and therefore avoid complaints of the customer. Furthermore this method can be used for controlling, optimizing and automating the production process. VOCs emitted by meat were investigated using PTR-MS to develop a rapid, non-destructive and quantitative technique for determination of the microbial contamination of meat. Meat samples (beef, pork and poultry) that were wrapped into different kinds of packages (air and vacuum) were stored in at 4 o C for up to 13 days. The emitted VOCs were measured as a function of storage time and identified partly. The concentration of many of the measured VOCs, e.g. sulfur compounds like methanethiol, dimethylsulfide and dimethyldisulfide, largely increased over the storage time. There were big differences in the emissions of normal air- and vacuum-packed meat. VOCs typically emitted by air-packaged meat were methanethiol, dimethylsulfide and dimethyldisulfide, while ethanol and methanol were found in vacuum-packaged meat. A comparison of the PTR-MS results with those obtained by a bacteriological examination performed at the same time showed strong correlations (up to 99 %) between the

  9. Analysis of volatile organic compounds in compost samples: A potential tool to determine appropriate composting time.

    Science.gov (United States)

    Zhu, Fengxiang; Pan, Zaifa; Hong, Chunlai; Wang, Weiping; Chen, Xiaoyang; Xue, Zhiyong; Yao, Yanlai

    2016-12-01

    Changes in volatile organic compound contents in compost samples during pig manure composting were studied using a headspace, solid-phase micro-extraction method (HS-SPME) followed by gas chromatography with mass spectrometric detection (GC/MS). Parameters affecting the SPME procedure were optimized as follows: the coating was carbon molecular sieve/polydimethylsiloxane (CAR/PDMS) fiber, the temperature was 60°C and the time was 30min. Under these conditions, 87 compounds were identified from 17 composting samples. Most of the volatile components could only be detected before day 22. However, benzenes, alkanes and alkenes increased and eventually stabilized after day 22. Phenol and acid substances, which are important factors for compost quality, were almost undetectable on day 39 in natural compost (NC) samples and on day 13 in maggot-treated compost (MC) samples. Our results indicate that the approach can be effectively used to determine the composting times by analysis of volatile substances in compost samples. An appropriate composting time not only ensures the quality of compost and reduces the loss of composting material but also reduces the generation of hazardous substances. The appropriate composting times for MC and NC were approximately 22days and 40days, respectively, during the summer in Zhejiang. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Julian; Mateo-Vivaracho, Laura; Cacho, Juan [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain); Ferreira, Vicente, E-mail: vferre@unizar.es [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain)

    2010-02-15

    This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R{sup 2} > 0.99), repeatability of the SPE method (RSD < 10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%.

  11. Analysis of Five Earthy-Musty Odorants in Environmental Water by HS-SPME/GC-MS

    Directory of Open Access Journals (Sweden)

    Zhen Ding

    2014-01-01

    Full Text Available The pressing issue of earthy and musty odor compounds in natural waters, which can affect the organoleptic properties of drinking water, makes it a public health concern. A simple and sensitive method for simultaneous analysis of five odorants in environmental water was developed by headspace solid-phase microextraction (HS-SPME coupled to chromatography-mass spectrometry (GC-MS, including geosmin (GSM and 2-methylisoborneol (2-MIB, as well as dimethyl trisulfide (DMTS, β-cyclocitral, and β-ionone. Based on the simple modification of original magnetic stirrer purchased from CORNING (USA, the five target compounds can be separated within 23 min, and the calibration curves show good linearity with a correlation coefficient above 0.999 (levels = 5. The limits of detection (LOD are all below 1.3 ng L−1, and the relative standard deviation (%RSD is between 4.4% and 9.9% (n = 7 and recoveries of the analytes from water samples are between 86.2% and 112.3%. In addition, the storage time experiment indicated that the concentrations did not change significantly for GSM and 2-MIB if they were stored in canonical environment. In conclusion, the method in this study could be applied for monitoring these five odorants in natural waters.

  12. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls

    International Nuclear Information System (INIS)

    Zapata, Julian; Mateo-Vivaracho, Laura; Cacho, Juan; Ferreira, Vicente

    2010-01-01

    This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R 2 > 0.99), repeatability of the SPE method (RSD < 10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%.

  13. Electrochemical stability of organic electrolytes in supercapacitors: Spectroscopy and gas analysis of decomposition products

    Energy Technology Data Exchange (ETDEWEB)

    Kurzweil, P.; Chwistek, M. [University of Applied Sciences, Kaiser-Wilhelm-Ring 23, D-92224 Amberg (Germany)

    2008-02-01

    The fundamental aging mechanisms in double-layer capacitors based on alkylammonium electrolytes in acetonitrile were clarified for the first time. After abusive testing at cell voltages above 4 V, ultracapacitors cast out a crystalline mass of residual electrolyte, organic acids, acetamide, aromatics, and polymer compounds. The mixture could be reproduced by electrolysis. The decomposition products of active carbon electrodes and electrolyte solution after a heat treatment at 70 C were identified by infrared and ultraviolet spectroscopy, liquid and headspace GC-MS, thermogravimetric analysis, and X-ray diffraction. The alkylammonium cation is destroyed by the elimination of ethene. The fluoroborate anion works as source of fluoride and hydrogenfluoride, and boric acid derivates. Acetonitrile forms acetamide, acetic and fluoroacetic acid, and derivates thereof. Due to the catalytic activity of the electrode, heterocyclic compounds are generated in the liquid phase. The etched aluminium support under the active carbon layer is locally destroyed by fluorination. Exploring novel electrolytes, ionic liquids were characterized by impedance spectroscopy. (author)

  14. Analysis of the essential oils from Calendula officinalis growing in Brazil using three different extraction procedures Análise por CG-EM do óleo essencial de Calendula officinalis cultivado no Brasil utilizando-se três diferentes processos de extração

    Directory of Open Access Journals (Sweden)

    Zilda Cristina Gazim

    2008-09-01

    Full Text Available Terpenes and aroma volatiles from flowers of Calendula officinalis cultivated in southeastern Brazil were obtained by steam distillation (SD, headspace-cold finger (HS-CF extraction and headspace solid-phase microextraction (HS-SPME coupled with gas chromatography and mass spectrometric analysis. The dried flowers contained 0.1% oil. Kovats indices and mass spectra were used to identify 27 individual components in the various volatile fractions. The main components present in the volatile fractions of the C. officinalis flowers, obtained by SD, HS-SPME, and HS-CF, were δ-cadinene (22.5, 22.1, and 18.4 % and γ-cadinene (8.9, 25.4, and 24.9 % while 20.4 % of α-cadinol was seen only after SD extraction.Terpenos e aromas voláteis das flores de Calendula officinalis cultivados no sudoeste do Brasil foram isolados por arraste a vapor (SD, dedo frio (HS-CF e micro extração em fase sólida (HS-SPME acoplada à espectrometria de massas. As flores secas da C. officinalis contêm 0,1% de óleo essencial e foram identificadas 27 substâncias químicas através do cálculo do índice de Kováts e interpretação dos espectros de massas. As substâncias majoritárias presentes no óleo essencial das flores de C. officinalis, obtido por SD, HS-SPME e HS-CF foram δ-cadinene (22,5; 22,1 e 18,4 % γ-cadinene (8,9, 25,4 e 24,9 % e 20.4 % de α-cadinol foi observado apenas na extração por arraste a vapor.

  15. HS-SPME-GC-MS ANALYSIS OF VOLATILE AND SEMI-VOLATILE COMPOUNDS FROM DRIED LEAVES OF Mikania glomerata Sprengel

    Directory of Open Access Journals (Sweden)

    Esmeraldo A. Cappelaro

    2015-03-01

    Full Text Available This paper reports on the identification of volatile and semi-volatile compounds and a comparison of the chromatographic profiles obtained by Headspace Solid-Phase Microextraction/Gas Chromatography with Mass Spectrometry detection (HS-SPME-GC-MS of dried leaves of Mikania glomerata Sprengel (Asteraceae, also known as 'guaco.' Three different types of commercial SPME fibers were tested: polydimethylsiloxane (PDMS, polydimethylsiloxane/divinylbenzene (PDMS/DVB and polyacrylate (PA. Fifty-nine compounds were fully identified by HS-SPME-HRGC-MS, including coumarin, a marker for the quality control of guaco-based phytomedicines; most of the other identified compounds were mono- and sesquiterpenes. PA fibers performed better in the analysis of coumarin, while PDMS-DVB proved to be the best choice for a general and non-selective analysis of volatile and semi-volatile guaco-based compounds. The SPME method is faster and requires a smaller sample than conventional hydrodistillation of essential oils, providing a general overview of the volatile and semi-volatile compounds of M. glomerata.

  16. Effects of Fire Suppression Agents and Weathering in the Analysis of Fire Debris by HS-MS eNose

    Directory of Open Access Journals (Sweden)

    Barbara Falatová

    2018-06-01

    Full Text Available In arson attacks the detection of ignitable liquid residues (ILRs at fire scenes provides key evidence since ignitable liquids, such as gasoline, are commonly used to initiate the fire. In most forensic laboratories gas chromatography-mass spectrometry is employed for the analysis of ILRs. When a fire occurs, suppression agents are used to extinguish the fire and, before the scene is investigated, the samples at the scene are subjected to a variety of processes such as weathering, which can significantly modify the chemical composition and thus lead to erroneous conclusions. In order to avoid this possibility, the application of chemometric tools that help the analyst to extract useful information from data is very advantageous. The study described here concerned the application of a headspace-mass spectrometry electronic nose (HS-MS eNose combined with chemometric tools to determine the presence/absence of gasoline in weathered fire debris samples. The effect of applying two suppression agents (Cafoam Aquafoam AF-6 and Pyro-chem PK-80 Powder and delays in the sampling time (from 0 to 48 h were studied. It was found that, although the suppression systems affect the mass spectra, the HS-MS eNose in combination with suitable pattern recognition chemometric tools, such as linear discriminant analysis, is able to identify the presence of gasoline in any of the studied situations (100% correct classification.

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

    Science.gov (United States)

    Kamalabadi, Mahdie; Mohammadi, Abdorreza; Alizadeh, Naader

    2016-08-15

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

  18. Large-volume constant-concentration sampling technique coupling with surface-enhanced Raman spectroscopy for rapid on-site gas analysis.

    Science.gov (United States)

    Zhang, Zhuomin; Zhan, Yisen; Huang, Yichun; Li, Gongke

    2017-08-05

    In this work, a portable large-volume constant-concentration (LVCC) sampling technique coupling with surface-enhanced Raman spectroscopy (SERS) was developed for the rapid on-site gas analysis based on suitable derivatization methods. LVCC sampling technique mainly consisted of a specially designed sampling cell including the rigid sample container and flexible sampling bag, and an absorption-derivatization module with a portable pump and a gas flowmeter. LVCC sampling technique allowed large, alterable and well-controlled sampling volume, which kept the concentration of gas target in headspace phase constant during the entire sampling process and made the sampling result more representative. Moreover, absorption and derivatization of gas target during LVCC sampling process were efficiently merged in one step using bromine-thiourea and OPA-NH 4 + strategy for ethylene and SO 2 respectively, which made LVCC sampling technique conveniently adapted to consequent SERS analysis. Finally, a new LVCC sampling-SERS method was developed and successfully applied for rapid analysis of trace ethylene and SO 2 from fruits. It was satisfied that trace ethylene and SO 2 from real fruit samples could be actually and accurately quantified by this method. The minor concentration fluctuations of ethylene and SO 2 during the entire LVCC sampling process were proved to be gas targets from real samples by SERS. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Comparative analysis of the aroma chemicals of Melissa officinalis using hydrodistillation and HS-SPME techniques

    Directory of Open Access Journals (Sweden)

    Shakeel-u- Rehman

    2017-05-01

    Full Text Available Headspace solid-phase micro extraction (HS-SPME coupled with gas chromatography–mass spectrometry (GC–MS has been used for the chemical analysis of Melissa officinalis (leaves cultivated in Institute Germplasm. The HS-SPME analysis led to the identification of 22 components constituting 99.1% of the total volatile constituents present in the leaves whereas its hydrodistillate led to the identification of 24 volatile constituents constituting 98.1% of the volatile material. The chemical composition of the SPME and hydrodistilled extract of M. officinalis leaves comprised mainly of oxygenated monoterpenes (78.5% and 57.8% respectively and sesquiterpene hydrocarbons (14.9% and 29.7% respectively. The major components identified in the HS-SPME extract were citronellal (31.1%, citronellol (18.3%, β-caryophyllene (12.0%, (E-citral (11.9%, (Z-citral (9.6%, geraniol (3.6%, (Z-β-ocimene (3.1% and 1-octen-3-ol (2.0% whereas hydrodistilled essential oil was rich in (Z-citral (19.6%, β-caryophyllene (13.2%, (E-citral (11.2%, citronellal (10.2%, germacrene-d (8.3%, δ-3-carene (5.0%, 6-methyl-5-hepten-2-one (3.7% and citronellyl acetate (3.7%. The comparative analysis of volatile constituents of M. officinalis leaf extract using HS-SPME and hydrodistillation techniques shows both qualitative as well as quantitative differences. The current study is the first report involving rapid analysis of volatile components of M. officinalis by HS-SPME.

  20. New insight on biological interaction analysis: new nanocrystalline mixed metal oxide SPME fiber for GC-FID analysis of BTEX and its application in human hemoglobin-benzene interaction studies.

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    Reza Hosseinzadeh

    Full Text Available Nanocrystalline mixed metal oxides (MMO of various metal cations were synthesized and were used for coating a piece of copper wire as a new high sensitive solid phase micro extraction (SPME fiber in extraction and determination of BTEX compounds from the headspace of aqueous samples prior to GC-FID analysis. Under optimum extraction conditions, the proposed fiber exhibited low detection limits, and quantification limits, good reproducibility, simple and fast preparation method, high fiber capacity and high thermal and mechanical durability. These are some of the most important advantages of the new fiber. The proposed fiber was used for human hemoglobin upon interaction with benzene. Binding isotherm, Scatchard and Klotz logarithmic plots were constructed using HS-SPME-GC data, accurately. The obtained binding isotherm analyzed using Hill method. The Hill parameters have been obtained by calculating saturation parameter from the ratio of measured chromatographic peak areas in the presence and absence of hemoglobin. In this interaction, Hill coefficient and Hill constant determined as (nH = 6.14 and log KH = 6.47 respectively. These results reveal the cooperativity of hemoglobin upon interaction with benzene.