Identification and measurement of chlorinated organic pesticides in water by electron-capture gas chromatography

USGS Publications Warehouse

Lamar, William L.; Goerlitz, Donald F.; Law, LeRoy M.

1965-01-01

Pesticides, in minute quantities, may affect the regimen of streams, and because they may concentrate in sediments, aquatic organisms, and edible aquatic foods, their detection and their measurement in the parts-per-trillion range are considered essential. In 1964 the U.S. Geological Survey at Menlo Park, Calif., began research on methods for monitoring pesticides in water. Two systems were selected--electron-capture gas chromatography and microcoulometric-titration gas chromatography. Studies on these systems are now in progress. This report provides current information on the development and application of an electron-capture gas chromatographic procedure. This method is a convenient and extremely sensitive procedure for the detection and measurement of organic pesticides having high electron affinities, notably the chlorinated organic pesticides. The electron-affinity detector is extremely sensitive to these substances but it is not as sensitive to many other compounds. By this method, the chlorinated organic pesticide may be determined on a sample of convenient size in concentrations as low as the parts-per-trillion range. To insure greater accuracy in the identifications, the pesticides reported were separated and identified by their retention times on two different types of gas chromatographic columns.

Identification of chemical warfare agents from vapor samples using a field-portable capillary gas chromatography/membrane-interfaced electron ionization quadrupole mass spectrometry instrument with Tri-Bed concentrator.

PubMed

Nagashima, Hisayuki; Kondo, Tomohide; Nagoya, Tomoki; Ikeda, Toru; Kurimata, Naoko; Unoke, Shohei; Seto, Yasuo

2015-08-07

A field-portable gas chromatograph-mass spectrometer (Hapsite ER system) was evaluated for the detection of chemical warfare agents (CWAs) in the vapor phase. The system consisted of Tri-Bed concentrator gas sampler (trapping time: 3s(-1)min), a nonpolar low thermal-mass capillary gas chromatography column capable of raising temperatures up to 200°C, a hydrophobic membrane-interfaced electron ionization quadrupole mass spectrometer evacuated by a non-evaporative getter pump for data acquisition, and a personal computer for data analysis. Sample vapors containing as little as 22μg sarin (GB), 100μg soman (GD), 210μg tabun (GA), 55μg cyclohexylsarin (GF), 4.8μg sulfur mustard, 390μg nitrogen mustard 1, 140μg of nitrogen mustard 2, 130μg nitrogen mustard 3, 120μg of 2-chloroacetophenone and 990μg of chloropicrin per cubic meter could be confirmed after Tri-Bed micro-concentration (for 1min) and automated AMDIS search within 12min. Using manual deconvolution by background subtraction of neighboring regions on the extracted ion chromatograms, the above-mentioned CWAs could be confirmed at lower concentration levels. The memory effects were also examined and we found that blister agents showed significantly more carry-over than nerve agents. Gasoline vapor was found to interfere with the detection of GB and GD, raising the concentration limits for confirmation in the presence of gasoline by both AMDIS search and manual deconvolution; however, GA and GF were not subject to interference by gasoline. Lewisite 1, and o-chlorobenzylidene malononitrile could also be confirmed by gas chromatography, but it was hard to quantify them. Vapors of phosgene, chlorine, and cyanogen chloride could be confirmed by direct mass spectrometric detection at concentration levels higher than 2, 140, and 10mg/m(3) respectively, by bypassing the micro-concentration trap and gas chromatographic separation. Copyright © 2015 Elsevier B.V. All rights reserved.

Advanced liquid chromatography-mass spectrometry interface based on electron ionization.

PubMed

Cappiello, A; Famiglini, G; Pierini, E; Palma, P; Trufelli, H

2007-07-15

Major progress in interfacing liquid chromatography and electron ionization mass spectrometry is presented. The minimalism of the first prototype, called the Direct-EI interface, has been widely refined, improved, and applied to modern instrumentation. The simple interfacing principle is based on the straight connection between a nanoHPLC system and a mass spectrometer equipped with an EI source forming a solid and reliable unicum resembling the immediacy and straightforwardness of GC/MS. The interface shows a superior performance in the analysis of small-medium molecular weight compounds, especially when compared to its predecessors, and a unique trait that excels particularly in the following aspects: (1) It delivers high-quality, fully library matchable mass spectra of most sub-1 kDa molecules amenable by HPLC. (2) It is a chemical ionization free interface (unless operated intentionally) with accurate reproduction of the expected isotope ion abundances. (3) Response is never influenced by matrix components in the sample or in the mobile phase (nonvolatile salts are also well accepted). A deep evaluation of these aspects is presented and discussed in detail. Other characteristics of the interface performance such as limits of detections, range of linear response, and intra- and interday signal stability were also considered. The usefulness of the interface has been tested in a few real-world applications where matrix components played a detrimental role with other LC/MS techniques.

Qualitative analysis of seized synthetic cannabinoids and synthetic cathinones by gas chromatography triple quadrupole tandem mass spectrometry.

PubMed

Gwak, Seongshin; Arroyo-Mora, Luis E; Almirall, José R

2015-02-01

Designer drugs are analogues or derivatives of illicit drugs with a modification of their chemical structure in order to circumvent current legislation for controlled substances. Designer drugs of abuse have increased dramatically in popularity all over the world for the past couple of years. Currently, the qualitative seized-drug analysis is mainly performed by gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) in which most of these emerging designer drug derivatives are extensively fragmented not presenting a molecular ion in their mass spectra. The absence of molecular ion and/or similar fragmentation pattern among these derivatives may cause the equivocal identification of unknown seized-substances. In this study, the qualitative identification of 34 designer drugs, mainly synthetic cannabinoids and synthetic cathinones, were performed by gas chromatography-triple quadrupole-tandem mass spectrometry with two different ionization techniques, including electron ionization (EI) and chemical ionization (CI) only focusing on qualitative seized-drug analysis, not from the toxicological point of view. The implementation of CI source facilitates the determination of molecular mass and the identification of seized designer drugs. Developed multiple reaction monitoring (MRM) mode may increase sensitivity and selectivity in the analysis of seized designer drugs. In addition, CI mass spectra and MRM mass spectra of these designer drug derivatives can be used as a potential supplemental database along with EI mass spectral database. Copyright © 2014 John Wiley & Sons, Ltd.

A simple and sensitive quantitation of N,N-dimethyltryptamine by gas chromatography with surface ionization detection.

PubMed

Ishii, A; Seno, H; Suzuki, O; Hattori, H; Kumazawa, T

1997-01-01

A simple and sensitive method for determination of N,N-dimethyltryptamine (DMT) by gas chromatography (GC) with surface ionization detection (SID) is presented. Whole blood or urine, containing DMT and gramine (internal standard), was subjected to solid-phase extraction with a Sep-Pak C18 cartridge before analysis by GC-SID. The calibration curve was linear in the DMT range of 1.25-20 ng/mL blood or urine. The detection limit of DMT was about 0.5 ng/mL (10 pg on-column). The recovery of both DMT and gramine spiked in biological fluids was above 86%.

Analysis of acylcarnitines as their N-demethylated ester derivatives by gas chromatography-chemical ionization mass spectrometry.

PubMed

Huang, Z H; Gage, D A; Bieber, L L; Sweeley, C C

1991-11-15

A novel approach to the analysis of acylcarnitines has been developed. It involves a direct esterification using propyl chloroformate in aqueous propanol followed by ion-pair extraction with potassium iodide into chloroform and subsequent on-column N-demethylation of the resulting acylcarnitine propyl ester iodides. The products, acyl N-demethylcarnitine propyl esters, are volatile and are easily analyzed by gas chromatography-chemical ionization mass spectrometry. For medium-chain-length (C4-C12) acylcarnitine standards, detection limits are demonstrated to be well below 1 ng starting material using selected ion monitoring. Well-separated gas chromatographic peaks and structure-specific mass spectra are obtained with samples of synthetic and biological origin. Seven acylcarnitines have been characterized in the urine of a patient suffering from medium-chain acyl-CoA dehydrogenase deficiency.

Determination of photoionization cross-sections of different organic molecules using gas chromatography coupled to single-photon ionization (SPI) time-of-flight mass spectrometry (TOF-MS) with an electron-beam-pumped rare gas excimer light source (EBEL): influence of molecular structure and analytical implications.

PubMed

Eschner, Markus S; Zimmermann, Ralf

2011-07-01

This work describes a fast and reliable method for determination of photoionization cross-sections (PICS) by means of gas chromatography (GC) coupled to single-photon ionization mass spectrometry (SPI-MS). Photoionization efficiency (PIE) data for 69 substances was obtained at a photon energy of 9.8 ± 0.4 eV using an innovative electron-beam-pumped rare gas excimer light source (EBEL) filled with argon. The investigated analytes comprise 12 alkylbenzenes as well as 11 other substituted benzenes, 23 n-alkanes, ten polyaromatic hydrocarbons, seven aromatic heterocycles, and six polyaromatic heterocycles. Absolute PICS for each substance at 9.8 eV are calculated from the relative photoionization efficiencies of the compounds with respect to benzene, whose photoionization cross-section data is well known. Furthermore, a direct correlation between the type of benzene substituents and their absolute PICS is presented and discussed in depth. Finally, comparison of previously measured photoionization cross-sections for 20 substances shows good agreement with the data of the present work.

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

USGS Publications Warehouse

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

1967-01-01

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

Determination of clebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry.

PubMed

Robinson, P R; Jones, M D; Maddock, J

1988-11-18

A procedure for the analysis of clebopride in plasma using capillary gas chromatography-negative-ion chemical ionization mass spectrometry has been developed. Employing an ethoxy analogue as internal standard, the two compounds were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyryl imidazole produced volatile monoheptafluorobutyryl derivatives whose ammonia negative-ion mass spectra proved ideal for selected-ion monitoring. The recovery of clebopride from plasma at 0.536 nmol/l was found to be 85.5 +/- 0.9% (n = 3) whilst measurement down to 0.268 nmol/l was possible with a coefficient of variation of 7.9%. Plasma levels of the compound are reported in two volunteers following ingestion of 1 mg of clebopride as the malate salt.

Determination of Pesticides by Gas Chromatography Combined with Mass Spectrometry Using Femtosecond Lasers Emitting at 267, 400, and 800 nm as the Ionization Source.

PubMed

Yang, Xixiang; Imasaka, Tomoko; Imasaka, Totaro

2018-04-03

A standard sample mixture containing 51 pesticides was separated by gas chromatography (GC), and the constituents were identified by mass spectrometry (MS) using femtosecond lasers emitting at 267, 400, and 800 nm as the ionization source. A two-dimensional display of the GC/MS was successfully used for the determination of these compounds. A molecular ion was observed for 38 of the compounds at 267 nm and for 30 of the compounds at 800 nm, in contrast to 27 among 50 compounds when electron ionization was used. These results suggest that the ultraviolet laser is superior to the near-infrared laser for molecular weight determinations and for a more reliable analysis of these compounds. In order to study the conditions for optimal ionization, the experimental data were examined using the spectral properties (i.e., the excitation and ionization energies and absorption spectra for the neutral and ionized species) obtained by quantum chemical calculations. A few molecules remained unexplained by the currently reported rules, requiring additional rules for developing a full understanding of the femtosecond ionization process. The pesticides in the homogenized matrix obtained from kabosu ( citrus sphaerocarpa) were measured using lasers emitting at 267 and 800 nm. The pesticides were clearly separated and measured on the two-dimensional display, especially for the data measured at 267 nm, suggesting that this technique would have potential for use in the practical trace analysis of the pesticides in the environment.

A sensitive gas chromatography detector based on atmospheric pressure chemical ionization by a dielectric barrier discharge.

PubMed

Kirk, Ansgar T; Last, Torben; Zimmermann, Stefan

2017-02-03

In this work, we present a novel concept for a gas chromatography detector utilizing an atmospheric pressure chemical ionization which is initialized by a dielectric barrier discharge. In general, such a detector can be simple and low-cost, while achieving extremely good limits of detection. However, it is non-selective apart from the use of chemical dopants. Here, a demonstrator manufactured entirely from fused silica capillaries and printed circuit boards is shown. It has a size of 75×60×25mm 3 and utilizes only 2W of power in total. Unlike other known discharge detectors, which require high-purity helium, this detector can theoretically be operated using any gas able to form stable ion species. Here, purified air is used. With this setup, limits of detection in the low parts-per-billion range have been obtained for acetone. Copyright © 2017 Elsevier B.V. All rights reserved.

Shock-wave structure in a partially ionized gas

NASA Technical Reports Server (NTRS)

Lu, C. S.; Huang, A. B.

1974-01-01

The structure of a steady plane shock in a partially ionized gas has been investigated using the Boltzmann equation with a kinetic model as the governing equation and the discrete ordinate method as a tool. The effects of the electric field induced by the charge separation on the shock structure have also been studied. Although the three species of an ionized gas travel with approximately the same macroscopic velocity, the individual distribution functions are found to be very different. In a strong shock the atom distribution function may have double peaks, while the ion distribution function has only one peak. Electrons are heated up much earlier than ions and atoms in a partially ionized gas. Because the interactions of electrons with atoms and with ions are different, the ion temperature can be different from the atom temperature.

Multiplexed electronically programmable multimode ionization detector for chromatography

DOEpatents

Wise, M.B.; Buchanan, M.V.

1988-05-19

Method and apparatus for detecting and differentiating organic compounds based on their electron affinity. An electron capture detector cell (ECD) is operated in a plurality of multiplexed electronically programmable operating modes to alter the detector response during a single sampling cycle to acquire multiple simultaneous chromatograms corresponding to each of the different operating modes. The cell is held at a constant subatmospheric pressure while the electron collection bias voltage applied to the cell is modulated electronically to allow acquisition of multiple chromatograms for a single sample elution from a chromatograph representing three distinctly different response modes. A system is provided which automatically controls the programmed application of bias pulses at different intervals and/or amplitudes to switch the detector from an ionization mode to the electron capture mode and various degrees therebetween to provide an improved means of tuning an ECD for multimode detection and improved specificity. 6 figs.

Analysis of waterborne paints by gas chromatography-mass spectrometry with a temperature-programmable pyrolyzer.

PubMed

Nakamura, S; Takino, M; Daishima, S

2001-04-06

Gas chromatography-mass spectrometry (GC-MS) with a temperature-programmable pyrolyzer was used for the analysis of waterborne paints. Evolved gas analysis (EGA) profiles of the waterborne paints were obtained by this temperature-programmed pyrolysis directly coupled with MS via a deactivated metal capillary tube. The EGA profile suggested the optimal thermal desorption conditions for solvents and additives and the subsequent optimal pyrolysis temperature for the remaining polymeric material. Polymers were identified from pyrograms with the assistance of a new polymer library. The solvents were identified from the electron ionization mass spectra with the corresponding chemical ionization mass spectra. The additive was identified as zinc pyrithione by comparison with authentic standard. Zinc pyrithione cannot be analyzed by GC-MS as it is. However, the thermal decomposition products of zinc pyrithione could be detected. The information on the decomposition temperature and products was useful for the identification of the original compound.

Comparison of different mass spectrometric approaches coupled to gas chromatography for the analysis of organochlorine pesticides in serum samples.

PubMed

Fang, Jing; Wu, Qian; Zhao, Yun; Zhao, Hongzhi; Xu, Shunqing; Cai, Zongwei

2017-01-01

Gas chromatography-triple quadrupole mass spectrometry (GC-QqQMS) was applied for the determination of eight organochlorine pesticides (OCPs) in human serum. OCPs were extracted from the serum sample by solid phase extraction (SPE) and analyzed by gas chromatography mass spectrometry (GC-MS) or gas chromatography tandem mass spectrometry (GC-MS/MS). Electron ionization (EI) and negative chemical ionization (NCI) under two data acquisition modes, namely selected ion monitoring (SIM) and multiple reaction monitoring (MRM), were compared. The use of MRM generally provided higher selectivity and sensitivity because less interference from the sample matrix existed. The EI mode is more suitable for less electronegative compounds such as dichlorodiphenyldichloroethanes (DDDs) with detection limits ranging from 0.0060 to 0.060ng/mL. In the NCI mode, MRM analysis provided good and lower detection limits (0.0011-0.0030ng/mL) for pesticides containing more chlorines. The methods were validated by analyzing the pesticides in spiked serum at different levels with recoveries ranged from 83% to 116% and relative standard deviations of less than 10%. The developed method was applied for the determination of the OCPs in real human serum samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Multiplexed electronically programmable multimode ionization detector for chromatography

DOEpatents

Wise, Marcus B.; Buchanan, Michelle V.

1989-01-01

Method and apparatus for detecting and differentiating organic compounds based on their electron affinity. An electron capture detector cell (ECD) is operated in a plurality of multiplexed electroncially programmable operating modes to alter the detector response during a single sampling cycle to acquire multiple simultaneous chromatograms corresponding to each of the different operating modes. The cell is held at a constant subatmospheric pressure while the electron collection bias voltage applied to the cell is modulated electronically to allow acquisition of multiple chromatograms for a single sample elution from a chromatograph representing three distinctly different response modes. A system is provided which automatically controls the programmed application of bias pulses at different intervals and/or amplitudes to switch the detector from an ionization mode to the electron capture mode and various degrees therebetween to provide an improved means of tuning an ECD for multimode detection and improved specificity.

Gas Chromatography.

ERIC Educational Resources Information Center

Karasek, Francis W.; And Others

1984-01-01

This review covers fundamental developments in gas chromatography during 1982 and 1983. Literature is considered under these headings: columns; liguid phases; solid supports; sorption processes and solvents; open tubular column gas chromatography; instrumentation; high-resolution columns and applications; other techniques; qualitative and…

A Laboratory Experiment To Measure Henry's Law Constants of Volatile Organic Compounds with a Bubble Column and a Gas Chromatography Flame Ionization Detector (GC-FID)

ERIC Educational Resources Information Center

Lee, Shan-Hu; Mukherjee, Souptik; Brewer, Brittany; Ryan, Raphael; Yu, Huan; Gangoda, Mahinda

2013-01-01

An undergraduate laboratory experiment is described to measure Henry's law constants of organic compounds using a bubble column and gas chromatography flame ionization detector (GC-FID). This experiment is designed for upper-division undergraduate laboratory courses and can be implemented in conjunction with physical chemistry, analytical…

Lipids and Fatty Acids in Algae: Extraction, Fractionation into Lipid Classes, and Analysis by Gas Chromatography Coupled with Flame Ionization Detector (GC-FID).

PubMed

Guihéneuf, Freddy; Schmid, Matthias; Stengel, Dagmar B

2015-01-01

Despite the number of biochemical studies exploring algal lipids and fatty acid biosynthesis pathways and profiles, analytical methods used by phycologists for this purpose are often diverse and incompletely described. Potential confusion and potential variability of the results between studies can therefore occur due to change of protocols for lipid extraction and fractionation, as well as fatty acid methyl esters (FAME) preparation before gas chromatography (GC) analyses. Here, we describe a step-by-step procedure for the profiling of neutral and polar lipids using techniques such as solid-liquid extraction (SLE), thin-layer chromatography (TLC), and gas chromatography coupled with flame ionization detector (GC-FID). As an example, in this protocol chapter, analyses of neutral and polar lipids from the marine microalga Pavlova lutheri (an EPA/DHA-rich haptophyte) will be outlined to describe the distribution of fatty acid residues within its major lipid classes. This method has been proven to be a reliable technique to assess changes in lipid and fatty acid profiles in several other microalgal species and seaweeds.

Design for gas chromatography-corona discharge-ion mobility spectrometry.

PubMed

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

2012-11-20

A corona discharge ionization-ion mobility spectrometry (CD-IMS) with a novel sample inlet system was designed and constructed as a detector for capillary gas chromatography. In this design, a hollow needle was used instead of a solid needle which is commonly used for corona discharge creation, helping us to have direct axial interfacing for GC-IMS. The capillary column was passed through the needle, resulting in a reaction of effluents with reactant ions on the upstream side of the corona discharge ionization source. Using this sample introduction design, higher ionization efficiency was achieved relative to the entrance direction through the side of the drift tube. In addition, the volume of the ionization region was reduced to minimize the resistance time of compounds in the ionization source, increasing chromatographic resolution of the instrument. The effects of various parameters such as drift gas flow, makeup gas flow, and column tip position inside the needle were investigated. The designed instrument was exhaustively validated in terms of sensitivity, resolution, and reproducibility by analyzing the standard solutions of methyl isobutyl ketone, heptanone, nonanone, and acetophenone as the test compounds. The results obtained by CD-IMS detector were compared with those of the flame ionization detector, which revealed the capability of the proposed GC-IMS for two-dimensional separation (based on the retention time and drift time information) and identification of an analyte in complex matrixes.

Increasing Polyaromatic Hydrocarbon (PAH) Molecular Coverage during Fossil Oil Analysis by Combining Gas Chromatography and Atmospheric-Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS)

PubMed Central

Benigni, Paolo; DeBord, J. Daniel; Thompson, Christopher J.; Gardinali, Piero; Fernandez-Lima, Francisco

2016-01-01

Thousands of chemically distinct compounds are encountered in fossil oil samples that require rapid screening and accurate identification. In the present paper, we show for the first time, the advantages of gas chromatography (GC) separation in combination with atmospheric-pressure laser ionization (APLI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the screening of polyaromatic hydrocarbons (PAHs) in fossil oils. In particular, reference standards of organics in shale oil, petroleum crude oil, and heavy sweet crude oil were characterized by GC-APLI-FT-ICR MS and APLI-FT-ICR MS. Results showed that, while APLI increases the ionization efficiency of PAHs, when compared to other ionization sources, the complexity of the fossil oils reduces the probability of ionizing lower-concentration compounds during direct infusion. When gas chromatography precedes APLI-FT-ICR MS, an increase (more than 2-fold) in the ionization efficiency and an increase in the signal-to-noise ratio of lower-concentration fractions are observed, giving better molecular coverage in the m/z 100–450 range. That is, the use of GC prior to APLI-FT-ICR MS resulted in higher molecular coverage, higher sensitivity, and the ability to separate and characterize molecular isomers, while maintaining the ultrahigh resolution and mass accuracy of the FT-ICR MS separation. PMID:27212790

Penning Ionization Electron Spectroscopy in Glow Discharge: A New Dimension for Gas Chromatography Detectors

NASA Technical Reports Server (NTRS)

Sheverev, V. A.; Khromov, N. A.; Kojiro, D. R.; Fonda, Mark (Technical Monitor)

2002-01-01

Admixtures to helium of 100 ppm and 5 ppm of nitrogen, and 100 ppm and 10 ppm of carbon monoxide were identified and measured in the helium discharge afterglow using an electrical probe placed into the plasma. For nitrogen and carbon monoxide gases, the measured electron energy spectra display distinct characteristic peaks (fingerprints). Location of the peaks on the energy scale is determined by the ionization energies of the analyte molecules. Nitrogen and carbon monoxide fingerprints were also observed in a binary mixture of these gases in helium, and the relative concentration analytes has been predicted. The technically simple and durable method is considered a good candidate for a number of analytical applications, and in particular, in GC and for analytical flight instrumentation.

Gas chromatography-electron ionization-mass spectrometry quantitation of valproic acid and gabapentin, using dried plasma spots, for therapeutic drug monitoring in in-home medical care.

PubMed

Ikeda, Kayo; Ikawa, Kazuro; Yokoshige, Satoko; Yoshikawa, Satoshi; Morikawa, Norifumi

2014-12-01

A simple and sensitive gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) method using dried plasma spot testing cards was developed for determination of valproic acid and gabapentin concentrations in human plasma from patients receiving in-home medical care. We have proposed that a simple, easy and dry sampling method is suitable for in-home medical patients for therapeutic drug monitoring. Therefore, in the present study, we used recently developed commercially available easy handling cards: Whatman FTA DMPK-A and Bond Elut DMS. In-home medical care patients can collect plasma using these simple kits. The spots of plasma on the cards were extracted into methanol and then evaporated to dryness. The residues were trimethylsilylated using N-methyl-N-trimethylsilyltrifluoroacetamide. For GC-EI-MS analysis, the calibration curves on both cards were linear from 10 to 200 µg/mL for valproic acid, and from 0.5 to 10 µg/mL for gabapentin. Intra- and interday precisions in plasma were both ≤13.0% (coefficient of variation), and the accuracy was between 87.9 and 112% for both cards within the calibration curves. The limits of quantification were 10 µg/mL for valproic acid and 0.5 µg/mL for gabapentin on both cards. We believe that the present method will be useful for in-home medical care. Copyright © 2014 John Wiley & Sons, Ltd.

Investigation of ionization-induced electron injection in a wakefield driven by laser inside a gas cell

DOE PAGES

Audet, T. L.; Hansson, M.; Lee, P.; ...

2016-02-16

Ionization-induced electron injection was investigated experimentally by focusing a driving laser pulse with a maximum normalized potential of 1.2 at different positions along the plasma density profile inside a gas cell, filled with a gas mixture composed of 99%H 2+1%N 2. Changing the laser focus position relative to the gas cell entrance controls the accelerated electron bunch properties, such as the spectrum width, maximum energy, and accelerated charge. Simulations performed using the 3D particle-in-cell code WARP with a realistic density profile give results that are in good agreement with the experimental ones. Lastly, we discuss the interest of this regimemore » for optimizing the bunch charge in a selected energy window.« less

Fragmentation pathways and structural characterization of organophosphorus compounds related to the Chemical Weapons Convention by electron ionization and electrospray ionization tandem mass spectrometry.

PubMed

Hosseini, Seyed Esmaeil; Saeidian, Hamid; Amozadeh, Ali; Naseri, Mohammad Taghi; Babri, Mehran

2016-12-30

For unambiguous identification of Chemical Weapons Convention (CWC)-related chemicals in environmental samples, the availability of mass spectra, interpretation skills and rapid microsynthesis of suspected chemicals are essential requirements. For the first time, the electron ionization single quadrupole and electrospray ionization tandem mass spectra of a series of O-alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates (Scheme 1, cpd 4) were studied for CWC verification purposes. O-Alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates were prepared through a microsynthetic method and were analyzed using electron ionization and electrospray ionization mass spectrometry with gas and liquid chromatography, respectively, as MS-inlet systems. General EI and ESI fragmentation pathways were proposed and discussed, and collision-induced dissociation studies of the protonated derivatives of these compounds were performed to confirm proposed fragment ion structures by analyzing mass spectra of deuterated analogs. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as McLafferty rearrangement, hydrogen rearrangement and a previously unknown intramolecular electrophilic aromatic substitution reaction. The EI and ESI fragmentation routes of the synthesized compounds 4 were investigated with the aim of detecting and identifying CWC-related chemicals during on-site inspection and/or off-site analysis and toxic chemical destruction monitoring. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Identification of Abscisic Acid in Tulipa gesneriana L. by Gas-Liquid Chromatography with Electron Capture and Combined Gas-Liquid Chromatography and Mass Spectrometry

PubMed Central

Terry, Paul H.; Aung, Louis H.; De Hertogh, August A.

1982-01-01

A major growth inhibitory substance of tulip bulbs (Tulipa gesneriana L. cv Paul Richter) has been unequivocally shown to be abscisic acid (ABA). The ABA methyl ester of the free ether-soluble acid fractions of tulip organs had the identical retention time on gas-liquid chromatography with electron capture detector as authentic ABA methyl ester. In addition, the mass spectra were the same. On a unit dry matter basis, the basalplate and floral shoot contained 3.6 and 2.6 times more ABA than the fleshy scales, respectively. PMID:16662721

Intercomparison of infrared cavity leak-out spectroscopy and gas chromatography-flame ionization for trace analysis of ethane.

PubMed

Thelen, Sven; Miekisch, Wolfram; Halmer, Daniel; Schubert, Jochen; Hering, Peter; Mürtz, Manfred

2008-04-15

Comparison of two different methods for the measurement of ethane at the parts-per-billion (ppb) level is reported. We used cavity leak-out spectroscopy (CALOS) in the 3 microm wavelength region and gas chromatography-flame ionization detection (GC-FID) for the analysis of various gas samples containing ethane fractions in synthetic air. Intraday and interday reproducibilities were studied. Intercomparing the results of two series involving seven samples with ethane mixing ratios ranging from 0.5 to 100 ppb, we found a reasonable agreement between both methods. The scatter plot of GC-FID data versus CALOS data yields a linear regression slope of 1.07 +/- 0.03. Furthermore, some of the ethane mixtures were checked over the course of 1 year, which proved the long-term stability of the ethane mixing ratio. We conclude that CALOS shows equivalent ethane analysis precision compared to GC-FID, with the significant advantage of a much higher time resolution (<1 s) since there is no requirement for sample preconcentration. This opens new analytical possibilities, e.g., for real-time monitoring of ethane traces in exhaled human breath.

Capillary atmospheric pressure electron capture ionization (cAPECI): a highly efficient ionization method for nitroaromatic compounds.

PubMed

Derpmann, Valerie; Mueller, David; Bejan, Iustinian; Sonderfeld, Hannah; Wilberscheid, Sonja; Koppmann, Ralf; Brockmann, Klaus J; Benter, Thorsten

2014-03-01

We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2(-) or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2(-) leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.

Herschel Galactic plane survey of ionized gas traced by [NII

NASA Astrophysics Data System (ADS)

Yildiz, Umut; Goldsmith, Paul; Pineda, Jorge; Langer, William

2015-01-01

Far infrared and sub-/millimeter atomic & ionic fine structure and molecular rotational lines are powerful tracers of star formation on both Galactic and extragalactic scales. Although CO lines trace cool to moderately warm molecular gas, ionized carbon [CII] produces the strongest lines, which arise from almost all reasonably warm (T>50 K) parts of the ISM. However, [CII] alone cannot distinguish highly ionized gas from weakly ionized gas. [NII] plays a significant role in star formation as it is produced only in ionized regions; in [HII] regions as well as diffuse ionized gas. The ionization potential of nitrogen (14.5 eV) is greater than that of hydrogen (13.6 eV), therefore the ionized nitrogen [NII] lines reflect the effects of massive stars, with possible enhancement from X-ray and shock heating from the surroundings. Two far-infrared 122 um and 205 um [NII] fine structure spectral lines are targeted via Photodetector Array Camera and Spectrometer (PACS) onboard Herschel Space Observatory. The sample consists of 149 line-of-sight (LOS) positions in the Galactic plane. These positions overlap with the [CII] 158 um observations obtained with the GOT C+ survey. With a reasonable assumption that the emission from both 122 um and 205 um lines originate in the same gas; [NII] 122/205 um line ratio indicates the a good measure of the electron density of each of the LOS positions. [NII] detections are mainly toward the Galactic center direction and the [NII] electron densities are found between 7-50 cm^-3, which is enhanced WIM (Warm Ionized Medium). WIM densities are expected to be much lower (~1 cm-3), therefore non-detections toward the opposite side of the Galactic Center shows abundant of this gas. The pixel to pixel variation of the emission within a single Herschel pointing is relatively small, which is interpreted as the [NII] emission comes from an extended gas. It is important to quantify what fraction of [CII] emission arises in the ionized gas. Thus, with

Determination of selected fatty acids in dried sweat spot using gas chromatography with flame ionization detection.

PubMed

Kanďár, Roman; Drábková, Petra; Andrlová, Lenka; Kostelník, Adam; Čegan, Alexander

2016-11-01

A method is described for the determination of fatty acids in dried sweat spot and plasma samples using gas chromatography with flame ionization detection. Plasma and dried sweat spot samples were obtained from a group of blood donors. The sweat was collected from each volunteer during exercise. Sweat was spotted onto collection paper containing butylated hydroxytoluene. Fatty acids were derivatized with acetyl chloride in methanol to form methyl esters of fatty acids. The fatty acids in dried sweat spot samples treated with butylated hydroxytoluene and stored at -20°C were stable for 3 months. Our results indicate that sweat contains, among fatty acids with short chain, also fatty acids with long chain and unsaturated fatty acids. Linear relationships between percentage content of selected fatty acids in dried sweat spot and plasma were observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of bacterial fatty acids by flow modulated comprehensive two-dimensional gas chromatography with parallel flame ionization detector/mass spectrometry.

PubMed

Gu, Qun; David, Frank; Lynen, Frédéric; Rumpel, Klaus; Xu, Guowang; De Vos, Paul; Sandra, Pat

2010-06-25

Comprehensive two-dimensional gas chromatography (GCxGC) offers an interesting tool for profiling bacterial fatty acids. Flow modulated GCxGC using a commercially available system was evaluated, different parameters such as column flows and modulation time were optimized. The method was tested on bacterial fatty acid methyl esters (BAMEs) from Stenotrophomonas maltophilia LMG 958T by using parallel flame ionization detector (FID)/mass spectrometry (MS). The results are compared to data obtained using a thermal modulated GCxGC system. The data show that flow modulated GCxGC-FID/MS method can be applied in a routine environment and offers interesting perspectives for chemotaxonomy of bacteria.

Ionized gas at the edge of the central molecular zone

NASA Astrophysics Data System (ADS)

Langer, W. D.; Goldsmith, P. F.; Pineda, J. L.; Velusamy, T.; Requena-Torres, M. A.; Wiesemeyer, H.

2015-04-01

Context. The edge of the central molecular zone (CMZ) is the location where massive dense molecular clouds with large internal velocity dispersions transition to the surrounding more quiescent and lower CO emissivity region of the Galaxy. Little is known about the ionized gas surrounding the molecular clouds and in the transition region. Aims: We determine the properties of the ionized gas at the edge of the CMZ near Sgr E using observations of N+ and C+. Methods: We observed a small portion of the edge of the CMZ near Sgr E with spectrally resolved [C ii] 158 μm and [N ii] 205 μm fine structure lines at six positions with the GREAT instrument on SOFIA and in [C ii] using Herschel HIFI on-the-fly strip maps. We use the [N ii] spectra along with a radiative transfer model to calculate the electron density of the gas and the [C ii] maps to illuminate the morphology of the ionized gas and model the column density of CO-dark H2. Results: We detect two [C ii] and [N ii] velocity components, one along the line of sight to a CO molecular cloud at - 207 km s-1 associated with Sgr E and the other at -174 km s-1 outside the edge of another CO cloud. From the [N ii] emission we find that the average electron density is in the range of ~5 to 21 cm-3 for these features. This electron density is much higher than that of the disk's warm ionized medium, but is consistent with densities determined for bright diffuse H ii nebula. The column density of the CO-dark H2 layer in the -207 km s-1 cloud is ~1-2 × 1021 cm-2 in agreement with theoretical models. The CMZ extends further out in Galactic radius by ~7 to 14 pc in ionized gas than it does in molecular gas traced by CO. Conclusions: The edge of the CMZ likely contains dense hot ionized gas surrounding the neutral molecular material. The high fractional abundance of N+ and high electron density require an intense EUV field with a photon flux of order 106 to 107 photons cm-2 s-1, and/or efficient proton charge exchange with

Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal

PubMed Central

Zuber, Jan; Kroll, Marius M.; Rathsack, Philipp; Otto, Matthias

2016-01-01

Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. PMID:27066076

Both gas chromatography and an electronic nose reflect chemical polymorphism of juniper shrubs browsed or avoided by sheep.

PubMed

Markó, Gábor; Novák, Ildikó; Bernáth, Jeno; Altbäcker, Vilmos

2011-07-01

Chemical polymorphism may contribute to variation in browsing damage by mammalian herbivores. Earlier, we demonstrated that essential oil concentration in juniper, Juniperus communis, was negatively associated with herbivore browsing. The aim of the present study was to characterize the volatile chemical composition of browsed and non-browsed J. communis. By using either gas chromatography with flame ionization detection (GC-FID) or an electronic nose device, we could separate sheep-browsed or non-browsed juniper shrubs by their essential oil pattern and complex odor matrix. The main components of the essential oil from J. communis were monoterpenes. We distinguished three chemotypes, dominated either by α-pinene, sabinene, or δ-3-carene. Shrubs belonging to the α-pinene- or sabinene-dominated groups were browsed, whereas all individuals with the δ-3-carene chemotype were unused by the local herbivores. The electronic nose also separated the browsed and non-browsed shrubs indicating that their odor matrix could guide sheep browsing. Responses of sheep could integrate the post-ingestive effects of plant secondary metabolites with sensory experience that stems from odor-phytotoxin interactions. Chemotype diversity could increase the survival rate in the present population of J. communis as certain shrubs could benefit from relatively better chemical protection against the herbivores.

The absorption of energetic electrons by molecular hydrogen gas

NASA Technical Reports Server (NTRS)

Cravens, T. E.; Victor, G. A.; Dalgarno, A.

1975-01-01

The processes by which energetic electrons lose energy in a weakly ionized gas of molecular hydrogen are analyzed, and calculations are carried out taking into account the discrete nature of the excitation processes. The excitation, ionization, and heating efficiencies are computed for electrons with energies up to 100 eV absorbed in a gas with fractional ionizations up to 0.01, and the mean energy per pair of neutral hydrogen atoms is calculated.

Development of a gas chromatography method for the determination of isotretinoin and its degradation products in pharmaceuticals.

PubMed

Lima, Eliana Martins; Diniz, Danielle G Almeida; Antoniosi-Filho, Nelson R

2005-07-15

This paper describes the development of a gas chromatography (GC) method used for the assay of isotretinoin in its isolated form and in pharmaceutical formulations. Isotretinoin soft and hard gelatin capsules were prepared with various excipients. The performance of the proposed gas chromatography method was compared to that of traditional high performance liquid chromatography (HPLC) systems for this substance, and the GC parameters were established based on several preliminary tests, including thermal analysis of isotretinoin. Results showed that gas chromatography-flame ionization detector (GC-FID) exhibited a separation efficiency superior to that of HPLC, particularly for separating isotretinoin degradation products. This method was proven to be effectively applicable to stability evaluation assays of isotretinoin and isotretinoin based pharmaceuticals.

Rapid determination of the isomeric truxillines in illicit cocaine via capillary gas chromatography/flame ionization detection and their use and implication in the determination of cocaine origin and trafficking routes.

PubMed

Mallette, Jennifer R; Casale, John F

2014-10-17

The isomeric truxillines are a group of minor alkaloids present in all illicit cocaine samples. The relative amount of truxillines in cocaine is indicative of the variety of coca used for cocaine processing, and thus, is useful in source determination. Previously, the determination of isomeric truxillines in cocaine was performed with a gas chromatography/electron capture detection method. However, due to the tedious sample preparation as well as the expense and maintenance required of electron capture detectors, the protocol was converted to a gas chromatography/flame-ionization detection method. Ten truxilline isomers (alpha-, beta-, delta-, epsilon-, gamma-, omega, zeta-, peri-, neo-, and epi-) were quantified relative to a structurally related internal standard, 4',4″-dimethyl-α-truxillic acid dimethyl ester. The method was shown to have a linear response from 0.001 to 1.00 mg/mL and a lower detection limit of 0.001 mg/mL. In this method, the truxillines are directly reduced with lithium aluminum hydride and then acylated with heptafluorobutyric anhydride prior to analysis. The analysis of more than 100 cocaine hydrochloride samples is presented and compared to data obtained by the previous methodology. Authentic cocaine samples obtained from the source countries of Colombia, Bolivia, and Peru were also analyzed, and comparative data on more than 23,000 samples analyzed over the past 10 years with the previous methodology is presented. Published by Elsevier B.V.

Characterization of low-molecular weight iodine-terminated polyethylenes by gas chromatography/mass spectrometry and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with the use of derivatization.

PubMed

Zaikin, Vladimir G; Borisov, Roman S; Polovkov, Nikolai Yu; Zhilyaev, Dmitry I; Vinogradov, Aleksei A; Ivanyuk, Aleksei V

2013-01-01

Gas chromatography/mass spectrometry (GC/MS) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry, in conjunction with various derivatization approaches, have been applied to structure determination of individual oligomers and molecular-mass distributions (MMD) in low-molecular mass polyethylene having an iodine terminus. Direct GC/MS analysis has shown that the samples under investigation composed of polyethyelene-iodides (major components) and n-alkanes. Exchange reaction with methanol in the presence of NaOH gave rise to methoxy-derivatives and n-alkenes. Electron ionization mass spectra have shown that the former contained terminal methoxy groups indicating the terminal position of the iodine atom in the initial oligomers. MMD parameters have been determined with the aid of MALDI mass spectrometry followed by preliminary derivatization-formation of covalently bonded charge through the reaction of iodides with triphenylphosphine, trialkylamines, pyridine or quinoline. The mass spectra revealed well-resolved peaks for cationic parts of derivatized oligomers allowing the determination of MMD. The latter values have been compared with those calculated from GC/MS data.

Electron energy deposition in N2 gas

NASA Technical Reports Server (NTRS)

Fox, J. L.; Victor, G. A.

1988-01-01

The processes by which energetic electrons lose energy in a weakly ionized gas of molecular nitrogen are analyzed and calculations are carried out taking into account the discrete nature of the excitation processes. The excitation, ionization, dissociation and heating efficiencies are computed for energies up to 200 eV absorbed in a gas with fractional ionizations varying from 10(-6) to 10(-2). Individual vibrational excitations up to the seventh vibrational level are presented.

SFC-APLI-(TOF)MS: Hyphenation of Supercritical Fluid Chromatography to Atmospheric Pressure Laser Ionization Mass Spectrometry.

PubMed

Klink, Dennis; Schmitz, Oliver Johannes

2016-01-05

Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons.

Internal standards for use in the comprehensive analysis of polychlorinated aromatic hydrocarbons using gas chromatography combined with multiphoton ionization mass spectrometry.

PubMed

Li, Adan; Imasaka, Totaro

2016-10-28

To decrease health-risks to humans, non-toxic compounds were evaluated for use as internal standards for calibrating data obtained by gas chromatography/multiphoton ionization mass spectrometry (GC-MPI-MS) using an ultraviolet femtosecond laser as the ionization source. The retention time in the mass chromatogram was calibrated using a retention index, in which a series of n-alkanes was employed as internal standards for evaluating the retention times for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs). To compensate for changes in signal intensity in MPI-MS, the dependence of signal intensity on the laser pulse energy was investigated for the dioxin-like compounds, in addition to five non-toxic aromatic hydrocarbons, that were used as internal standards. Based on their similar behavior,the non-toxic PCDD/PCDF, its 13 C-isotope, and pentachlorobenzene behave similarly, we conclude that they can be used for calibrating the signal intensities in MPI-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

Analysis of 62 synthetic cannabinoids by gas chromatography-mass spectrometry with photoionization.

PubMed

Akutsu, Mamoru; Sugie, Ken-Ichi; Saito, Koichi

2017-01-01

Gas chromatography-mass spectrometry (GC-MS) in electron ionization (EI) mode is one of the most commonly used techniques for analysis of synthetic cannabinoids, because the GC-EI-MS spectra contain characteristic fragment ions for identification of a compound; however, the information on its molecular ions is frequently lacking. To obtain such molecular ion information, GC-MS in chemical ionization (CI) mode is frequently used. However, GC-CI-MS requires a relatively tedious process using reagent gas such as methane or isobutane. In this study, we show that GC-MS in photoionization (PI) mode provided molecular ions in all spectra of 62 synthetic cannabinoids, and 35 of the 62 compounds showed only the molecular radical cations. Except for the 35 compounds, the PI spectra showed very simple patterns with the molecular peak plus only a few fragment peak(s). An advantage is that the ion source for GC-PI-MS can easily be used for GC-EI-MS as well. Therefore, GC-EI/PI-MS will be a useful tool for the identification of synthetic cannabinoids contained in a dubious product. To the best of our knowledge, this is the first report to use GC-PI-MS for analysis of synthetic cannabinoids.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of chlorinated pesticides in aquatic tissue by capillary-column gas chromatography with electron-capture detection

USGS Publications Warehouse

Leiker, Thomas J.; Madsen, J.E.; Deacon, J.R.; Foreman, W.T.

1995-01-01

A method for the determination of chlorinated organic compounds in aquatic tissue by dual capillary-column gas chromatography with electron-capture detection is described. Whole-body-fish or corbicula tissue is homogenized, Soxhlet extracted, lipid removed by gel permeation chromatography, and fractionated using alumina/silica adsorption chromatography. The extracts are analyzed by dissimilar capillary-column gas chromatography with electron-capture detection. The method reporting limits are 5 micrograms per kilogram (μg/kg) for chlorinated compounds, 50 μg/kg for polychlorinated biphenyls, and 200 μg/kg for toxaphene.

Evaluation of a novel helium ionization detector within the context of (low-)flow modulation comprehensive two-dimensional gas chromatography.

PubMed

Franchina, Flavio A; Maimone, Mariarosa; Sciarrone, Danilo; Purcaro, Giorgia; Tranchida, Peter Q; Mondello, Luigi

2015-07-10

The present research is focused on the use and evaluation of a novel helium ionization detector, defined as barrier discharge ionization detector (BID), within the context of (low-)flow modulation comprehensive two-dimensional gas chromatography (FM GC×GC). The performance of the BID device was compared to that of a flame ionization detector (FID), under similar FM GC×GC conditions. Following development and optimization of the FM GC×GC method, the BID was subjected to fine tuning in relation to acquisition frequency and discharge flow. Moreover, the BID performance was measured and compared to that of the FID, in terms of extra-column band broadening, sensitivity and dynamic range. The comparative study was carried out by using standard compounds belonging to different chemical classes, along with a sample of diesel fuel. Advantages and disadvantages of the BID system, also within the context of FM GC×GC, are critically discussed. In general, the BID system was characterized by a more limited dynamic range and increased sensitivity, compared to the FID. Additionally, BID and FID contribution to band broadening was found to be similar under the operational conditions applied. Particular attention was devoted to the behaviour of the FM GC×GC-BID system toward saturated and aromatic hydrocarbons, for a possible future use in the field of mineral-oil food contamination research. Copyright © 2015 Elsevier B.V. All rights reserved.

Analysis of human plasma lipids by using comprehensive two-dimensional gas chromatography with dual detection and with the support of high-resolution time-of-flight mass spectrometry for structural elucidation.

PubMed

Salivo, Simona; Beccaria, Marco; Sullini, Giuseppe; Tranchida, Peter Q; Dugo, Paola; Mondello, Luigi

2015-01-01

The main focus of the present research is the analysis of the unsaponifiable lipid fraction of human plasma by using data derived from comprehensive two-dimensional gas chromatography with dual quadrupole mass spectrometry and flame ionization detection. This approach enabled us to attain both mass spectral information and analyte percentage data. Furthermore, gas chromatography coupled with high-resolution time-of-flight mass spectrometry was used to increase the reliability of identification of several unsaponifiable lipid constituents. The synergism between both the high-resolution gas chromatography and mass spectrometry processes enabled us to attain a more in-depth knowledge of the unsaponifiable fraction of human plasma. Additionally, information was attained on the fatty acid and triacylglycerol composition of the plasma samples, subjected to investigation by using comprehensive two-dimensional gas chromatography with dual quadrupole mass spectrometry and flame ionization detection and high-performance liquid chromatography with atmospheric pressure chemical ionization quadrupole mass spectrometry, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comprehensive two-dimensional gas chromatography with flame ionization and time-of-flight mass spectrometry detection: qualitative and quantitative analysis of West Australian sandalwood oil.

PubMed

Shellie, Robert; Marriott, Philip; Morrison, Paul

2004-09-01

The use of gas chromatography (GC)-mass spectrometry (MS), GC-time-of-flight MS (TOFMS), comprehensive two-dimensional GC (GCxGC)-flame ionization detection (FID), and GCxGC-TOFMS is discussed for the characterization of the eight important representative components, including Z-alpha-santalol, epi-alpha-bisabolol, Z-alpha-trans-bergamotol, epi-beta-santalol, Z-beta-santalol, E,E-farnesol, Z-nuciferol, and Z-lanceol, in the oil of west Australian sandalwood (Santalum spicatum). Single-column GC-MS lacks the resolving power to separate all of the listed components as pure peaks and allow precise analytical measurement of individual component abundances. With enhanced peak resolution capabilities in GCxGC, these components are sufficiently well resolved to be quantitated using flame ionization detection, following initial characterization of components by using GCxGC-TOFMS.

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): review.

PubMed

Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J

2015-09-03

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a "soft" ion source for preserving highly diagnostic molecular ion is desirable, as compared to the "hard" ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. Copyright © 2015. Published by Elsevier B.V.

Establishment of analysis method for methane detection by gas chromatography

NASA Astrophysics Data System (ADS)

Liu, Xinyuan; Yang, Jie; Ye, Tianyi; Han, Zeyu

2018-02-01

The study focused on the establishment of analysis method for methane determination by gas chromatography. Methane was detected by hydrogen flame ionization detector, and the quantitative relationship was determined by working curve of y=2041.2x+2187 with correlation coefficient of 0.9979. The relative standard deviation of 2.60-6.33% and the recovery rate of 96.36%∼105.89% were obtained during the parallel determination of standard gas. This method was not quite suitable for biogas content analysis because methane content in biogas would be over the measurement range in this method.

Highly sensitive and selective analysis of urinary steroids by comprehensive two-dimensional gas chromatography combined with positive chemical ionization quadrupole mass spectrometry

PubMed Central

Zhang, Ying; Tobias, Herbert J.; Brenna, J. Thomas

2014-01-01

Comprehensive two dimensional gas chromatography (GC×GC) provides greater separation space than conventional GC. Because of fast peak elution, a time of flight mass spectrometer (TOFMS) is the usual structure-specific detector of choice. The quantitative capabilities of a novel GC×GC fast quadrupole MS were investigated with electron ionization (EI), and CH4 or NH3 positive chemical ionization (PCI) for analysis of endogenous urinary steroids targeted in anti-doping tests. Average precisions for steroid quantitative analysis from replicate urine extractions were 6% (RSD) for EI and 8% for PCI-NH3. The average limits of detection (LOD) calculated by quantification ions for 12 target steroids spiked into steroid-free urine matrix (SFUM) were 2.6 ng mL−1 for EI, 1.3 ng mL−1 for PCI-CH4, and 0.3 ng mL−1 for PCI-NH3, all in mass scanning mode. The measured limits of quantification (LOQ) with full mass scan GC×GC-qMS were comparable with the LOQ values measured by one-dimensional GC-MS in single ion monitoring (SIM) mode. PCI-NH3 yields fewer fragments and greater (pseudo)molecular ion abundances than EI or PCI-CH4. These data show a benchtop GC×GC-qMS system has the sensitivity, specificity, and resolution to analyze urinary steroids at normal urine concentrations, and that PCI-NH3, not currently available on most GC×GC-TOFMS instruments, is of particular value for generation of structure-specific ions. PMID:22606686

Role of plasma electrons in the generation of a gas discharge plasma

NASA Astrophysics Data System (ADS)

Gruzdev, V. A.; Zalesski, V. G.; Rusetski, I. S.

2012-12-01

The role of different ionization mechanisms in penning-type gas discharges used to generate an emitting plasma in plasma electron sources is considered. It is shown that, under certain conditions, a substantial contribution to the process of gas ionization is provided by plasma electrons.

Reversal electron attachment ionizer for detection of trace species

NASA Technical Reports Server (NTRS)

Bernius, Mark T. (Inventor); Chutjian, Ara (Inventor)

1990-01-01

An in-line reversal electron, high-current ionizer capable of focusing a beam of electrons to a reversal region and executing a reversal of said electrons, such that the electrons possess zero kinetic energy at the point of reversal, may be used to produce both negative and positive ions. A sample gas is introduced at the point of electron reversal for low energy electron-(sample gas) molecule attachment with high efficiency. The attachment process produces negative ions from the sample gas, which includes species present in trace (minute) amounts. These ions are extracted efficiently and directed to a mass analyzer where they may be detected and identified. The generation and detection of positive ions is accomplished in a similar fashion with minimal adjustment to potentials applied to the apparatus.

Reversal electron attachment ionizer for detection of trace species

NASA Technical Reports Server (NTRS)

Bernius, Mark T. (Inventor); Chutjian, Ara (Inventor)

1989-01-01

An in-line reversal electron, high-current ionizer capable of focusing a beam of electrons to a reversal region and executing a reversal of the electrons, such that the electrons possess zero kinetic energy at the point of reversal, may be used to produce both negative and positive ions. A sample gas is introduced at the point of electron reversal for low energy electron-(sample gas) molecule attachment with high efficiency. The attachment process produces negative ions from the sample gas, which includes species present in trace (minute) amounts. These ions are extracted efficiently and directed to a mass analyzer where they may be detected and identified. The generation and detection of positive ions is accomplished in a similar fashion with minimal adjustment to potentials applied to the apparatus.

Gas chromatography/mass spectrometry comprehensive analysis of organophosphorus, brominated flame retardants, by-products and formulation intermediates in water.

PubMed

Cristale, Joyce; Quintana, Jordi; Chaler, Roser; Ventura, Francesc; Lacorte, Silvia

2012-06-08

A multiresidue method based on gas chromatography coupled to quadrupole mass spectrometry was developed to determine organophosphorus flame retardants, polybromodiphenyl ethers (BDEs 28, 47, 99, 100, 153, 154, 183 and 209), new brominated flame retardants, bromophenols, bromoanilines, bromotoluenes and bromoanisoles in water. Two ionization techniques (electron ionization--EI, and electron capture negative ionization--ECNI) and two acquisition modes (selected ion monitoring--SIM, and selected reaction monitoring--SRM) were compared as regards to mass spectral characterization, sensitivity and quantification capabilities. The highest sensitivity, at expenses of identification capacity, was obtained by GC-ECNI-MS/SIM for most of the compounds analyzed, mainly for PBDEs and decabromodiphenyl ethane while GC-EI-MS/MS in SRM was the most selective technique and permitted the identification of target compounds at the pg level, and identification capabilities increased when real samples were analyzed. This method was further used to evaluate the presence and behavior of flame retardants within a drinking water treatment facility. Organophosphorus flame retardants were the only compounds detected in influent waters at levels of 0.32-0.03 μg L⁻¹, and their elimination throughout the different treatment stages was evaluated. Copyright © 2012 Elsevier B.V. All rights reserved.

Use of a microwave diagnostics technique to measure the temperature of an axisymmetric ionized gas flow

NASA Astrophysics Data System (ADS)

Tsel'Sov, Iu. G.; Kondrat'ev, A. S.

1990-12-01

A method is developed for determining the temperature of an ionized gas on the basis of electron-density sounding. This technique is used to measure the cross-sectional temperature distribution of an axisymmetric ionized gas flow using microwave diagnostics.

Identification of volatiles from pineapple (Ananas comosus L.) pulp by comprehensive two-dimensional gas chromatography and gas chromatography/mass spectrometry.

PubMed

Pedroso, Marcio P; Ferreira, Ernesto C; Hantao, Leandro W; Bogusz, Stanislau; Augusto, Fabio

2011-07-01

Combining qualitative data from the chromatographic structure of 2-D gas chromatography with flame ionization detection (GC×GC-FID) and that from gas chromatography-mass spectrometry (GC/MS) should result in a more accurate assignment of the peak identities than the simple analysis by GC/MS, where coelution of analytes is unavoidable in highly complex samples (rendering spectra unsuitable for qualitative purposes) or for compounds in very low concentrations. Using data from GC×GC-FID combined with GC/MS can reveal coelutions that were not detected by mass spectra deconvolution software. In addition, some compounds can be identified according to the structure of the GC×GC-FID chromatogram. In this article, the volatile fractions of fresh and dehydrated pineapple pulp were evaluated. The extraction of the volatiles was performed by dynamic headspace extraction coupled to solid-phase microextraction (DHS-SPME), a technique appropriate for slurries or solid matrices. Extracted analytes were then analyzed by GC×GC-FID and GC/MS. The results obtained using both techniques were combined to improve compound identifications. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seasonal variation of gastroprotective terpenoids in Maytenus robusta (Celastraceae) quantified by gas chromatography-flame ionization detection (GC-FID).

PubMed

Zermiani, Tailyn; Junior, Antonio A S; Ferreira, Renê A; Wagner, Theodoro M; Machado, Marina S; Cechinel-Filho, Valdir; Niero, Rivaldo

2016-11-01

The triterpenes friedelin (1), β-friedelinol (2) and 3,15-dioxo-21α-hydroxyfriedelane (3) in the aerial parts of Maytenus robusta, a Brazilian medicinal plant with antiulcer potential, were seasonally quantified by gas chromatography flame-ionization detection (GC-FID) using an external standard. The method was found to be linear, precise and sensitive. Compounds 1 and 2 were found in M. robusta leaves and branches, with highest concentrations in the leaves collected in autumn, i.e. 3.21 ± 0.16 and 12.60 ± 1.49 mg g-1 dry weight of 1 and 2, respectively. On the other hand, compound 3 was found only in the branches, with the highest concentrations in winter and autumn (0.21 ± 0.01 and 0.20 ± 0.02 mg g-1). The results allow to define the optimal season and plant parts for the collection of M. robusta as a phytotherapeutic drug.

Observation of increased space-charge limited thermionic electron emission current by neutral gas ionization in a weakly-ionized deuterium plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hollmann, E. M.; Yu, J. H.; Doerner, R. P.

2015-09-14

The thermionic electron emission current emitted from a laser-produced hot spot on a tungsten target in weakly-ionized deuterium plasma is measured. It is found to be one to two orders of magnitude larger than expected for bipolar space charge limited thermionic emission current assuming an unperturbed background plasma. This difference is attributed to the plasma being modified by ionization of background neutrals by the emitted electrons. This result indicates that the allowable level of emitted thermionic electron current can be significantly enhanced in weakly-ionized plasmas due to the presence of large neutral densities.

Injection and trapping of tunnel-ionized electrons into laser-produced wakes.

PubMed

Pak, A; Marsh, K A; Martins, S F; Lu, W; Mori, W B; Joshi, C

2010-01-15

A method, which utilizes the large difference in ionization potentials between successive ionization states of trace atoms, for injecting electrons into a laser-driven wakefield is presented. Here a mixture of helium and trace amounts of nitrogen gas was used. Electrons from the K shell of nitrogen were tunnel ionized near the peak of the laser pulse and were injected into and trapped by the wake created by electrons from majority helium atoms and the L shell of nitrogen. The spectrum of the accelerated electrons, the threshold intensity at which trapping occurs, the forward transmitted laser spectrum, and the beam divergence are all consistent with this injection process. The experimental measurements are supported by theory and 3D OSIRIS simulations.

Gas Chromatography.

ERIC Educational Resources Information Center

Cram, Stuart P.; And Others

1980-01-01

Selects fundamental developments in theory, methodology, and instrumentation in gas chromatography (GC). A special section reviews GC in the People's Republic of China. Over 1,000 references are cited. (CS)

Qualitative and quantitative analysis of pyrolysis oil by gas chromatography with flame ionization detection and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

PubMed

Sfetsas, Themistoklis; Michailof, Chrysa; Lappas, Angelos; Li, Qiangyi; Kneale, Brian

2011-05-27

Pyrolysis oils have attracted a lot of interest, as they are liquid energy carriers and general sources of chemicals. In this work, gas chromatography with flame ionization detector (GC-FID) and two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) techniques were used to provide both qualitative and quantitative results of the analysis of three different pyrolysis oils. The chromatographic methods and parameters were optimized and solvent choice and separation restrictions are discussed. Pyrolysis oil samples were diluted in suitable organic solvent and were analyzed by GC×GC-TOFMS. An average of 300 compounds were detected and identified in all three samples using the ChromaToF (Leco) software. The deconvoluted spectra were compared with the NIST software library for correct matching. Group type classification was performed by use of the ChromaToF software. The quantification of 11 selected compounds was performed by means of a multiple-point external calibration curve. Afterwards, the pyrolysis oils were extracted with water, and the aqueous phase was analyzed both by GC-FID and, after proper change of solvent, by GC×GC-TOFMS. As previously, the selected compounds were quantified by both techniques, by means of multiple point external calibration curves. The parameters of the calibration curves were calculated by weighted linear regression analysis. The limit of detection, limit of quantitation and linearity range for each standard compound with each method are presented. The potency of GC×GC-TOFMS for an efficient mapping of the pyrolysis oil is undisputable, and the possibility of using it for quantification as well has been demonstrated. On the other hand, the GC-FID analysis provides reliable results that allow for a rapid screening of the pyrolysis oil. To the best of our knowledge, very few papers have been reported with quantification attempts on pyrolysis oil samples using GC×GC-TOFMS most of which make use of the

Determination of nitrosourea compounds in brain tissue by gas chromatography and electron capture detection.

PubMed

Hassenbusch, S J; Colvin, O M; Anderson, J H

1995-07-01

A relatively simple, high-sensitivity gas chromatographic assay is described for nitrosourea compounds, such as BCNU [1,3-bis(2-chloroethyl)-1-nitrosourea] and MeCCNU [1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea], in small biopsy samples of brain and other tissues. After extraction with ethyl acetate, secondary amines in BCNU and MeCCNU are derivatized with trifluoroacetic anhydride. Compounds are separated and quantitated by gas chromatography using a capillary column with temperature programming and an electron capture detector. Standard curves of BCNU indicate a coefficient of variance of 0.066 +/- 0.018, a correlation coefficient of 0.929, and an extraction efficiency from whole brain of 68% with a minimum detectable amount of 20 ng in 5-10 mg samples. The assay has been facile and sensitive in over 1000 brain biopsy specimens after intravenous and intraarterial infusions of BCNU.

Headspace gas chromatography with flame ionization detection (HS-GC-FID) for the determination of dissolved methane in wastewater.

PubMed

Beale, D J; Tjandraatmadja, G; Toifl, M; Goodman, N

2014-01-01

There is currently a need for a simple, accurate and reproducible method that quantifies the amount of dissolved methane in wastewater in order to realize the potential methane that can be recovered and account for any emissions. This paper presents such a method, using gas chromatography with flame ionization detection fitted with a GS-Gas PRO column coupled with a headspace auto sampler. A practical limit of detection for methane of 0.9 mg L(-1), with a retention time of 1.24 min, was obtained. It was found that the reproducibility and accuracy of the method increased significantly when samples were collected using an in-house constructed bailer sampling device and with the addition of 100 μL hydrochloric acid (HCl) and 25% sodium chloride (NaCl) and sonication for 30 min prior to analysis. Analysis of wastewater samples and wastewater sludge collected from a treatment facility were observed to range from 12.51 to 15.79 mg L(-1) (relative standard deviation (RSD) 8.1%) and 17.56 to 18.67 mg L(-1) (RSD 3.4%) respectively. The performance of this method was validated by repeatedly measuring a mid-level standard (n=8; 10 mg L(-1)), with an observed RSD of 4.6%.

High-quality electron beams from beam-driven plasma accelerators by wakefield-induced ionization injection.

PubMed

Martinez de la Ossa, A; Grebenyuk, J; Mehrling, T; Schaper, L; Osterhoff, J

2013-12-13

We propose a new and simple strategy for controlled ionization-induced trapping of electrons in a beam-driven plasma accelerator. The presented method directly exploits electric wakefields to ionize electrons from a dopant gas and capture them into a well-defined volume of the accelerating and focusing wake phase, leading to high-quality witness bunches. This injection principle is explained by example of three-dimensional particle-in-cell calculations using the code OSIRIS. In these simulations a high-current-density electron-beam driver excites plasma waves in the blowout regime inside a fully ionized hydrogen plasma of density 5×10(17)cm-3. Within an embedded 100  μm long plasma column contaminated with neutral helium gas, the wakefields trigger ionization, trapping of a defined fraction of the released electrons, and subsequent acceleration. The hereby generated electron beam features a 1.5 kA peak current, 1.5  μm transverse normalized emittance, an uncorrelated energy spread of 0.3% on a GeV-energy scale, and few femtosecond bunch length.

Simultaneous determination of organophosphorus pesticides in fruits and vegetables using atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry.

PubMed

Cheng, Zhipeng; Dong, Fengshou; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Pan, Xinglu; Gan, Jay; Zheng, Yongquan

2017-09-15

This paper describes the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for the simultaneous determination of organophosphorus pesticides in apple, pear, tomato, cucumber and cabbage. Soft ionization with atmospheric pressure ionization source was compared with traditional electron impact ionization (EI). The sensitivity of GC coupled to atmospheric pressure ionization (APGC) for all the analytes was enhanced by 1.0-8.2 times. The ionization modes with atmospheric pressure ionization source was studied by comparing the charge-transfer and proton-transfer conditions. The optimized QuEChERs method was used to pretreat the samples. The calibration curves were found linear from 10 to 1000μg/L, obtaining correlation coefficients higher than 0.9845. Satisfactory mean recovery values, in the range of 70.0-115.9%, and satisfactory precision, with all RSD r <19.7% and all RSD R values <19.5% at the three fortified concentration levels for all the fifteen OPPs. The results demonstrate the potential of APGC-QTOF-MS for routine quantitative analysis of organophosphorus pesticide in fruits and vegetables. Copyright © 2017 Elsevier Ltd. All rights reserved.

Online Simultaneous Hydrogen/Deuterium Exchange of Multitarget Gas-Phase Molecules by Electrospray Ionization Mass Spectrometry Coupled with Gas Chromatography.

PubMed

Jeong, Eun Sook; Cha, Eunju; Cha, Sangwon; Kim, Sunghwan; Oh, Han Bin; Kwon, Oh-Seung; Lee, Jaeick

2017-11-21

In this study, a hydrogen/deuterium (H/D) exchange method using gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) was first investigated as a novel tool for online H/D exchange of multitarget analytes. The GC and ESI source were combined with a homemade heated column transfer line. GC-ESI/MS-based H/D exchange occurs in an atmospheric pressure ion source as a result of reacting the gas-phase analyte eluted from GC with charged droplets of deuterium oxide infused as the ESI spray solvent. The consumption of the deuterated solvent at a flow rate of 2 μL min -1 was more economical than that in online H/D exchange methods reported to date. In-ESI-source H/D exchange by GC-ESI/MS was applied to 11 stimulants with secondary amino or hydroxyl groups. After H/D exchange, the spectra of the stimulants showed unexchanged, partially exchanged, and fully exchanged ions showing various degrees of exchange. The relative abundances corrected for naturally occurring isotopes of the fully exchanged ions of stimulants, except for etamivan, were in the range 24.3-85.5%. Methylephedrine and cyclazodone showed low H/D exchange efficiency under acidic, neutral, and basic spray solvent conditions and nonexchange for etamivan with an acidic phenolic OH group. The in-ESI-source H/D exchange efficiency by GC-ESI/MS was sufficient to determine the number of hydrogen by elucidation of fragmentation from the spectrum. Therefore, this online H/D exchange technique using GC-ESI/MS has potential as an alternative method for simultaneous H/D exchange of multitarget analytes.

Electron- and positron-impact ionization of inert gases

NASA Astrophysics Data System (ADS)

Campeanu, R. I.; Walters, H. R. J.; Whelan, Colm T.

2018-06-01

Triple-differential cross sections (TDCS) are presented for the electron and positron impact ionization of inert gas atoms in a range of geometries where a number of significant few body effects compete to define the shape of the TDCS. Using both positrons and electrons as projectiles has opened up the possibility of performing complementary studies which could effectively isolate competing interactions which cannot be separately detected in an experiment with a single projectile. A comparison is presented between theory and the recent experiments of [Gavin, deLucio, and DuBois, Phys. Rev. A 95, 062703 (2017), 10.1103/PhysRevA.95.062703] for e± and contrasted with the results from earlier electron experiments. For the special case of xenon(5 p ), cross sections are presented for both electron- and positron-impact ionization in kinematics where the electron case appears well understood. The kinematics are then varied in order to focus on the possible role of distortion, exchange, and target wave-function effects.

Electron ionization and dissociation of aliphatic amino acids

NASA Astrophysics Data System (ADS)

Papp, P.; Shchukin, P.; Kočíšek, J.; Matejčík, Š.

2012-09-01

We present experimental and theoretical study of electron ionization and dissociative ionization to the gas phase amino acids valine, leucine, and isoleucine. A crossed electron/molecular beams technique equipped with quadrupole mass analyzer has been applied to measure mass spectra and ion efficiency curves for formation of particular ions. From experimental data the ionization energies of the molecules and the appearance energies of the fragment ions were determined. Ab initio calculations (Density Functional Theory and G3MP2 methods) were performed in order to calculate the fragmentation paths and interpret the experimental data. The experimental ionization energies of parent molecules [P]+ 8.91 ± 0.05, 8.85 ± 0.05, and 8.79 ± 0.05 eV and G3MP2 ionization energies (adiabatic) of 8.89, 8.88, and 8.81 eV were determined for valine, leucine, and isoleucine, respectively, as well as the experimental and theoretical threshold energies for dissociative ionization channels. The comparison of experimental data with calculations resulted in identification of the ions as well as the neutral fragments formed in the dissociative reactions. Around 15 mass/charge ratio fragments were identified from the mass spectra by comparison of experimental appearance energies with calculated reaction enthalpies for particular dissociative reactions.

Analysis of aldehydes in beer by gas-diffusion microextraction: characterization by high-performance liquid chromatography-diode-array detection-atmospheric pressure chemical ionization-mass spectrometry.

PubMed

Gonçalves, Luís Moreira; Magalhães, Paulo Jorge; Valente, Inês Maria; Pacheco, João Grosso; Dostálek, Pavel; Sýkora, David; Rodrigues, José António; Barros, Aquiles Araújo

2010-06-11

In this work, a recently developed extraction technique for sample preparation aiming the analysis of volatile and semi-volatile compounds named gas-diffusion microextraction (GDME) is applied in the chromatographic analysis of aldehydes in beer. Aldehydes-namely acetaldehyde (AA), methylpropanal (MA) and furfural (FA)-were simultaneously extracted and derivatized with 2,4-dinitrophenylhydrazine (DNPH), then the derivatives were separated and analyzed by high-performance liquid chromatography with spectrophotometric detection (HPLC-UV). The identity of the eluted compounds was confirmed by high-performance liquid chromatography-atmospheric pressure chemical ionization-mass-spectrometry detection in the negative ion mode (HPLC-APCI-MS). The developed methodology showed good repeatability (ca. 5%) and linearity as well as good limits of detection (AA-12.3, FA-1.5 and MA 5.4microgL(-1)) and quantification (AA-41, FA-4.9 and MA 18microgL(-1)); it also appears to be competitive in terms of speed and cost of analysis. Copyright 2010 Elsevier B.V. All rights reserved.

Gas chromatography in space

NASA Technical Reports Server (NTRS)

Akapo, S. O.; Dimandja, J. M.; Kojiro, D. R.; Valentin, J. R.; Carle, G. C.

1999-01-01

Gas chromatography has proven to be a very useful analytical technique for in situ analysis of extraterrestrial environments as demonstrated by its successful operation on spacecraft missions to Mars and Venus. The technique is also one of the six scientific instruments aboard the Huygens probe to explore Titan's atmosphere and surface. A review of gas chromatography in previous space missions and some recent developments in the current environment of fiscal constraints and payload size limitations are presented.

Quantification of short- and medium-chain chlorinated paraffins in environmental samples by gas chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Gao, Wei; Wu, Jing; Wang, Yawei; Jiang, Guibin

2016-06-24

Chlorinated paraffins (CPs) are technical products produced and used in bulk for a number of purposes. However, the analysis of CPs is challenging, as they are complex mixtures of compounds and isomers. We herein report the development of an analytical method for the analysis of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) using quadrupole time-of-flight high-resolution mass spectrometry (GC-NCI-qTOF-HRMS). This method employs gas chromatography with a chemical ionization source working in negative mode. The linear relationship between chlorination and the CP total response factors was applied to quantify the CP content and the congener group distribution patterns. In a single injection, 24 SCCP formula groups and 24 MCCP formula groups were quantified. Extraction of accurate masses using qTOF-HRMS allowed the SCCPs and MCCPs to be distinguished, with interference from other chemicals (e.g., PCBs) being largely avoided. The SCCP and MCCP detection limits were 24-81ng/mL and 27-170ng/mL, respectively. Comparison of the obtained results with analytical results from gas chromatography coupled with electron capture negative ionization low-resolution mass spectrometry (GC-ECNI-LRMS) indicate that the developed technique is a more accurate and convenient method for the analysis of CPs in samples from a range of matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

Ionization Injection of Electrons into a Plasma Wakefield Accelerator at FACET

NASA Astrophysics Data System (ADS)

Clayton, Chris; E-200 At Facet Collaboration

2013-10-01

In the PWFA experiments at FACET, a low ionization-potential (IP) metal vapor gas (Li) is confined within a heat-pipe oven by a higher IP buffer gas (typically He). The Li is easily field-ionized by the FACET beam. A non-linear wake is formed in the blowout regime when the 20.3 GeV bunch containing 2e10 electrons in a σz ~ 30 μm is focused to a (vacuum) σr < 25 near the ~ 10cm-long boundary region. There the Li density rises from zero up to the oven's 30cm-long flat-topped density of 2.5e17 cm-3. To obtain a mono-energetic beam from accelerated ionization-injected electrons at the far end of the oven--the goal of this experiment--it is necessary for the FACET beam to have a betatron pinch just where the flat-topped region begins; i.e., where the wake wavelength is no longer changing. If the buffer gas contains a mixture of He and a moderate IP gas, the ``impurity'' gases will also be field ionized and potentially contribute more charge to the injected bunch than with He alone. Moderate IP gases were added to the He buffer gas: 10%, 20%, and 50% Ar (balance He) and 30% Ne (balance He) have been used. Evidence for ionization injection and acceleration appears through the observation of distinct features, characterized by their very narrow size and thus angular spread, at the image plane of a magnetic imaging spectrometer. Analysis aimed at characterizing these features with respect to energy, charge, and angular spread is underway and will be presented. This work was supported by the DOE and the NSF.

[Development of methods for determining acrylamide in food products by gas-liquid chromatography].

PubMed

Bessonov, V V; Malinkin, A D; Perederiaev, O I; Bogachuk, M N; Volkovich, S V; Medvedev, Iu V

2011-01-01

The method of determination of acrylamide in various food (milk powder, potato chips, instant coffee) by gas-liquid chromatography after pre-bromination was developed. Studies have shown the possibility of using bromination of acrylamide to give it the necessary properties for better extraction, purification and detection. Also revealed the possibility of qualitative and quantitative determine a acrylamide in food by gas-liquid chromatography with detection by electron capture detector.

Unified first principles description from warm dense matter to ideal ionized gas plasma: electron-ion collisions induced friction.

PubMed

Dai, Jiayu; Hou, Yong; Yuan, Jianmin

2010-06-18

Electron-ion interactions are central to numerous phenomena in the warm dense matter (WDM) regime and at higher temperature. The electron-ion collisions induced friction at high temperature is introduced in the procedure of ab initio molecular dynamics using the Langevin equation based on density functional theory. In this framework, as a test for Fe and H up to 1000 eV, the equation of state and the transition of electronic structures of the materials with very wide density and temperature can be described, which covers a full range of WDM up to high energy density physics. A unified first principles description from condensed matter to ideal ionized gas plasma is constructed.

Gas Chromatography-Tandem Mass Spectrometry of Lignin Pyrolyzates with Dopant-Assisted Atmospheric Pressure Chemical Ionization and Molecular Structure Search with CSI:FingerID

NASA Astrophysics Data System (ADS)

Larson, Evan A.; Hutchinson, Carolyn P.; Lee, Young Jin

2018-06-01

Dopant-assisted atmospheric pressure chemical ionization (dAPCI) is a soft ionization method rarely used for gas chromatography-mass spectrometry (GC-MS). The current study combines GC-dAPCI with tandem mass spectrometry (MS/MS) for analysis of a complex mixture such as lignin pyrolysis analysis. To identify the structures of volatile lignin pyrolysis products, collision-induced dissociation (CID) MS/MS using a quadrupole time-of-flight mass spectrometer (QTOFMS) and pseudo MS/MS through in-source collision-induced dissociation (ISCID) using a single stage TOFMS are utilized. To overcome the lack of MS/MS database, Compound Structure Identification (CSI):FingerID is used to interpret CID spectra and predict best matched structures from PubChem library. With this approach, a total of 59 compounds were positively identified in comparison to only 22 in NIST database search of GC-EI-MS dataset. This study demonstrates the effectiveness of GC-dAPCI-MS/MS to overcome the limitations of traditional GC-EI-MS analysis when EI-MS database is not sufficient. [Figure not available: see fulltext.

[Determination and analysis of toluene diisocyanate metabolites in mice using gas chromatography-mass spectrometry].

PubMed

Ji, Yu-Bin; Ji, Chen-Feng; Zou, Xiang; Liu, Hui-Xin

2007-09-01

In the present research we used gas chromatography-mass spectrometry (G C-MS) to determine metabolites of toluene diisocyanate (TDI) in mice and deduce the pathway for toluene diisocyanate metabolism in the organism. Conditions for TDI chromatography: Supelco PTETM-5 chromatographic column (30 mm x 0.25 mm x 0.25 microm); initial column temperature: 90 degrees C, which was maintained for 30 min, then the temperature was increased at a rate of 40 degrees C x min(-1) to 280 degrees C, and maintained for 5.25 min; temperature for the vaporizing chamber: 250 degrees C; carrier gas: helium flowing at 1.0 microL x min(-1). Conditions for chromatography of TDI metabolites in the organism: 94% methyl, 4% ethenyl-bonded-phase fused-silica capillary column (30 + 2 m x 0.25 + 0.02 mm); initial column temperature: 30 degrees C, which was maintained for 5 min, after and then was increased at a rate of 80 degrees C x min(-1) to 280 degrees C, and maintained for 5 min; temperature for the vaporizing chamber: 250 degrees C; carrier gas: helium flowing at 1.0 microL x min(-1). Conditions for mass spectrometry: EI for ionization; 70 eV for ionization energy; 280 degrees C for connecting tube temperature; 35-350 micro for range of scanning; and 1.0 microL for sample size. The results showed that 2 ,4-toluene diisocyanate was metabolized into 2,4-diaminotoluene. Under the conditions selected for GC-MS, TDI metabolites in the organism can be isolated and identified.

A Novel Method for Profiling and Quantifying Short- and Medium-Chain Chlorinated Paraffins in Environmental Samples Using Comprehensive Two-Dimensional Gas Chromatography-Electron Capture Negative Ionization High-Resolution Time-of-Flight Mass Spectrometry.

PubMed

Xia, Dan; Gao, Lirong; Zheng, Minghui; Tian, Qichang; Huang, Huiting; Qiao, Lin

2016-07-19

Chlorinated paraffins (CPs) are complex technical mixtures containing thousands of isomers. Analyzing CPs in environmental matrices is extremely challenging. CPs have broad, unresolved profiles when analyzed by one-dimensional gas chromatography (GC). Comprehensive two-dimensional GC (GC×GC) can separate CPs with a high degree of orthogonality. A novel method for simultaneously profiling and quantifying short- and medium-chain CPs, using GC×GC coupled with electron capture negative ionization high-resolution time-of-flight mass spectrometry, was developed. The method allowed 48 CP formula congener groups to be analyzed highly selectively in one injection through accurate mass measurements of the [M - Cl](-) ions in full scan mode. The correlation coefficients (R(2)) for the linear calibration curves for different chlorine contents were 0.982 for short-chain CPs and 0.945 for medium-chain CPs. The method was successfully used to determine CPs in sediment and fish samples. By using this method, with enhanced chromatographic separation and high mass resolution, interferences between CP congeners and other organohalogen compounds, such as toxaphene, are minimized. New compounds, with the formulas C9H14Cl6 and C9H13Cl7, were found in sediment and biological samples for the first time. The method was shown to be a powerful tool for the analysis of CPs in environmental samples.

Ionization in MHD-Gas interactions

NASA Astrophysics Data System (ADS)

Wilson, A.; Diver, D. A.

2013-09-01

The study of partially ionized plasmas is important in a number of astrophysical situations and is vital for the study of laboratory plasmas. The interactions between a neutral gas and a plasma define a hybrid medium that has aspects of each, but does not only sustain the pure modes of the individual species. Previously we have shown that momentum coupling between the gas and the magnetized plasma alters the behaviour of both; as an extension of that simulation, we present results for the extension to the coupling in which the relative motion between the species provides enough kinetic energy in the flow to allow a measure of species exchange Alfvén ionization (AI) (also known as critical velocity ionization), allowing the ionization fraction to evolve as the dynamics evolve.

Simultaneous determination of methanol, acetaldehyde, acetone, and ethanol in human blood by gas chromatography with flame ionization detection.

PubMed

Schlatter, J; Chiadmi, F; Gandon, V; Chariot, P

2014-01-01

Methanol, acetaldehyde, acetone, and ethanol, which are commonly used as biomarkers of several diseases, in acute intoxications, and forensic settings, can be detected and quantified in biological fluids. Gas chromatography (GC)-mass spectrometry techniques are complex, require highly trained personnel and expensive materials. Gas chromatographic determinations of ethanol, methanol, and acetone have been reported in one study with suboptimal accuracy. Our objective was to improve the assessment of these compounds in human blood using GC with flame ionization detection. An amount of 50 µl of blood was diluted with 300 µl of sterile water, 40 µl of 10% sodium tungstate, and 20 µl of 1% sulphuric acid. After centrifugation, 1 µl of the supernatant was injected into the gas chromatograph. We used a dimethylpolysiloxane capillary column of 30 m × 0.25 mm × 0.25 µm. We observed linear correlations from 7.5 to 240 mg/l for methanol, acetaldehyde, and acetone and from 75 to 2400 mg/l for ethanol. Precision at concentrations 15, 60, and 120 mg/l for methanol, acetaldehyde, and acetone and 150, 600, and 1200 mg/ml for ethanol were 0.8-6.9%. Ranges of accuracy were 94.7-98.9% for methanol, 91.2-97.4% for acetaldehyde, 96.1-98.7% for acetone, and 105.5-111.6% for ethanol. Limits of detection were 0.80 mg/l for methanol, 0.61 mg/l for acetaldehyde, 0.58 mg/l for acetone, and 0.53 mg/l for ethanol. This method is suitable for routine clinical and forensic practices.

A Miniaturized Linear Wire Ion Trap with Electron Ionization and Single Photon Ionization Sources

NASA Astrophysics Data System (ADS)

Wu, Qinghao; Tian, Yuan; Li, Ailin; Andrews, Derek; Hawkins, Aaron R.; Austin, Daniel E.

2017-05-01

A linear wire ion trap (LWIT) with both electron ionization (EI) and single photon ionization (SPI) sources was built. The SPI was provided by a vacuum ultraviolet (VUV) lamp with the ability to softly ionize organic compounds. The VUV lamp was driven by a pulse amplifier, which was controlled by a pulse generator, to avoid the detection of photons during ion detection. Sample gas was introduced through a leak valve, and the pressure in the system is shown to affect the signal-to-noise ratio and resolving power. Under optimized conditions, the limit of detection (LOD) for benzene was 80 ppbv using SPI, better than the LOD using EI (137 ppbv). System performance was demonstrated by distinguishing compounds in different classes from gasoline.

Combined Determination of Poly-β-Hydroxyalkanoic and Cellular Fatty Acids in Starved Marine Bacteria and Sewage Sludge by Gas Chromatography with Flame Ionization or Mass Spectrometry Detection

PubMed Central

Odham, Göran; Tunlid, Anders; Westerdahl, Gunilla; Mårdén, Per

1986-01-01

Extraction of lipids from bacterial cells or sewage sludge samples followed by simple and rapid extraction procedures and room temperature esterification with pentafluorobenzylbromide allowed combined determinations of poly-β-hydroxyalkanoate constituents and fatty acids. Capillary gas chromatography and flame ionization or mass spectrometric detection was used. Flame ionization permitted determination with a coefficient of variation ranging from 10 to 27% at the picomolar level, whereas quantitative chemical ionization mass spectrometry afforded sensitivities for poly-β-hydroxyalkanoate constituuents in the attomolar range. The latter technique suggests the possibility of measuring such components in bacterial assemblies with as few as 102 cells. With the described technique using flame ionization detection, it was possible to study the rapid formation of poly-β-hydroxyalkanoate during feeding of a starved marine bacterium isolate with a complex medium or glucose and correlate the findings to changes in cell volumes. Mass spectrometric detection of short β-hydroxy acids in activated sewage sludge revealed the presence of 3-hydroxybutyric, 3-hydroxyhexanoic, and 3-hydroxyoctanoic acids in the relative proportions of 56, 5 and 39%, respectively. No odd-chain β-hydroxy acids were found. PMID:16347181

E-beam ionized channel guiding of an intense relativistic electron beam

DOEpatents

Frost, Charles A.; Godfrey, Brendon B.; Kiekel, Paul D.; Shope, Steven L.

1988-01-01

An IREB is guided through a curved path by ionizing a channel in a gas with electrons from a filament, and confining the electrons to the center of the path with a magnetic field extending along the path. The magnetic field is preferably generated by a solenoid extending along the path.

Weakly ionized cosmic gas: Ionization and characterization

NASA Technical Reports Server (NTRS)

Rosenberg, M.; Mendis, D. A.; Chow, V. W.

1994-01-01

Since collective plasma behavior may determine important transport processes (e.g., plasma diffusion across a magnetic field) in certain cosmic environments, it is important to delineate the parameter space in which weakly ionized cosmic gases may be characterized as plasmas. In this short note, we do so. First, we use values for the ionization fraction given in the literature, wherein the ionization is generally assumed to be due primarily to ionization by cosmic rays. We also discuss an additional mechanism for ionization in such environments, namely, the photoelectric emission of electrons from cosmic dust grains in an interstellar Far Ultra Violet (FUV) radiation field. Simple estimates suggest that under certain conditions this mechanism may dominate cosmic ray ionization, and possibly also the photoionization of metal atoms by the interstellar FUV field, and thereby lead to an enhanced ionization level.

Use of hydrogen as a carrier gas for the analysis of steroids with anabolic activity by gas chromatography-mass spectrometry.

PubMed

Muñoz-Guerra, J A; Prado, P; García-Tenorio, S Vargas

2011-10-14

Due to the impact in the media and the requirements of sensitivity and robustness, the detection of the misuse of forbidden substances in sports is a really challenging area for analytical chemistry, where any study focused on enhancing the performance of the analytical methods will be of great interest. The aim of the present study was to evaluate the usefulness of using hydrogen instead of helium as a carrier gas for the analysis of anabolic steroids by gas chromatography-mass spectrometry with electron ionization. There are several drawbacks related with the use of helium as a carrier gas: it is expensive, is a non-renewable resource, and has limited availability in many parts of the world. In contrast, hydrogen is readily available using a hydrogen generator or high-pressure bottled gas, and allows a faster analysis without loss of efficiency; nevertheless it should not be forgotten that due to its explosiveness hydrogen must be handled with caution. Throughout the study the impact of the change of the carrier gas will be evaluated in terms of: performance of the chromatographic system, saving of time and money, impact on the high vacuum in the analyzer, changes in the fragmentation behaviour of the analytes, and finally consequences for the limits of detection achieved with the method. Copyright © 2011 Elsevier B.V. All rights reserved.

E-beam ionized channel guiding of an intense relativistic electron beam

DOEpatents

Frost, C.A.; Godfrey, B.B.; Kiekel, P.D.; Shope, S.L.

1988-05-10

An IREB is guided through a curved path by ionizing a channel in a gas with electrons from a filament, and confining the electrons to the center of the path with a magnetic field extending along the path. The magnetic field is preferably generated by a solenoid extending along the path. 2 figs.

Identification of V-type nerve agents in vapor samples using a field-portable capillary gas chromatography/membrane-interfaced electron ionization quadrupole mass spectrometry instrument with Tri-Bed concentrator and fluoridating conversion tube.

PubMed

Ohrui, Y; Nagoya, T; Kurimata, N; Sodeyama, M; Seto, Y

2017-07-01

A field-portable gas chromatography-mass spectrometry (GC-MS) system (Hapsite ER) was evaluated for the detection of nonvolatile V-type nerve agents (VX and Russian VX (RVX)) in the vapor phase. The Hapsite ER system consists of a Tri-Bed concentrator gas sampler, a nonpolar low thermal-mass capillary GC column and a hydrophobic membrane-interfaced electron ionization quadrupole mass spectrometer evacuated by a non-evaporative getter pump. The GC-MS system was attached to a VX-G fluoridating conversion tube containing silver nitrate and potassium fluoride. Sample vapors of VX and RVX were converted into O-ethyl methylphosphonofluoridate (EtGB) and O-isobutyl methylphosphonofluoridate (iBuGB), respectively. These fluoridated derivatives were detected within 10 min. No compounds were detected when the VX and RVX samples were analyzed without the conversion tube. A vapor sample of tabun (GA) was analyzed, in which GA and O-ethyl N,N-dimethylphosphoramidofluoridate were detected. The molar recovery percentages of EtGB and iBuGB from VX and RVX vapors varied from 0.3 to 17%, which was attributed to variations in the vaporization efficiency of the glass vapor container. The conversion efficiencies of the VX-G conversion tube for VX and RVX to their phosphonate derivatives were estimated to be 40%. VX and RVX vapors were detected at concentrations as low as 0.3 mg m -3 . Gasoline vapor was found to interfere with the analyses of VX and RVX. In the presence of 160 mg m -3 gasoline, the detection limits of VX and RVX vapor were increased to 20 mg m -3 . Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Improvement of mineral oil saturated and aromatic hydrocarbons determination in edible oil by liquid-liquid-gas chromatography with dual detection.

PubMed

Zoccali, Mariosimone; Barp, Laura; Beccaria, Marco; Sciarrone, Danilo; Purcaro, Giorgia; Mondello, Luigi

2016-02-01

Mineral oils, which are mainly composed of saturated hydrocarbons and aromatic hydrocarbons, are widespread food contaminants. Liquid chromatography coupled to gas chromatography with flame ionization detection represents the method of choice to determine these two families. However, despite the high selectivity of this technique, the presence of olefins (particularly squalene and its isomers) in some samples as in olive oils, does not allow the correct quantification of the mineral oil aromatic hydrocarbons fraction, requiring additional off-line tools to eliminate them. In the present research, a novel on-line liquid chromatography coupled to gas chromatography method is described for the determination of hydrocarbon contamination in edible oils. Two different liquid chromatography columns, namely a silica one (to retain the bulk of the matrix) and a silver-ion one (which better retains the olefins), were coupled in series to obtain the mineral oil aromatic hydrocarbons hump free of interfering peaks. Furthermore, the use of a simultaneous dual detection, flame ionization detector and triple quadrupole mass spectrometer allowed us not only to quantify the mineral oil contamination, but also to evaluate the presence of specific markers (i.e. hopanes) to confirm the petrogenic origin of the contamination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas-phase ionization energetics, electron-transfer kinetics, and ion solvation thermochemistry of decamethylmetallocenes, chromocene, and cobaltocene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryan, M.F.; Richardson, D.E.; Lichtenberger, D.L.

1994-04-01

The gas-phase free energies of ionization, [Delta]G[sub i][degrees] for Cp*[sub 2]Mn, Cp*[sub 2]Fe, Cp*[sub 2]Ni, Cp*[sub 2]Os, Cp[sub 2]Cr, and Cp[sub 2]Co (Cp = [eta][sup 5]-cyclopentadienyl, Cp[sup *] = [eta][sup 5]-pentamethylcyclopentadienyl) have been determined by using the electron-transfer equilibrium (ETE) technique and Fourier transform ion cyclotron resonance mass spectrometry. The high-resolution valence photoelectron spectra of bis(benzene)chromium(0), Bz[sub 2]Cr, Cp*[sub 2]Os, and Cp*[sub 2]Ru have also been measured. Most of the [Delta]G[sub i][degrees] values are referenced to the estimated [Delta]G[sub i][degrees] value of Bz[sub 2]Cr, for which the narrow first ionization band at 5.473 [+-] 0.005 eV is assigned as themore » adiabatic ionization potential. The [Delta]S[sub i][degrees] for ionization of Bz[sub 2]Cr is assumed to be equal to the electronic entropy change, [Delta]S[sub elec][degrees] (=1.4 cal mol[sup [minus]1] K[sup [minus]1]), and the difference between the integrated heat capacities for Bz[sub 2]Cr and Bz[sub 2]Cr[sup +] is also assumed to be negligible near room temperature [Delta]H[sub i,0][degrees] [approx] [Delta]H[sub i,350][degrees], leading to [Delta]G[sub i][degrees] (Bz[sub 2]-Cr) = 125.6 [+-] 1.0 kcal mol[sup [minus]1]. Through the use of thermochemical cycles, estimates are given for the average heterolytic and homolytic M-Cp bond disruption enthalpies of Cp[sub 2]Cr[sup +/0] and Cp[sub 2]Co[sup +/0]. 46 refs., 7 figs., 4 tabs.« less

Determination of alkylphenols by gas chromatography, elution liquid chromatography, and gel permeation chromatography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wittmann, S.; Decsy, Z.; Regensperger, S.

1984-01-01

The separation and determination of groups of alkylphenols with C/sub 15/-C/sub 33/ isoalkane chains by gas chromatography, elution liquid chromatography, and gel permeation chromatography are described. Paraffinic hydrocarbons, monoalkylphenols, dialkylphenols, and bis(hydroxyphenyl)alkanes were identified in industrial alkylphenols by mass spectrometry. 7 references, 3 figures, 2 tables.

Electron-Impact Ionization and Dissociative Ionization of Biomolecules

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Chaban, Galina M.; Dateo, Christopher E.

2006-01-01

It is well recognized that secondary electrons play an important role in radiation damage to humans. Particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. Our study of electron-impact ionization of DNA fragments uses the improved binary-encounter dipole model and covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3(sup prime)- and C5 (sup prime)-deoxyribose-phospate cross sections, differing by less than 5%. Investigation of tandem double lesion initiated by electron-impact dissociative ionization of guanine, followed by proton reaction with the cytosine in the Watson-Crick pair, is currently being studied to see if tandem double lesion can be initiated by electron impact. Up to now only OH-induced tandem double lesion has been studied.

Determination of Poly-β-Hydroxybutyrate and Poly-β-Hydroxyvalerate in Activated Sludge by Gas-Liquid Chromatography

PubMed Central

Comeau, Yves; Hall, Kenneth J.; Oldham, William K.

1988-01-01

A convenient gas-liquid chromatography procedure to quantify poly-β-hydroxybutyrate and poly-β-hydroxyvalerate in activated sludge was developed by combining lyophilization of the samples, purification of the chloroform phase by water reextraction, and the use of capillary columns. With a flame ionization detector the sensitivity was estimated at 10−5 g/liter. PMID:16347745

Quantification, dissipation behavior and risk assessment of ethion in green pea by gas chromatography-electron capture detector.

PubMed

Jan, Ishrat; Dar, Alamgir A; Mubashir, Sofi; Alam Wani, Ashraf; Mukhtar, Malik; Sofi, Khurshid A; Dar, Irshad H; Sofi, Javid A

2018-05-01

Residue investigation was carried out to scrutinize the persistence, dissipation behavior, half-life, and risk assessment of ethion on green pea fruit by spraying ethion at the fruiting stage followed by another application at 10 day intervals. The samples were extracted by using a quick, easy, low-cost, effective, rugged, and safe method, and the residues of ethion were analyzed by gas chromatography with electron capture detection. Here we report a novel, accurate, and cost-effective gas chromatography method for the determination of average deposits of ethion on green pea. The initial deposits were found to be 4.65 mg/kg following the application of insecticide. Residues of ethion reached below the detection limit of 0.10 mg/kg after 25 days at recommended dosage. The half-life of ethion was found to be 4.62 days. For risk assessment studies, the 25th day will be safe for consumers for the consumption of green peas. The developed method is simple, sensitive, selective, and repeatable and can be extended for ethion-based standardization of herbal formulations containing green pea and its use in pesticide industries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Separation and identification of 5 glycosidic flavor precursors in tobacco by ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry].

PubMed

Wu, Xinhua; Zhu, Ruizhi; Ren, Zhuoying; Wang, Kai; Mou, Dingrong; Wei, Wanzhi; Miao, Mingming

2009-11-01

A qualitative method for the identification of 5 main glycosidic flavor precursors in tobacco was developed by using ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI MS/MS) and gas chromatography-mass spectrometry (GC-MS). The glycosidic flavor precursors in tobacco were extracted with methanol, cleaned up with an XAD-2 column. The aglycones were later released by enzyme-mediated hydrolysis under the condition of pH 5. The 5 volatile aglycone moieties were identified by GC-MS standard spectra library. The precursor ions of glycosides were determined by using electrospray ionization mass spectrometry in negative ion mode, then the 5 glycosidic flavor precursors were identified by using product ion scan (MS2) finally, using UPLC-ESI MS/MS, separation and identification of 5 glycosidic flavor precursors were accomplished on an RP-C,8 column in the multiple reaction monitoring (MRM) mode by using methanol and acetic acid-ammonium acetate aqueous solution as eluent. This work lays a foundation for the analysis of glycosidic flavor precursors without the standards by using liquid chromatography-mass spectrometry.

[Gas chromatography with a Pulsed discharge helium ionization detector for measurement of molecular hydrogen(H2) in the atmosphere].

PubMed

Luan, Tian; Fang, Shuang-xi; Zhou, Ling-xi; Wang, Hong-yang; Zhang, Gen

2015-01-01

A high precision GC system with a pulsed discharge helium ionization detector was set up based on the commercial Agilent 7890A gas chromatography. The gas is identified by retention time and the concentration is calculated through the peak height. Detection limit of the system is about 1 x 10(-9) (mole fraction, the same as below). The standard deviation of 140 continuous injections with a standard cylinder( concentration is roughly 600 x 10(-9)) is better than 0.3 x 10(-9). Between 409.30 x 10(-9) and 867.74 x 10(-9) molecular hydrogen mole fractions and peak height have good linear response. By using two standards to quantify the air sample, the precision meets the background molecular hydrogen compatibility goal within the World Meteorological Organization/Global Atmosphere Watch (WMO/GAW) program. Atmospheric molecular hydrogen concentration at Guangzhou urban area was preliminarily measured by this method from January to November 2013. The results show that the atmospheric molecular hydrogen mole fraction varies from 450 x 10(-9) to 700 x 10(-9) during the observation period, with the lowest value at 14:00 (Beijing time, the same as below) and the peak value at 20:00. The seasonal variation of atmospheric hydrogen at Guangzhou area was similar with that of the same latitude stations in northern hemisphere.

Determination of glucosinolates in rapeseed and Thlaspi caerulescens plants by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

PubMed

Tolrà, R P; Alonso, R; Poschenrieder, C; Barceló, D; Barceló, J

2000-08-11

Liquid chromatography-atmospheric pressure chemical ionization mass spectrometry was used to identify glucosinolates in plant extracts. Optimization of the analytical conditions and the determination of the method detection limit was performed using commercial 2-propenylglucosinolate (sinigrin). Optimal values for the following parameters were determined: nebulization pressure, gas temperature, flux of drying gas, capillar voltage, corona current and fragmentor conditions. The method detection limit for sinigrin was 2.85 ng. For validation of the method the glucosinolates in reference material (rapeseed) from the Community Bureau of Reference Materials (BCR) were analyzed. The method was applied for the determination of glucosinolates in Thlaspi caerulescens plants.

Analysis of anabolic steroids in urine by gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry with chlorobenzene as dopant.

PubMed

Hintikka, Laura; Haapala, Markus; Kuuranne, Tiia; Leinonen, Antti; Kostiainen, Risto

2013-10-18

A gas chromatography-microchip atmospheric pressure photoionization-tandem mass spectrometry (GC-μAPPI-MS/MS) method was developed for the analysis of anabolic androgenic steroids in urine as their trimethylsilyl derivatives. The method utilizes a heated nebulizer microchip in atmospheric pressure photoionization mode (μAPPI) with chlorobenzene as dopant, which provides high ionization efficiency by producing abundant radical cations with minimal fragmentation. The performance of GC-μAPPI-MS/MS was evaluated with respect to repeatability, linearity, linear range, and limit of detection (LOD). The results confirmed the potential of the method for doping control analysis of anabolic steroids. Repeatability (RSD<10%), linearity (R(2)≥0.996) and sensitivity (LODs 0.05-0.1ng/mL) were acceptable. Quantitative performance of the method was tested and compared with that of conventional GC-electron ionization-MS, and the results were in good agreement. Copyright © 2013 Elsevier B.V. All rights reserved.

Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

PubMed

Hayen, Heiko; Michels, Antje; Franzke, Joachim

2009-12-15

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better.

A highly sensitive electron spectrometer for crossed-beam collisional ionization: A retarding-type magnetic bottle analyzer and its application to collision-energy resolved Penning ionization electron spectroscopy

NASA Astrophysics Data System (ADS)

Yamakita, Yoshihiro; Tanaka, Hideyasu; Maruyama, Ryo; Yamakado, Hideo; Misaizu, Fuminori; Ohno, Koichi

2000-08-01

A highly sensitive electron energy analyzer which utilizes a "magnetic bottle" combined with a retarding electrostatic field has been developed for Penning ionization electron spectroscopy. A beam of metastable rare-gas atoms is crossed with a continuous supersonic sample beam in the source region of the analyzer. The emitted electrons are collected by an inhomogeneous magnetic field (the magnetic bottle effect) with a high efficiency of nearly 4π solid angle, which is more than 103 times higher than that of a conventional hemispherical analyzer. The kinetic energy of electrons is analyzed by scanning the retarding field in a flight tube of the analyzer in the presence of a weak magnetic field. The velocity of the metastable atoms can also be resolved by a time-of-flight method in the present instrument. Examples of Penning ionization electron energy spectra as a function of collision energy are presented for Ar and N2 with metastable He*(2 3S) atoms. This instrument has opened the possibility for extensive studies of Penning ionization electron spectroscopy for low-density species, such as clusters, ions, electronically excited species, unstable or transient species, and large molecules with low volatility.

Rapid direct analysis to discriminate geographic origin of extra virgin olive oils by flash gas chromatography electronic nose and chemometrics.

PubMed

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.

Ultra-low emittance electron beam generation using ionization injection in a plasma beatwave accelerator

NASA Astrophysics Data System (ADS)

Schroeder, Carl; Benedetti, Carlo; Esarey, Eric; Leemans, Wim

2017-10-01

Ultra-low emittance beams can be generated using ionization injection of electrons into a wakefield excited by a plasma beatwave accelerator. This all-optical method of electron beam generation uses three laser pulses of different colors. Two long-wavelength laser pulses, with frequency difference equal to the plasma frequency, resonantly drive a plasma wave without fully ionizing a gas. A short-wavelength injection laser pulse (with a small ponderomotive force and large peak electric field), co-propagating and delayed with respect to the beating long-wavelength lasers, ionizes a fraction of the remaining bound electrons at a trapped wake phase, generating an electron beam that is accelerated in the wakefield. Using the beating of long-wavelength pulses to generate the wakefield enables atomically-bound electrons to remain at low ionization potentials, reducing the required amplitude of the ionization pulse, and, hence, the initial transverse momentum and emittance of the injected electrons. An example is presented using two lines of a CO2 laser to form a plasma beatwave accelerator to drive the wake and a frequency-doubled Ti:Al2O3 laser for ionization injection. Supported by the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Ionizing gas breakdown waves in strong electric fields.

NASA Technical Reports Server (NTRS)

Klingbeil, R.; Tidman, D. A.; Fernsler, R. F.

1972-01-01

A previous analysis by Albright and Tidman (1972) of the structure of an ionizing potential wave driven through a dense gas by a strong electric field is extended to include atomic structure details of the background atoms and radiative effects, especially, photoionization. It is found that photoionization plays an important role in avalanche propagation. Velocities, electron densities, and temperatures are presented as a function of electric field for both negative and positive breakdown waves in nitrogen.

Determination of C6-C10 aromatic hydrocarbons in water by purge-and-trap capillary gas chromatography

USGS Publications Warehouse

Eganhouse, R.P.; Dorsey, T.F.; Phinney, C.S.; Westcott, A.M.

1993-01-01

A method is described for the determination of the C6-C10 aromatic hydrocarbons in water based on purge-and-trap capillary gas chromatography with flame ionization and mass spectrometric detection. Retention time data and 70 eV mass spectra were obtained for benzene and all 35 C7-C10 aromatic hydrocarbons. With optimized chromatographic conditions and mass spectrometric detection, benzene and 33 of the 35 alkylbenzenes can be identified and measured in a 45-min run. Use of a flame ionization detector permits the simultaneous determination of benzene and 26 alkylbenzenes.

Air ionization as a control technology for off-gas emissions of volatile organic compounds.

PubMed

Kim, Ki-Hyun; Szulejko, Jan E; Kumar, Pawan; Kwon, Eilhann E; Adelodun, Adedeji A; Reddy, Police Anil Kumar

2017-06-01

High energy electron-impact ionizers have found applications mainly in industry to reduce off-gas emissions from waste gas streams at low cost and high efficiency because of their ability to oxidize many airborne organic pollutants (e.g., volatile organic compounds (VOCs)) to CO 2 and H 2 O. Applications of air ionizers in indoor air quality management are limited due to poor removal efficiency and production of noxious side products, e.g., ozone (O 3 ). In this paper, we provide a critical evaluation of the pollutant removal performance of air ionizing system through comprehensive review of the literature. In particular, we focus on removal of VOCs and odorants. We also discuss the generation of unwanted air ionization byproducts such as O 3 , NOx, and VOC oxidation intermediates that limit the use of air-ionizers in indoor air quality management. Copyright © 2017. Published by Elsevier Ltd.

Quantitative Detection of Trace Explosive Vapors by Programmed Temperature Desorption Gas Chromatography-Electron Capture Detector

PubMed Central

Field, Christopher R.; Lubrano, Adam; Woytowitz, Morgan; Giordano, Braden C.; Rose-Pehrsson, Susan L.

2014-01-01

The direct liquid deposition of solution standards onto sorbent-filled thermal desorption tubes is used for the quantitative analysis of trace explosive vapor samples. The direct liquid deposition method yields a higher fidelity between the analysis of vapor samples and the analysis of solution standards than using separate injection methods for vapors and solutions, i.e., samples collected on vapor collection tubes and standards prepared in solution vials. Additionally, the method can account for instrumentation losses, which makes it ideal for minimizing variability and quantitative trace chemical detection. Gas chromatography with an electron capture detector is an instrumentation configuration sensitive to nitro-energetics, such as TNT and RDX, due to their relatively high electron affinity. However, vapor quantitation of these compounds is difficult without viable vapor standards. Thus, we eliminate the requirement for vapor standards by combining the sensitivity of the instrumentation with a direct liquid deposition protocol to analyze trace explosive vapor samples. PMID:25145416

Quantitative detection of trace explosive vapors by programmed temperature desorption gas chromatography-electron capture detector.

PubMed

Field, Christopher R; Lubrano, Adam; Woytowitz, Morgan; Giordano, Braden C; Rose-Pehrsson, Susan L

2014-07-25

The direct liquid deposition of solution standards onto sorbent-filled thermal desorption tubes is used for the quantitative analysis of trace explosive vapor samples. The direct liquid deposition method yields a higher fidelity between the analysis of vapor samples and the analysis of solution standards than using separate injection methods for vapors and solutions, i.e., samples collected on vapor collection tubes and standards prepared in solution vials. Additionally, the method can account for instrumentation losses, which makes it ideal for minimizing variability and quantitative trace chemical detection. Gas chromatography with an electron capture detector is an instrumentation configuration sensitive to nitro-energetics, such as TNT and RDX, due to their relatively high electron affinity. However, vapor quantitation of these compounds is difficult without viable vapor standards. Thus, we eliminate the requirement for vapor standards by combining the sensitivity of the instrumentation with a direct liquid deposition protocol to analyze trace explosive vapor samples.

Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemical ionization.

PubMed

Ovchinnikova, Olga S; Van Berkel, Gary J

2010-06-30

An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

Theoretical predictions of properties and gas-phase chromatography behaviour of carbonyl complexes of group-6 elements Cr, Mo, W, and element 106, Sg.

PubMed

Pershina, V; Anton, J

2013-05-07

Fully relativistic, four-component density functional theory electronic structure calculations were performed for M(CO)6 of group-6 elements Cr, Mo, W, and element 106, Sg, with an aim to predict their adsorption behaviour in the gas-phase chromatography experiments. It was shown that seaborgium hexacarbonyl has a longer M-CO bond, smaller ionization potential, and larger polarizability than the other group-6 molecules. This is explained by the increasing relativistic expansion and destabilization of the (n - 1)d AOs with increasing Z in the group. Using results of the calculations, adsorption enthalpies of the group-6 hexacarbonyls on a quartz surface were predicted via a model of physisorption. According to the results, -ΔHads should decrease from Mo to W, while it should be almost equal--within the experimental error bars--for W and Sg. Thus, we expect that in the future gas-phase chromatography experiments it will be almost impossible--what concerns ΔHads--to distinguish between the W and Sg hexacarbonyls by their deposition on quartz.

Amonia gas: an improved reagent for chemical ionization mass spectrometry of bile acid methyl ester acetates

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeMark, B.R.; Klein, P.D.

1981-01-01

The ammonia chemical ionization mass spectra of 28 methyl ester acetate derivatives of bile acids and related compounds have been determined by gas-liquid chromatography-mass spectrometry. Advantages of ammonia ionization over the previously studied isobutane ionization include a 130 to 270% enhancement in the sensitivity of base peak monitoring, and direct determination of molecular weight from the base peak (M + NH/sub 4//sup +/) in the mass spectrum of any of the derivatives. Minor ions in the ammonia spectra also allow selective detection of 3-keto compounds and can indicate unsaturation or double bond conjugation in the molecule. The significance of thesemore » studies for the detection and quantitation of bile acids is discussed. 2 tables.« less

CF3+ fragmentation by electron impact ionization of perfluoro-propyl-vinyl-ethers, C5F10O, in gas phase

NASA Astrophysics Data System (ADS)

Kondo, Yusuke; Ishikawa, Kenji; Hayashi, Toshio; Miyawaki, Yudai; Takeda, Keigo; Kondo, Hiroki; Sekine, Makoto; Hori, Masaru

2015-04-01

The gas phase fragmentations of perfluoro-propyl-vinyl ether (PPVE, C5F10O) are studied experimentally. Dominant fragmentations of PPVE are found to be the result of a dissociative ionization reaction, i.e., CF3+ via direct bond cleavage, and C2F3O- and C3F7O- via electron attachment. Regardless of the appearance energy of around 14.5 eV for the dissociative ionization of CF3+, the observed ion efficiency for the CF3+ ion was extremely large the order of 10-20 cm-2, compared with only 10-21 cm-2 for the other channels. PPVE characteristically generated CF3+ as the largest abundant ion are advantageous for use of feedstock gases in plasma etching processes.

A gas chromatography/high-resolution mass spectrometry (GC/HRMS) method for determination of polybrominated diphenyl ethers in fish.

PubMed

Alaee, M; Sergeant, D B; Ikonomou, M G; Luross, J M

2001-09-01

A method for the determination of polybrominated diphenyl ethers (PBDEs) in biota for routine analysis is described. The mass spectroscopic (MS) evaluation of 23 brominated diphenyl ethers, under electron ionization and electron capture negative ion conditions using magnetic sector and quadrupole mass spectrometers, showed that high-resolution mass spectrometry (HRMS) under electron ionization conditions was the most reliable technique, with high selectivity and adequate sensitivity. The instrument detection limit for this method ranged for individual congeners between 4.8 and 0.1 pg for 3-bromodiphenyl ether (BDE-2) and 2,3',4,4'-tetrabromodiphenyl ether (BDE-66), respectively, and method detection limit for each homologue group ranged between 5 pg/g for salmon certified reference material (CRM) and 93 pg/g for lake trout CRM. The effectiveness of this method was evaluated by analyzing the occurrence of PBDEs in commercially available CRMs comprising Lake Ontario lake trout, Pacific herring, and sockeye salmon. The average coefficients of variation for the replicate analyses of PDBEs in several tissue samples were: 25% for lake trout, 36% for Pacific herring, and 34% for sockeye salmon. The average deviations in the inter-laboratory study were: 14% for lake trout, 15% for Pacific herring, and 37% for sockeye salmon. Results indicated that the described method, based on gas chromatography/high-resolution mass spectrometry, is reliable for determining PBDE concentrations in biological tissues.

Ionic liquid stationary phases for gas chromatography.

PubMed

Poole, Colin F; Poole, Salwa K

2011-04-01

This article provides a summary of the development of ionic liquids as stationary phases for gas chromatography beginning with early work on packed columns that established details of the retention mechanism and established working methods to characterize selectivity differences compared with molecular stationary phases through the modern development of multi-centered cation and cross-linked ionic liquids for high-temperature applications in capillary gas chromatography. Since there are many reviews on ionic liquids dealing with all aspects of their chemical and physical properties, the emphasis in this article is placed on the role of gas chromatography played in the design of ionic liquids of low melting point, high thermal stability, high viscosity, and variable selectivity for separations. Ionic liquids provide unprecedented opportunities for extending the selectivity range and temperature-operating range of columns for gas chromatography, an area of separation science that has otherwise been almost stagnant for over a decade. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionization enhancement in atmospheric pressure chemical ionization and suppression in electrospray ionization between target drugs and stable-isotope-labeled internal standards in quantitative liquid chromatography/tandem mass spectrometry.

PubMed

Liang, H R; Foltz, R L; Meng, M; Bennett, P

2003-01-01

The phenomena of ionization suppression in electrospray ionization (ESI) and enhancement in atmospheric pressure chemical ionization (APCI) were investigated in selected-ion monitoring and selected-reaction monitoring modes for nine drugs and their corresponding stable-isotope-labeled internal standards (IS). The results showed that all investigated target drugs and their co-eluting isotope-labeled IS suppress each other's ionization responses in ESI. The factors affecting the extent of suppression in ESI were investigated, including structures and concentrations of drugs, matrix effects, and flow rate. In contrast to the ESI results, APCI caused seven of the nine investigated target drugs and their co-eluting isotope-labeled IS to enhance each other's ionization responses. The mutual ionization suppression or enhancement between drugs and their isotope-labeled IS could possibly influence assay sensitivity, reproducibility, accuracy and linearity in quantitative liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). However, calibration curves were linear if an appropriate IS concentration was selected for a desired calibration range to keep the response factors constant. Copyright 2003 John Wiley & Sons, Ltd.

Multiresidue analysis of pesticides in traditional Chinese medicines using gas chromatography - negative chemical ionization tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

In this study, a residue analysis method for the simultaneous determination of 107 pesticides in the traditional Chinese medicines (TCMs), Angelica sinensis, Angelica dahurica, Leonurus heterophyllus Sweet, Pogostemon cablin, and Lonicera japonica Thunb, was developed using gas chromatography couple...

Trace analysis of impurities in bulk gases by gas chromatography-pulsed discharge helium ionization detection with "heart-cutting" technique.

PubMed

Weijun, Yao

2007-10-12

A method has been developed for the detection of low-nL/L-level impurities in bulk gases such as H(2), O(2), Ar, N(2), He, methane, ethylene and propylene, respectively. The solution presented here is based upon gas chromatography-pulsed discharge helium ionization detection (GC-PDHID) coupled with three two-position valves, one two-way solenoid valve and four packed columns. During the operation, the moisture and heavy compounds are first back-flushed via a pre-column. Then the trace impurities (except CO(2) which is diverted to a separate analytical column for separation and detection) together with the matrix enter onto a main column, followed by the heart-cut of the impurities onto a longer analytical column for complete separation. Finally the detection is performed by PDHID. This method has been applied to different bulk gases and the applicability of detecting impurities in H(2), Ar, and N(2) are herewith demonstrated. As an example, the resulting detection limit of 100 nL/L and a dynamic range of 100-1000 nL/L have been obtained using an Ar sample containing methane.

Development, optimization, validation and application of faster gas chromatography - flame ionization detector method for the analysis of total petroleum hydrocarbons in contaminated soils.

PubMed

Zubair, Abdulrazaq; Pappoe, Michael; James, Lesley A; Hawboldt, Kelly

2015-12-18

This paper presents an important new approach to improving the timeliness of Total Petroleum Hydrocarbon (TPH) analysis in the soil by Gas Chromatography - Flame Ionization Detector (GC-FID) using the CCME Canada-Wide Standard reference method. The Canada-Wide Standard (CWS) method is used for the analysis of petroleum hydrocarbon compounds across Canada. However, inter-laboratory application of this method for the analysis of TPH in the soil has often shown considerable variability in the results. This could be due, in part, to the different gas chromatography (GC) conditions, other steps involved in the method, as well as the soil properties. In addition, there are differences in the interpretation of the GC results, which impacts the determination of the effectiveness of remediation at hydrocarbon-contaminated sites. In this work, multivariate experimental design approach was used to develop and validate the analytical method for a faster quantitative analysis of TPH in (contaminated) soil. A fractional factorial design (fFD) was used to screen six factors to identify the most significant factors impacting the analysis. These factors included: injection volume (μL), injection temperature (°C), oven program (°C/min), detector temperature (°C), carrier gas flow rate (mL/min) and solvent ratio (v/v hexane/dichloromethane). The most important factors (carrier gas flow rate and oven program) were then optimized using a central composite response surface design. Robustness testing and validation of model compares favourably with the experimental results with percentage difference of 2.78% for the analysis time. This research successfully reduced the method's standard analytical time from 20 to 8min with all the carbon fractions eluting. The method was successfully applied for fast TPH analysis of Bunker C oil contaminated soil. A reduced analytical time would offer many benefits including an improved laboratory reporting times, and overall improved clean up

Photo-triggering and secondary electron produced ionization in electric discharge ArF* excimer lasers

NASA Astrophysics Data System (ADS)

Xiong, Zhongmin; Kushner, Mark J.

2011-10-01

Electric discharge excimer lasers are sustained in multi-atmosphere attaching gas mixtures that are typically preionized to enable a reproducible, uniform glow, which maximizes optical quality and gain. This preionization is often accomplished using UV light produced by a corona discharge within the plasma cavity. To quantify the relationship between corona discharge properties and those of the laser discharge, the triggering of electron avalanche by preionizing UV light in an electric discharge-pumped ArF* excimer laser was numerically investigated using a two-dimensional model. The preionizing UV fluxes were generated by a corona-bar discharge driven by the same voltage pulse as the main discharge sustained in a multi-atmospheric Ne/Ar/Xe/F2 gas mixture. The resulting peak photo-electron density in the inter-electrode spacing is around 108 cm-3, and its distribution is biased toward the UV source. The preionization density increases with increasing dielectric constant and capacitance of the corona bar. The symmetry and uniformity of the discharge are, however, improved significantly once the main avalanche develops. In addition to bulk electron impact ionization, the ionization generated by sheath accelerated secondary electrons was found to be important in sustaining the discharge current at experimentally observed values. At peak current, the magnitude of the ionization by sheath accelerated electrons is comparable to that from bulk electron impact in the vicinity of the cathode.

Coupling gas chromatography and electronic nose detection for detailed cigarette smoke aroma characterization.

PubMed

Rambla-Alegre, Maria; Tienpont, Bart; Mitsui, Kazuhisa; Masugi, Eri; Yoshimura, Yuta; Nagata, Hisanori; David, Frank; Sandra, Pat

2014-10-24

Aroma characterization of whole cigarette smoke samples using sensory panels or electronic nose (E-nose) devices is difficult due to the masking effect of major constituents and solvent used for the extraction step. On the other hand, GC in combination with olfactometry detection does not allow to study the delicate balance and synergetic effect of aroma solutes. To overcome these limitations a new instrumental set-up consisting of heart-cutting gas chromatography using a capillary flow technology based Deans switch and low thermal mass GC in combination with an electronic nose device is presented as an alternative to GC-olfactometry. This new hyphenated GC-E-nose configuration is used for the characterization of cigarette smoke aroma. The system allows the transfer, combination or omission of selected GC fractions before injection in the E-nose. Principal component analysis (PCA) and discriminant factor analysis (DFA) allowed clear visualizing of the differences among cigarette brands and classifying them independently of their nicotine content. Omission and perceptual interaction tests could also be carried out using this configuration. The results are promising and suggest that the GC-E-nose hyphenation is a good approach to measure the contribution level of individual compounds to the whole cigarette smoke. Copyright © 2014 Elsevier B.V. All rights reserved.

Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry.

PubMed

Santa, Tomofumi

2011-01-01

Liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is one of the most prominent analytical techniques owing to its inherent selectivity and sensitivity. In LC/ESI-MS/MS, chemical derivatization is often used to enhance the detection sensitivity. Derivatization improves the chromatographic separation, and enhances the mass spectrometric ionization efficiency and MS/MS detectability. In this review, an overview of the derivatization reagents which have been applied to LC/ESI-MS/MS is presented, focusing on the applications to low molecular weight compounds. 2010 John Wiley & Sons, Ltd.

High-temperature gas chromatography-mass spectrometry for skin surface lipids profiling.

PubMed

Michael-Jubeli, Rime; Bleton, Jean; Baillet-Guffroy, Arlette

2011-01-01

Skin surface lipids (SSLs) arising from both sebaceous glands and skin removal form a complex lipid mixture composed of free fatty acids and neutral lipids. High-temperature gas chromatography coupled with electron impact or chemical ionization mass spectrometry was used to achieve a simple analytical protocol, without prior separation in classes and without prior cleavage of lipid molecules, in order to obtain simultaneously i) a qualitative characterization of the individual SSLs and ii) a quantitative evaluation of lipid classes. The method was first optimized with SSLs collected from the forehead of a volunteer. More than 200 compounds were identified in the same run. These compounds have been classified in five lipid classes: free fatty acids, hydrocarbons, waxes, sterols, and glycerides. The advantage to this method was it provided structural information on intact compounds, which is new for cholesteryl esters and glycerides, and to obtain detailed fingerprints of the major SSLs. These fingerprints were used to compare the SSL compositions from different body areas. The squalene/cholesterol ratio was used to determine the balance between sebaceous secretion and skin removal. This method could be of general interest in fields where complex lipid mixtures are involved.

Liquid Chromatography Electrospray Ionization Mass Spectrometric (LC-ESI-MS) and Desorption Electrospray Ionization Mass Spectrometric (DESI-MS) Identification of Chemical Warfare Agents in Consumer Products

DTIC Science & Technology

2007-06-01

T ACanadaY Approved for PublicR Distribution Uln& Liquid Chromatography Electrospray Ionization Mass Spectrometric ( LC -ESI- MS) and Desorption...consumer products with chemical warfare agents or other toxic chemicals. Liquid chromatography electrospray ionization mass spectrometry ( LC -ESI-MS) and...house LC -ESI-MS and LC -ESI-MS/MS methods were evaluated for the determination of chemical warfare agents in spiked bottled water samples. The

Computational Prediction of Electron Ionization Mass Spectra to Assist in GC/MS Compound Identification.

PubMed

Allen, Felicity; Pon, Allison; Greiner, Russ; Wishart, David

2016-08-02

We describe a tool, competitive fragmentation modeling for electron ionization (CFM-EI) that, given a chemical structure (e.g., in SMILES or InChI format), computationally predicts an electron ionization mass spectrum (EI-MS) (i.e., the type of mass spectrum commonly generated by gas chromatography mass spectrometry). The predicted spectra produced by this tool can be used for putative compound identification, complementing measured spectra in reference databases by expanding the range of compounds able to be considered when availability of measured spectra is limited. The tool extends CFM-ESI, a recently developed method for computational prediction of electrospray tandem mass spectra (ESI-MS/MS), but unlike CFM-ESI, CFM-EI can handle odd-electron ions and isotopes and incorporates an artificial neural network. Tests on EI-MS data from the NIST database demonstrate that CFM-EI is able to model fragmentation likelihoods in low-resolution EI-MS data, producing predicted spectra whose dot product scores are significantly better than full enumeration "bar-code" spectra. CFM-EI also outperformed previously reported results for MetFrag, MOLGEN-MS, and Mass Frontier on one compound identification task. It also outperformed MetFrag in a range of other compound identification tasks involving a much larger data set, containing both derivatized and nonderivatized compounds. While replicate EI-MS measurements of chemical standards are still a more accurate point of comparison, CFM-EI's predictions provide a much-needed alternative when no reference standard is available for measurement. CFM-EI is available at https://sourceforge.net/projects/cfm-id/ for download and http://cfmid.wishartlab.com as a web service.

Transport properties of initially neutral gas disturbed by intense electron beam

NASA Astrophysics Data System (ADS)

Angus, Justin; Swanekamp, Steve; Schumer, Joseph; Mosher, Dave; Ottinger, Paul

2013-10-01

The behavior of intense electron beams (those with current densities on the order of hundreds of kA/cm2 and beam rise times on the order of 100 ns) traveling through gaseous mediums depends strongly on the transport properties of the medium. For example, the conductivity of the medium, which is very sensitive to the ionization state and temperature of the gas, has a strong influence on the beam behavior through the plasma return current. Since the beam is responsible for ionizing and heating the gas, self-consistently solving for the gas transport properties and the beam propagation is essential for an accurate description of the system. An advanced gas chemistry model to describe the transport properties of a strongly disturbed gaseous system is presented in this work. A focal point of this work is an accurate description of the medium's conductivity as the gas progresses from its weakly ionized state, where swarm models are valid, to a strongly ionized state where the Spitzer-Harm model applies. NRL Karle Fellowship

Use of capillary gas chromatography with negative ion-chemical ionization mass spectrometry for the determination of perfluorocarbon tracers in the atmosphere.

PubMed

Cooke, K M; Simmonds TPG; Nickless, G; Makepeace, A P

2001-09-01

A sensitive and selective technique for the quantitative measurement of atmospheric perfluorocarbon trace species at the sub part per quadrillion (10(-15)) levels is presented. The method utilizes advances in adsorbent enrichment techniques coupled with benchtop capillary gas chromatography and negative ion-chemical ionization mass spectrometry. The development and enhancement of sampling technology for tracer experiments is described, and the results from background measurements and a preliminary field experiment are presented. The overall precision of the analytical method with respect to the preferred tracer for these atmospheric transport studies, perfluoromethylcyclohexane, was +/-1.7%. The background concentrations of perfluorodimethylcyclobutane, perfluoromethylcyclopentane, and perfluoromethylcyclohexane at a remote coastal location (Mace Head, Ireland, 53 degrees N, 10 degrees W) were found to be 2.5 (+/-0.4), 6.8 (+/-1.0), and 5.2 fL L(-1) (+/-1.3), respectively. Background concentrations within an urban conurbation (Bristol, U.K.) were slightly greater at 3.0 (+/-1.5), 8.1 (+/-1.8), and 6.3 fL L(-1) (+/-1.1), respectively.

Risk assessment, dissipation behavior and persistence of quinalphos in/on green pea by gas chromatography with electron capture detector.

PubMed

Dar, Alamgir A; Jan, Ishrat; Wani, Ashraf A; Mubashir, Sofi; Sofi, Khurshid A; Sofi, Javid A; Dar, Irshad H

2018-06-01

Chemical investigation was carried out to examine the risk assessment, dissipation behavior, persistence, and half-life period of quinalphos in/on green pea fruit by spraying quinalphos at fruiting stage followed by another application after 10-day interval. The samples were extracted by using the quick, easy, cheap, effective, rugged, and safe method, and the residues of quinalphos were analyzed by gas chromatography with electron capture detector. Herein, we report a novel, accurate, and cost-effective gas chromatography method for the determination of average deposits of quinalphos in/on green pea. The initial deposits and half-life of quinalphos were found to be 1.20 mg/kg and 2.77 days, respectively, following the application of insecticide. Residues of quinalphos reached below detection limit of 0.05 mg/kg after 10 days at recommended dosage. For risk assessment studies, the tenth day will be safe for consumers for consumption of green pea. The developed method is simple, selective, and repeatable, and it can be extended for quinalphos-based standardization of herbal formulations containing green pea and its use in pesticide industries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-field plasma acceleration in a high-ionization-potential gas

DOE PAGES

Corde, S.; Adli, E.; Allen, J. M.; ...

2016-06-17

Plasma accelerators driven by particle beams are a very promising future accelerator technology as they can sustain high accelerating fields over long distances with high energy efficiency. They rely on the excitation of a plasma wave in the wake of a drive beam. To generate the plasma, a neutral gas can be field-ionized by the head of the drive beam, in which case the distance of acceleration and energy gain can be strongly limited by head erosion. In our research, we overcome this limit and demonstrate that electrons in the tail of a drive beam can be accelerated by upmore » to 27 GeV in a high-ionization-potential gas (argon), boosting their initial 20.35 GeV energy by 130%. Particle-in-cell simulations show that the argon plasma is sustaining very high electric fields, of ~150 GV m -1, over ~20 cm. Lastly, the results open new possibilities for the design of particle beam drivers and plasma sources.« less

Electron impact ionization in the vicinity of comets

NASA Astrophysics Data System (ADS)

Cravens, T. E.; Kozyra, J. U.; Nagy, A. F.; Gombosi, T. I.; Kurtz, M.

1987-07-01

The solar wind interacts very strongly with the extensive cometary coma, and the various interaction processes are initiated by the ionization of cometary neutrals. The main ionization mechanism far outside the cometary bow shock is photoionization by solar extreme ultraviolet radiation.Electron distributions measured in the vicinity of comets Halley and Giacobini-Zinner by instruments on the VEGA and ICE spacecraft, respectively, are used to calculate electron impact ionization frequencies. Ionization by electrons is of comparable importance to photoionization in the magnetosheaths of Comets Halley and Giacobini-Zinner. The ionization frequency in the inner part of the cometary plasma region of comet Halley is several times greater than the photoionization value. Tables of ionization frequencies as functions of electron temperature are presented for H2O, CO2, CO, O, N2, and H.

Determination of iodopropynyl butylcarbamate in cosmetic formulations utilizing pulsed splitless injection, gas chromatography with electron capture detector.

PubMed

Palmer, Kevin B; LaFon, William; Burford, Mark D

2017-09-22

Current analytical methodology for iodopropynyl butylcarbamate (IPBC) analysis focuses on the use of liquid chromatography and mass spectrometer (LC-MS), but the high instrumentation and operator investment required has resulted in the need for a cost effective alternative methodology. Past publications investigating gas chromatography with electron capture detector (GC-ECD) for IPBC quantitation proved largely unsuccessful, likely due to the preservatives limited thermal stability. The use of pulsed injection techniques commonly used for trace analysis of thermally labile pharmaceutical compounds was successfully adapted for IPBC analysis and utilizes the selectivity of GC-ECD analysis. System optimization and sample preparation improvements resulted in substantial performance and reproducibility gains. Cosmetic formulations preserved with IPBC (50-100ppm) were solvated in toluene/isopropyl alcohol and quantified over the 0.3-1.3μg/ml calibration range. The methodology was robust (relative standard deviation 4%), accurate (98% recovery), and sensitive (limit of detection 0.25ng/ml) for use in routine testing of cosmetic formulation preservation. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of Total Petroleum Hydrocarbons in Australian Groundwater Through the Improvised Gas Chromatography-Flame Ionization Detection Technique.

PubMed

Faustorilla, Maria Vilma; Chen, Zuliang; Dharmarajan, Rajarathnam; Naidu, Ravendra

2017-09-01

Assessment of total petroleum hydrocarbons (TPHs) from contaminated sites demands routine and reliable measurement at trace levels. However, the detection limits of these methods need to be improved. This study developed the programmable temperature vaporization-large volume injection (PTV-LVI) method to quantify TPHs through gas chromatography-flame ionization detection. This configuration enhances the method sensitivity for trace level detections through large volume injections and pre-concentration of analytes along the injection liner. The method was evaluated for the three commonly observed hydrocarbon fractions: C10-C14, C15-C28 and C29-C36. In comparison with conventional injection methods (splitless and pulsed splitless), PTV-LVI showed R2 values > 0.999 with enhanced limits of detection and limits of quantification values. The method was applied to real samples for routine environmental monitoring of TPHs in an Australian contaminated site characterized by refueling station. Analysis of groundwater samples in the area showed a wide range of TPH concentrations as follows: 66-1,546,000 (C10-C14), 216-22,762 (C15-C28) and 105-2,103 (C29-C36) μg/L. This method has detected trace levels, thereby measuring a wider concentration range of TPHs. These more accurate measurements can lead to the appropriate application of risk assessments and remediation techniques. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Exploring petroleum hydrocarbons in groundwater by double solid phase extraction coupled to gas chromatography-flame ionization detector.

PubMed

Pindado Jiménez, Oscar; Pérez Pastor, Rosa Ma; Escolano Segovia, Olga; del Reino Querencia, Susana

2015-01-01

This work proposes an analytical procedure for measuring aliphatic and aromatic hydrocarbons fractions present in groundwater. In this method, hydrocarbons are solid phase extracted (SPE) twice from the groundwater and the resulting fractions are analyzed by gas chromatography with flame ionization detection. The first SPE disposes the hydrocarbons present in groundwater in organic solvents and the second SPE divides them into aliphatic and aromatic hydrocarbons. The validation study is carried out and its uncertainties are discussed. Identifying the main sources of uncertainty is evaluated through applying the bottom-up approach. Limits of detection for hydrocarbons ranges are below 5 µg L(-1), precision is not above of 30%, and acceptable recoveries are reached for aliphatic and aromatic fractions studied. The uncertainty due to volume of the sample, factor of calibration and recovery are the highest contributions. The expanded uncertainty range from 13% to 26% for the aliphatic hydrocarbons ranges and from 14% to 23% for the aromatic hydrocarbons ranges. As application, the proposed method is satisfactorily applied to a set of groundwater samples collected in a polluted area where there is evidence to present a high degree of hydrocarbons. The results have shown the range of aliphatic hydrocarbons >C21-C35 is the most abundant, with values ranging from 215 µg L(-1) to 354 µg L(-1), which it is associated to a contamination due to diesel. Copyright © 2014 Elsevier B.V. All rights reserved.

Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods.

PubMed

Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

2017-03-10

Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.

Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

PubMed Central

Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

2017-01-01

Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate. PMID:28281659

Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

NASA Astrophysics Data System (ADS)

Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

2017-03-01

Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.

Qualitative and quantitative determination of extractives in heartwood of Scots pine (Pinus sylvestris L.) by gas chromatography.

PubMed

Ekeberg, Dag; Flaete, Per-Otto; Eikenes, Morten; Fongen, Monica; Naess-Andresen, Carl Fredrik

2006-03-24

A method for quantitative determination of extractives from heartwood of Scots pine (Pinus sylvestris L.) using gas chromatography (GC) with flame ionization detection (FID) was developed. The limit of detection (LOD) was 0.03 mg/g wood and the linear range (r = 0.9994) was up to 10 mg/g with accuracy within +/- 10% and precision of 18% relative standard deviation. The identification of the extractives was performed using gas chromatography combined with mass spectrometry (GC-MS). The yields of extraction by Soxhlet were tested for solid wood, small particles and fine powder. Small particles were chosen for further analysis. This treatment gave good yields of the most important extractives: pinosylvin, pinosylvin monomethyl ether, resin acids and free fatty acids. The method is used to demonstrate the variation of these extractives across stems and differences in north-south direction.

Recent applications of gas chromatography with high-resolution mass spectrometry.

PubMed

Špánik, Ivan; Machyňáková, Andrea

2018-01-01

Gas chromatography coupled to high-resolution mass spectrometry is a powerful analytical method that combines excellent separation power of gas chromatography with improved identification based on an accurate mass measurement. These features designate gas chromatography with high-resolution mass spectrometry as the first choice for identification and structure elucidation of unknown volatile and semi-volatile organic compounds. Gas chromatography with high-resolution mass spectrometry quantitative analyses was previously focused on the determination of dioxins and related compounds using magnetic sector type analyzers, a standing requirement of many international standards. The introduction of a quadrupole high-resolution time-of-flight mass analyzer broadened interest in this method and novel applications were developed, especially for multi-target screening purposes. This review is focused on the development and the most interesting applications of gas chromatography coupled to high-resolution mass spectrometry towards analysis of environmental matrices, biological fluids, and food safety since 2010. The main attention is paid to various approaches and applications of gas chromatography coupled to high-resolution mass spectrometry for non-target screening to identify contaminants and to characterize the chemical composition of environmental, food, and biological samples. The most interesting quantitative applications, where a significant contribution of gas chromatography with high-resolution mass spectrometry over the currently used methods is expected, will be discussed as well. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Freeze drying for gas chromatography stationary phase deposition

DOEpatents

Sylwester, Alan P [Livermore, CA

2007-01-02

The present disclosure relates to methods for deposition of gas chromatography (GC) stationary phases into chromatography columns, for example gas chromatography columns. A chromatographic medium is dissolved or suspended in a solvent to form a composition. The composition may be inserted into a chromatographic column. Alternatively, portions of the chromatographic column may be exposed or filled with the composition. The composition is permitted to solidify, and at least a portion of the solvent is removed by vacuum sublimation.

Probing electron delays in above-threshold ionization

DOE PAGES

Zipp, Lucas J.; Natan, Adi; Bucksbaum, Philip H.

2014-11-21

Recent experiments have revealed attosecond delays in the emission of electrons from atoms ionized by extreme UV light, offering a glimpse into the ultrafast nature of light-induced electron dynamics. In this work, we extend these measurements to the strong-field above-threshold ionization (ATI) regime, by measuring delays in the photoemission of electrons from argon in the presence of an intense laser field. We probe the ATI process with a weak coherent reference, at half the laser frequency. The interfering ionization signal reveals the relative spectral phase of adjacent ATI channels, with an equivalent resolution of a few attoseconds. These relative delaysmore » depend on the strong field, and approach zero at higher intensity. Our phase measurements of ATI electrons show how strong fields alter ionization dynamics in atoms.« less

Electron Impact Excitation-Ionization of Molecules

NASA Astrophysics Data System (ADS)

Ali, Esam Abobakr A.

In the last few decades, the study of atomic collisions by electron-impact has made significant advances. The most difficult case to study is electron impact ionization of molecules for which many approximations have to be made and the validity of these approximations can only be checked by comparing with experiment. In this thesis, I have examined the Molecular three-body distorted wave (M3DW) or Molecular four-body distorted wave (M4DW) approximations for electron-impact ionization. These models use a fully quantum mechanical approach where all particles are treated quantum mechanically and the post collision interaction (PCI) is treated to all orders of perturbation. These electron impact ionization collisions play central roles in the physics and chemistry of upper atmosphere, biofuel, the operation of discharges and lasers, radiation induced damage in biological material like damage to DNA by secondary electrons, and plasma etching processes. For the M3DW model, I will present results for electron impact single ionization of small molecules such as Water, Ethane, and Carbon Dioxide and the much larger molecules Tetrahydrofuran, phenol, furfural, 1-4 Benzoquinone. I will also present results for the four-body problem in which there are two target electrons involved in the collision. M4DW results will be presented for dissociative excitation-ionization of orientated D2. I will show that M4DW calculations using a variational wave function for the ground state that included s- and p- orbital states give better agreement to the experimental measurements than a ground state approximated as a product of two 1s-type Dyson orbitals.

Target electron ionization in Li2+-Li collisions: A multi-electron perspective

NASA Astrophysics Data System (ADS)

Śpiewanowski, M. D.; Gulyás, L.; Horbatsch, M.; Kirchner, T.

2015-05-01

The recent development of the magneto-optical trap reaction-microscope has opened a new chapter for detailed investigations of charged-particle collisions from alkali atoms. It was shown that energy-differential cross sections for ionization from the outer-shell in O8+-Li collisions at 1500 keV/amu can be readily explained with the single-active-electron approximation. Understanding of K-shell ionization, however, requires incorporating many-electron effects. An ionization-excitation process was found to play an important role. We present a theoretical study of target electron removal in Li2+-Li collisions at 2290 keV/amu. The results indicate that in outer-shell ionization a single-electron process plays the dominant part. However, the K-shell ionization results are more difficult to interpret. On one hand, we find only weak contributions from multi-electron processes. On the other hand, a large discrepancy between experimental and single-particle theoretical results indicate that multi-electron processes involving ionization from the outer shell may be important for a complete understanding of the process. Work supported by NSERC, Canada and the Hungarian Scientific Research Fund.

Chemometrics comparison of gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry Daphnia magna metabolic profiles exposed to salinity.

PubMed

Parastar, Hadi; Garreta-Lara, Elba; Campos, Bruno; Barata, Carlos; Lacorte, Silvia; Tauler, Roma

2018-06-01

The performances of gas chromatography with mass spectrometry and of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry are examined through the comparison of Daphnia magna metabolic profiles. Gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with mass spectrometry were used to compare the concentration changes of metabolites under saline conditions. In this regard, a chemometric strategy based on wavelet compression and multivariate curve resolution-alternating least squares is used to compare the performances of gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry for the untargeted metabolic profiling of Daphnia magna in control and salinity-exposed samples. Examination of the results confirmed the outperformance of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry over gas chromatography with mass spectrometry for the detection of metabolites in D. magna samples. The peak areas of multivariate curve resolution-alternating least squares resolved elution profiles in every sample analyzed by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry were arranged in a new data matrix that was then modeled by partial least squares discriminant analysis. The control and salt-exposed daphnids samples were discriminated and the most relevant metabolites were estimated using variable importance in projection and selectivity ratio values. Salinity de-regulated 18 metabolites from metabolic pathways involved in protein translation, transmembrane cell transport, carbon metabolism, secondary metabolism, glycolysis, and osmoregulation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous determination of clebopride and a major metabolite N-desbenzylclebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry.

PubMed

Robinson, P R; Jones, M D; Maddock, J; Rees, L W

1991-03-08

A procedure for the simultaneous assay of clebopride and its major metabolite N-desbenzylclebopride in plasma has been developed. The method utilizes capillary gas chromatography-negative-ion chemical ionization mass spectrometry with selected-ion monitoring of characteristic ions. Employing 2-ethoxy analogues as internal standards, the benzamides were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyric anhydride produced volatile mono- and diheptafluorobutyryl derivatives of clebopride and N-desbenzylclebopride, respectively. The methane negative-ion mass spectra of these derivatives exhibited intense high-mass ions ideal for specific quantitation of low levels in biological fluids. Using this procedure the recovery of the drug and metabolite from human plasma was found to be 84.4 +/- 1.5% (n = 3) and 77.4 +/- 4.7% (n = 3), respectively, at 0.5 ng/ml. Measurement of both compounds down to 0.10 ng/ml with a coefficient of variation of less than 10.5% is described. Plasma levels are reported in four volunteers up to 24 h following oral administration of 1 mg of clebopride malate salt.

Breakdown voltage reduction by field emission in multi-walled carbon nanotubes based ionization gas sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saheed, M. Shuaib M.; Muti Mohamed, Norani; Arif Burhanudin, Zainal, E-mail: zainabh@petronas.com.my

2014-03-24

Ionization gas sensors using vertically aligned multi-wall carbon nanotubes (MWCNT) are demonstrated. The sharp tips of the nanotubes generate large non-uniform electric fields at relatively low applied voltage. The enhancement of the electric field results in field emission of electrons that dominates the breakdown mechanism in gas sensor with gap spacing below 14 μm. More than 90% reduction in breakdown voltage is observed for sensors with MWCNT and 7 μm gap spacing. Transition of breakdown mechanism, dominated by avalanche electrons to field emission electrons, as decreasing gap spacing is also observed and discussed.

Comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones.

PubMed

Carnes, Stephanie; O'Brien, Stacey; Szewczak, Angelica; Tremeau-Cayel, Lauriane; Rowe, Walter F; McCord, Bruce; Lurie, Ira S

2017-09-01

A comparison of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography for the separation of synthetic cathinones has been conducted. Nine different mixtures of bath salts were analyzed in this study. The three different chromatographic techniques were examined using a general set of controlled synthetic cathinones as well as a variety of other synthetic cathinones that exist as positional isomers. Overall 35 different synthetic cathinones were analyzed. A variety of column types and chromatographic modes were examined for developing each separation. For the ultra high performance supercritical fluid chromatography separations, analyses were performed using a series of Torus and Trefoil columns with either ammonium formate or ammonium hydroxide as additives, and methanol, ethanol or isopropanol organic solvents as modifiers. Ultra high performance liquid chromatographic separations were performed in both reversed phase and hydrophilic interaction chromatographic modes using SPP C18 and SPP HILIC columns. Gas chromatography separations were performed using an Elite-5MS capillary column. The orthogonality of ultra high performance supercritical fluid chromatography, ultra high performance liquid chromatography, and gas chromatography was examined using principal component analysis. For the best overall separation of synthetic cathinones, the use of ultra high performance supercritical fluid chromatography in combination with gas chromatography is recommended. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative Analysis of Mixed Halogen Dioxins and Furans in Fire Debris Utilizing Atmospheric Pressure Ionization Gas Chromatography-Triple Quadrupole Mass Spectrometry.

PubMed

Organtini, Kari L; Myers, Anne L; Jobst, Karl J; Reiner, Eric J; Ross, Brian; Ladak, Adam; Mullin, Lauren; Stevens, Douglas; Dorman, Frank L

2015-10-20

Residential and commercial fires generate a complex mixture of volatile, semivolatile, and nonvolatile compounds. This study focused on the semi/nonvolatile components of fire debris to better understand firefighter exposure risks. Using the enhanced sensitivity of gas chromatography coupled to atmospheric pressure ionization-tandem mass spectrometry (APGC-MS/MS), complex fire debris samples collected from simulation fires were analyzed for the presence of potentially toxic polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs and PBDD/Fs). Extensive method development was performed to create multiple reaction monitoring (MRM) methods for a wide range of PXDD/Fs from dihalogenated through hexa-halogenated homologue groups. Higher halogenated compounds were not observed due to difficulty eluting them off the long column used for analysis. This methodology was able to identify both polyhalogenated (mixed bromo-/chloro- and polybromo-) dibenzo-p-dioxins and dibenzofurans in the simulated burn study samples collected, with the dibenzofuran species being the dominant compounds in the samples. Levels of these compounds were quantified as total homologue groups due to the limitations of commercial congener availability. Concentration ranges in household simulation debris were observed at 0.01-5.32 ppb (PXDFs) and 0.18-82.11 ppb (PBDFs). Concentration ranges in electronics simulation debris were observed at 0.10-175.26 ppb (PXDFs) and 0.33-9254.41 ppb (PBDFs). Samples taken from the particulate matter coating the firefighters' helmets contained some of the highest levels of dibenzofurans, ranging from 4.10 ppb to 2.35 ppm. The data suggest that firefighters and first responders at fire scenes are exposed to a complex mixture of potentially hundreds to thousands of different polyhalogenated dibenzo-p-dioxins and dibenzofurans that could negatively impact their health.

Determination of residual 1,4-dioxane in surfactants and cleaning agents using headspace single-drop microextraction followed by gas chromatography-flame ionization detection.

PubMed

Saraji, M; Shirvani, N

2017-02-01

Polyethoxylated surfactants are widely used in the formulation of different cleaning agents such as shampoo, dish washing and hand washing products and lotion formulation. During the production of polyethoxylated surfactants, 1,4-dioxane as a toxic and carcinogenic by-product is formed. A simple low-cost method based on headspace single-drop microextraction combined with gas chromatography-flame ionization detection was developed for the determination of 1,4-dioxane in surfactants and cleaning agents. In this method, 1,4-dioxane was extracted from 8.0 mL sample solution into a microdrop of an organic solvent, and then, it was injected to gas chromatography. The effects of such parameters as the solvent type, salt addition, microdrop volume, stirring rate, equilibrium time, extraction time and the temperature of sample solution on the extraction performance were studied and optimized. An ethoxylated surfactant containing 1,4-dioxane was used as the sample for the optimization of the extraction parameters. The linear range, determination coefficient, limit of detection and relative standard deviation of the method were 0.5-100 μg g -1 , 0.9977, 0.4 μg g -1 and 7.2% (n = 5), respectively. Different real samples including sodium lauryl ether sulphate, sodium lauryl sulphate (SLS), four brands of shampoo, and hand washing and dish washing liquids were analysed by the method. 1,4-Dioxane was detected at the concentration range of 2.4-201 μg g -1 in the samples, except dish washing liquid and SLS. A new method with the merits of simplicity, low cost, low organic solvent consumption, short analysis time, good repeatability and suitable detection limit was developed for the analysis of 1,4-dioxane in surfactants and cleaning agents. © 2016 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Quantification of isomerically summed hydrocarbon contributions to crude oil by carbon number, double bond equivalent, and aromaticity using gas chromatography with tunable vacuum ultraviolet ionization.

PubMed

Nowak, Jeremy A; Weber, Robert J; Goldstein, Allen H

2018-03-12

The ability to structurally characterize and isomerically quantify crude oil hydrocarbons relevant to refined fuels such as motor oil, diesel, and gasoline represents an extreme challenge for chromatographic and mass spectrometric techniques. This work incorporates two-dimensional gas chromatography coupled to a tunable vacuum ultraviolet soft photoionization source, the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source at the Lawrence Berkeley National Laboratory, with a time-of-flight mass spectrometer (GC × GC-VUV-TOF) to directly characterize and isomerically sum the contributions of aromatic and aliphatic species to hydrocarbon classes of four crude oils. When the VUV beam is tuned to 10.5 ± 0.2 eV, both aromatic and aliphatic crude oil hydrocarbons are ionized to reveal the complete chemical abundance of C 9 -C 30 hydrocarbons. When the VUV beam is tuned to 9.0 ± 0.2 eV only aromatic hydrocarbons are ionized, allowing separation of the aliphatic and aromatic fractions of the crude oil hydrocarbon chemical classes in an efficient manner while maintaining isomeric quantification. This technique provides an effective tool to determine the isomerically summed aromatic and aliphatic hydrocarbon compositions of crude oil, providing information that goes beyond typical GC × GC separations of the most dominant hydrocarbon isomers.

Application of elevated temperature-dispersive liquid-liquid microextraction for determination of organophosphorus pesticides residues in aqueous samples followed by gas chromatography-flame ionization detection.

PubMed

Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Rezaee Aghdam, Samaneh; Nouri, Nina; Bamorrowat, Mahdi

2016-12-01

In the present study, an elevated temperature, dispersive, liquid-liquid microextraction/gas chromatography-flame ionization detection was investigated for the determination, pre-concentration, and extraction of six organophosphorus pesticides (malathion, phosalone, dichlorvos, diazinon, profenofos, and chlorpyrifos) residues in fruit juice and aqueous samples. A mixture of 1,2-dibromoethane (extraction solvent) and dimethyl sulfoxide (disperser solvent) was injected rapidly into the sample solution heated at an elevated temperature. Analytical parameters, including enrichment factors (1600-2075), linearity (r>0.994), limits of detection (0.82-2.72ngmL(-1)) and quantification (2.60-7.36ngmL(-1)), relative standard deviations (<7%) and extraction recoveries (64-83%), showed the high efficiency of the method developed for analysis of the target analytes. The proposed procedure was used effectively to analyse selected analytes in river water and fruit juice, and diazinon was found at ngmL(-1) concentrations in apple juice. Copyright © 2016 Elsevier Ltd. All rights reserved.

Deep eutectic solvent based gas-assisted dispersive liquid-phase microextraction combined with gas chromatography and flame ionization detection for the determination of some pesticide residues in fruit and vegetable samples.

PubMed

Farajzadeh, Mir Ali; Sattari Dabbagh, Masoumeh; Yadeghari, Adeleh

2017-05-01

In this study, a gas-assisted dispersive liquid-phase microextraction method using a deep eutectic solvent as the extraction solvent combined with gas chromatography and flame ionization detection was developed for the extraction and determination of some pesticide residues in vegetable and fruit juice samples. In this method, choline chloride and 4-chlorophenol at a molar ratio of 1:2 were mixed. By heating and vortexing, a clear, water-immiscible, and homogeneous liquid was formed. The obtained deep eutectic solvent was added to an aqueous solution of the analytes in a conical test tube. Air was bubbled into the aqueous solution and a cloudy solution was obtained. During this step, the analytes were extracted into the fine droplets of the extraction solvent. After centrifugation, an aliquot of the settled phase was injected into the separation system. Under the optimum extraction conditions, enrichment factors, and extraction recoveries were obtained in the ranges of 247-355 and 49-71%, respectively. The obtained values for the limits of detection and quantification were in the ranges of 0.24-1.4 and 0.71-4.2 μg/L, respectively. The proposed method is simple, fast, efficient, and inexpensive. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Penning ionization electron spectroscopy of CO 2 clusters in collision with metastable rare gas atoms

NASA Astrophysics Data System (ADS)

Maruyama, Ryo; Tanaka, Hideyasu; Yamakita, Yoshihiro; Misaizu, Fuminori; Ohno, Koichi

2000-09-01

Penning ionization electron spectra (PIES) of CO 2 clusters have been observed for the first time. An unusually fast electron band with excess kinetic energies of 1.4-2.9 eV with respect to the monomer band for the ionic X state was observed for CO 2 clusters in collision with He*(2 3S) atoms. While for PIES with Ne*(3 3P), no such unusual band was observed. The unusual band is ascribed to autoionization into stable structures of ionic clusters to which direct ionization processes are almost impossible due to very small Franck-Condon overlaps associated with a very large geometry difference between the ionic and neutral clusters.

Ionization heating in rare-gas clusters under intense XUV laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arbeiter, Mathias; Fennel, Thomas

The interaction of intense extreme ultraviolet (XUV) laser pulses ({lambda}=32 nm, I=10{sup 11}-10{sup 14} W/cm{sup 2}) with small rare-gas clusters (Ar{sub 147}) is studied by quasiclassical molecular dynamics simulations. Our analysis supports a very general picture of the charging and heating dynamics in finite samples under short-wavelength radiation that is of relevance for several applications of free-electron lasers. First, up to a certain photon flux, ionization proceeds as a series of direct photoemission events producing a jellium-like cluster potential and a characteristic plateau in the photoelectron spectrum as observed in Bostedt et al. [Phys. Rev. Lett. 100, 133401 (2008)]. Second,more » beyond the onset of photoelectron trapping, nanoplasma formation leads to evaporative electron emission with a characteristic thermal tail in the electron spectrum. A detailed analysis of this transition is presented. Third, in contrast to the behavior in the infrared or low vacuum ultraviolet range, the nanoplasma energy capture proceeds via ionization heating, i.e., inner photoionization of localized electrons, whereas collisional heating of conduction electrons is negligible up to high laser intensities. A direct consequence of the latter is a surprising evolution of the mean energy of emitted electrons as function of laser intensity.« less

Simultaneous quantification of cannabinoids and metabolites in oral fluid by two-dimensional gas chromatography mass spectrometry

PubMed Central

Milman, Garry; Barnes, Allan J.; Lowe, Ross H.; Huestis, Marilyn A.

2010-01-01

Development and validation of a method for simultaneous identification and quantification of Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), cannabinol (CBN), and metabolites 11-hydroxy-THC (11-OH-THC) and 11-nor-9-carboxy-THC (THCCOOH) in oral fluid. Simultaneous analysis was problematic due to different physicochemical characteristics and concentration ranges. Neutral analytes, such as THC and CBD, are present in ng/mL, rather than pg/mL concentrations, as observed for the acidic THCCOOH biomarker in oral fluid. THCCOOH is not present in cannabis smoke, definitively differentiating cannabis use from passive smoke exposure. THC, 11-OH-THC, THCCOOH, CBD, and CBN quantification was achieved in a single oral fluid specimen collected with the Quantisal™ device. One mL oral fluid/buffer solution (0.25mL oral fluid and 0.75mL buffer) was applied to conditioned CEREX® Polycrom™ THC solid phase extraction (SPE) columns. After washing, THC, 11-OH-THC, CBD, and CBN were eluted with hexane/acetone/ethyl acetate (60:30:20, v/v/v), derivatized with N, O-bis-(trimethylsilyl) trifluoroacetamide and quantified by two-dimensional gas chromatography electron ionization mass spectrometry (2D-GCMS) with cold trapping. Acidic THCCOOH was separately eluted with hexane/ethyl acetate/acetic acid (75:25:2.5, v/v/v), derivatized with trifluoroacetic anhydride and hexafluoroisopropanol, and quantified by the more sensitive 2D-GCMS–electron capture negative chemical ionization (NCI-MS). Linearity was 0.5-50ng/mL for THC, 11-OH-THC, CBD and 1-50ng/mL for CBN. The linear dynamic range for THCCOOH was 7.5–500pg/mL. Intra-and inter-assay imprecision as percent RSD at three concentrations across the linear dynamic range were 0.3%-6.6%. Analytical recovery was within 13.8% of target. This new SPE 2D-GCMS assay achieved efficient quantification of five cannabinoids in oral fluid, including pg/mL concentrations of THCCOOH by combining differential elution, 2D-GCMS with electron

Analysis of small carbohydrates in several bioactive botanicals by gas chromatography with mass spectrometry and liquid chromatography with tandem mass spectrometry.

PubMed

Moldoveanu, Serban; Scott, Wayne; Zhu, Jeff

2015-11-01

Bioactive botanicals contain natural compounds with specific biological activity, such as antibacterial, antioxidant, immune stimulating, and taste improving. A full characterization of the chemical composition of these botanicals is frequently necessary. A study of small carbohydrates from the plant materials of 18 bioactive botanicals is further described. The study presents the identification of the carbohydrate using a gas chromatographic-mass spectrometric analysis that allows detection of molecules as large as maltotetraose, after changing them into trimethylsilyl derivatives. A number of carbohydrates in the plant (fructose, glucose, mannose, sucrose, maltose, xylose, sorbitol, and myo-, chiro-, and scyllo-inositols) were quantitated using a novel liquid chromatography with tandem mass spectrometric technique. Both techniques involved new method developments. The gas chromatography with mass spectrometric analysis involved derivatization and separation on a Rxi(®)-5Sil MS column with H2 as a carrier gas. The liquid chromatographic separation was obtained using a hydrophilic interaction type column, YMC-PAC Polyamine II. The tandem mass spectrometer used an electrospray ionization source in multiple reaction monitoring positive ion mode with the detection of the adducts of the carbohydrates with Cs(+) ions. The validated quantitative procedure showed excellent precision and accuracy allowing the analysis in a wide range of concentrations of the analytes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of polychlorinated biphenyls by fast gas chromatography.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alvarado, J. S.; Silzer, J.; Lemley, F.

1997-12-01

The separation of commercially available polychlorinated biphenyls (PCBs) by fast gas chromatography (fast GC) has been studied. Aroclor 1254 was separated by using two column types: DB-1 and SPB-608. The fast GC used a split-splitless injector to introduce the sample, followed by a cold trap at -90 C to focus the sample. Rapid heating was used to introduce the sample into the short chromatographic column to decrease band broadening. Hydrogen was the carrier gas at velocities of 100 to 125 cm s-1. Analyses were performed by using an electron capture detector (ECD). Separation was achieved with both columns in lessmore » than 6 min. With the greatly shortened run times, reproducibility can be tested quickly and consequently with low cost.« less

Electron-Impact Ionization Cross Section Database

National Institute of Standards and Technology Data Gateway

SRD 107 Electron-Impact Ionization Cross Section Database (Web, free access)   This is a database primarily of total ionization cross sections of molecules by electron impact. The database also includes cross sections for a small number of atoms and energy distributions of ejected electrons for H, He, and H2. The cross sections were calculated using the Binary-Encounter-Bethe (BEB) model, which combines the Mott cross section with the high-incident energy behavior of the Bethe cross section. Selected experimental data are included.

Two-dimensional gas chromatography-online hydrogenation for improved characterization of petrochemical samples.

PubMed

Potgieter, H; Bekker, R; Govender, A; Rohwer, E

2016-05-06

The Fischer-Tropsch (FT) process produces a variety of hydrocarbons over a wide carbon number range and during subsequent product workup a large variety of synthetic fuels and chemicals are produced. The complexity of the product slate obtained from this process is well documented and the high temperature FT (HT-FT) process products are spread over gas, oil and water phases. The characterization of these phases is very challenging even when using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS). Despite the increase in separation power, peak co-elution still occurs when samples containing isomeric compounds are analysed by comprehensive two dimensional GC. The separation of isomeric compounds with the same double bond equivalents is especially difficult since these compounds elute in a similar position on the GC×GC chromatogram and have identical molecular masses and similar fragmentation patterns in their electron ionization (EI) mass spectra. On-line hydrogenation after GC×GC separation is a possible way to distinguish between these isomeric compounds since the number of rings and alkene double bonds can be determined from the mass spectra of the compounds before and after hydrogenation. This paper describes development of a GC×GC method with post column hydrogenation for the determination of the backbone of cyclic/olefinic structures enabling us to differentiate between classes like dienes and cyclic olefins in complex petrochemical streams. Copyright © 2016 Elsevier B.V. All rights reserved.

The GBT Diffuse Ionized Gas Survey (GDIGS)

NASA Astrophysics Data System (ADS)

Luisi, Matteo; Anderson, Loren Dean; Liu, Bin; Bania, Thomas; Balser, Dana; Wenger, Trey; Haffner, Lawrence Matthew

2018-01-01

Diffuse ionized gas in the Galactic mid-plane known as the "Warm Ionized Medium" (WIM) makes up ~20% of the gas mass of the Milky Way and >90% of its ionized gas. It is the last major component of the interstellar medium (ISM) that has not yet been studied at high spatial and spectral resolution, and therefore many of its fundamental properties remain unclear. The Green Bank Telescope (GBT) Diffuse Ionized Gas Survey (GDIGS) is a new large survey of the Milky Way disk at C-band (4-8 GHz). The main goals of GDIGS are to investigate the properties of the WIM and to determine the connection between the WIM and high-mass star formation over the Galactic longitude and latitude range of 32 deg > l > -5 deg, |b| < 0.5 deg. We use the new VEGAS spectrometer to simultaneously observe 22 Hn-alpha radio recombination lines, 25 Hn-beta lines, 8 Hn-gamma lines, and 9 molecular lines (namely CH3OH and H2CO), and also continuum at ~60 frequencies. We average the Hn-alpha lines to produce Nyquist-sampled maps on a spatial grid of 1 arcmin, a velocity resolution of 0.5 km/s and rms sensitivities of ~3 mJy per beam. GDIGS observations are currently underway and are expected to be completed by late 2018. These data will allow us to: 1) Study for the first time the inner-Galaxy WIM unaffected by confusion from discrete HII regions, 2) determine the distribution of the inner Galaxy WIM, 3) investigate the ionization state of the WIM, 4) explore the connection between the WIM and HII regions, and 5) analyze the effect of leaked photons from HII regions on ISM dust temperatures.

Multiplex gas chromatography for use in space craft

NASA Technical Reports Server (NTRS)

Valentin, J. R.

1985-01-01

Gas chromatography is a powerful technique for the analysis of gaseous mixtures. Some limitations in this technique still exist which can be alleviated with multiplex gas chromatography (MGC). In MGC, rapid multiple sample injections are made into the column without having to wait for one determination to be finished before taking a new sample. The resulting data must then be reduced using computational methods such as cross correlation. In order to efficiently perform multiplexgas chromatography, experiments in the laboratory and on board future space craft, skills, equipment, and computer software were developed. Three new techniques for modulating, i.e., changing, sample concentrations were demonstrated by using desorption, decomposition, and catalytic modulators. In all of them, the need for a separate gas stream as the carrier was avoided by placing the modulator at the head of the column to directly modulate a sample stream. Finally, the analysis of an environmental sample by multiplex chromatography was accomplished by employing silver oxide to catalytically modulate methane in ambient air.

Influence of renormalization shielding on the electron-impact ionization process in dense partially ionized plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Mi-Young; Yoon, Jung-Sik; Jung, Young-Dae, E-mail: ydjung@hanyang.ac.kr

2015-04-15

The renormalization shielding effects on the electron-impact ionization of hydrogen atom are investigated in dense partially ionized plasmas. The effective projectile-target interaction Hamiltonian and the semiclassical trajectory method are employed to obtain the transition amplitude as well as the ionization probability as functions of the impact parameter, the collision energy, and the renormalization parameter. It is found that the renormalization shielding effect suppresses the transition amplitude for the electron-impact ionization process in dense partially ionized plasmas. It is also found that the renormalization effect suppresses the differential ionization cross section in the peak impact parameter region. In addition, it ismore » found that the influence of renormalization shielding on the ionization cross section decreases with an increase of the relative collision energy. The variations of the renormalization shielding effects on the electron-impact ionization cross section are also discussed.« less

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

NASA Technical Reports Server (NTRS)

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

1980-01-01

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

Variable pressure ionization detector for gas chromatography

DOEpatents

Buchanan, Michelle V.; Wise, Marcus B.

1988-01-01

Method and apparatus for differentiating organic compounds based on their electron affinity. An electron capture detector cell (ECD) is operated at pressures ranging from atmospheric to less than 1 torr. Through variation of the pressure within the ECD cell, the organic compounds are induced to either capture or emit electrons. Differentiation of isomeric compounds can be obtianed when, at a given pressure, one isomer is in the emission mode and the other is in the capture mode. Output of the ECD is recorded by chromatogram. The invention also includes a method for obtaining the zero-crossing pressure of a compound, defined as the pressure at which the competing emission and capture reactions are balanced and which may be correlated to the electron affinity of a compound.

Selectivity of Electronic Coherence and Attosecond Ionization Delays in Strong-Field Double Ionization

NASA Astrophysics Data System (ADS)

Kobayashi, Yuki; Reduzzi, Maurizio; Chang, Kristina F.; Timmers, Henry; Neumark, Daniel M.; Leone, Stephen R.

2018-06-01

Experiments are presented on real-time probing of coherent electron dynamics in xenon initiated by strong-field double ionization. Attosecond transient absorption measurements allow for characterization of electronic coherences as well as relative ionization timings in multiple electronic states of Xe+ and Xe2 + . A high degree of coherence g =0.4 is observed between P3 2 0-P3 0 0 of Xe2 + , whereas for other possible pairs of states the coherences are below the detection limits of the experiments. A comparison of the experimental results with numerical simulations based on an uncorrelated electron-emission model shows that the coherences produced by strong-field double ionization are more selective than predicted. Surprisingly short ionization time delays, 0.85 fs, 0.64 fs, and 0.75 fs relative to Xe+ formation, are also measured for the P2 3 , P0 3 , and P1 3 states of Xe2 + , respectively. Both the unpredicted selectivity in the formation of coherence and the subfemtosecond time delays of specific states provide new insight into correlated electron dynamics in strong-field double ionization.

Determination of methyltetrahydrophthalic anhydride in air using gas chromatography with electron-capture detection.

PubMed

Johyama, Y; Yokota, K; Fujiki, Y; Takeshita, T; Morimoto, K

1999-10-01

Methyltetrahydrophthalic anhydride (MTHPA) stimulates the production of specific IgE antibodies which can cause occupational allergy even at extremely low levels of exposure (15-22 micrograms/m3). Safe use in industry demands control of the levels of exposure causing allergic diseases. Thus, the air monitoring of MTHPA is very important, and sensitive methods are required to measure low air concentrations or short-time peak exposures. This paper outlines the use of silica-gel tubes for sampling airborne MTHPA vapour, followed by analysis using gas chromatography with electron-capture detection. No breakthrough was observed at 113, 217, 673 and 830 micrograms/m3 (sampling volume 30, 60, 60 and 20 l, respectively; relative humidity 40-55%). Concentrations > 1.0 microgram/m3 could be quantified at 20-min sampling with a sampling rate of 1 l/min. The present method can also be applied to measurements of exposure to hexahydrophthalic and methylhexahydrophthalic anhydride. The risk of MTHPA exposure in two condenser plants was also assessed by determining MTHPA levels in air of the workplace. In conclusion, our method was found to be reliable and sensitive, and can be applied to the evaluation of MTHPA exposure.

Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry peak sorting algorithm.

PubMed

Oh, Cheolhwan; Huang, Xiaodong; Regnier, Fred E; Buck, Charles; Zhang, Xiang

2008-02-01

We report a novel peak sorting method for the two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/TOF-MS) system. The objective of peak sorting is to recognize peaks from the same metabolite occurring in different samples from thousands of peaks detected in the analytical procedure. The developed algorithm is based on the fact that the chromatographic peaks for a given analyte have similar retention times in all of the chromatograms. Raw instrument data are first processed by ChromaTOF (Leco) software to provide the peak tables. Our algorithm achieves peak sorting by utilizing the first- and second-dimension retention times in the peak tables and the mass spectra generated during the process of electron impact ionization. The algorithm searches the peak tables for the peaks generated by the same type of metabolite using several search criteria. Our software also includes options to eliminate non-target peaks from the sorting results, e.g., peaks of contaminants. The developed software package has been tested using a mixture of standard metabolites and another mixture of standard metabolites spiked into human serum. Manual validation demonstrates high accuracy of peak sorting with this algorithm.

Gas Chromatography

NASA Astrophysics Data System (ADS)

Qian, Michael C.

Gas chromatography (GC) has many applications in the analysis of food products. GC has been used for the determination of fatty acids, triglycerides, cholesterol, gases, water, alcohols, pesticides, flavor compounds, and many more. While GC has been used for other food components such as sugars, oligosaccharides, amino acids, peptides, and vitamins, these substances are more suited to analysis by high performance liquid chromatography. GC is ideally suited to the analysis of volatile substances that are thermally stable. Substances such as pesticides and flavor compounds that meet these criteria can be isolated from a food and directly injected into the GC. For compounds that are thermally unstable, too low in volatility, or yield poor chromatographic separation due to polarity, a derivatization step must be done before GC analysis. The two parts of the experiment described here include the analysis of alcohols that requires no derivatization step, and the analysis of fatty acids which requires derivatization. The experiments specify the use of capillary columns, but the first experiment includes conditions for a packed column.

Detection of Extraplanar Diffuse Ionized Gas in M83

NASA Astrophysics Data System (ADS)

Boettcher, Erin; Gallagher, J. S., III; Zweibel, Ellen G.

2017-08-01

We present the first kinematic study of extraplanar diffuse ionized gas (eDIG) in the nearby, face-on disk galaxy M83 using optical emission-line spectroscopy from the Robert Stobie Spectrograph on the Southern African Large Telescope. We use a Markov Chain Monte Carlo method to decompose the [N II]λ λ 6548, 6583, Hα, and [S II]λ λ 6717, 6731 emission lines into H II region and diffuse ionized gas emission. Extraplanar, diffuse gas is distinguished by its emission-line ratios ([N II]λ6583/Hα ≳ 1.0) and its rotational velocity lag with respect to the disk ({{Δ }}v=-24 km s-1 in projection). With interesting implications for isotropy, the velocity dispersion of the diffuse gas, σ =96 km s-1, is a factor of a few higher in M83 than in the Milky Way and nearby, edge-on disk galaxies. The turbulent pressure gradient is sufficient to support the eDIG layer in dynamical equilibrium at an electron scale height of {h}z=1 kpc. However, this dynamical equilibrium model must be finely tuned to reproduce the rotational velocity lag. There is evidence of local bulk flows near star-forming regions in the disk, suggesting that the dynamical state of the gas may be intermediate between a dynamical equilibrium and a galactic fountain flow. As one of the first efforts to study eDIG kinematics in a face-on galaxy, this study demonstrates the feasibility of characterizing the radial distribution, bulk velocities, and vertical velocity dispersions in low-inclination systems. Based on observations made with the Southern African Large Telescope (SALT) under program 2015-2-SCI-004 (PI: E. Boettcher).

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

NASA Astrophysics Data System (ADS)

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

2011-11-01

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

Electron ionization of SiCl4

NASA Astrophysics Data System (ADS)

King, Simon J.; Price, Stephen D.

2011-02-01

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl4, in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl4. For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl4. Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl2+ fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl42+. The lowest energy dicationic precursor state, leading to SiCl3+ + Cl+ formation, lies 27.4 ± 0.3 eV above the ground state of SiCl4 and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Electron ionization of SiCl4.

PubMed

King, Simon J; Price, Stephen D

2011-02-21

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl(4), in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl(4). For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl(4). Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl(2) (+) fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl(4) (2+). The lowest energy dicationic precursor state, leading to SiCl(3) (+) + Cl(+) formation, lies 27.4 ± 0.3 eV above the ground state of SiCl(4) and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for simultaneous determination of fifteen organochlorine pesticides in soil and water.

PubMed

Cheng, Zhipeng; Dong, Fengshou; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Pan, Xinglu; Zheng, Yongquan

2016-02-26

In this study, the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry (APGC-QTOF-MS) has been investigated for simultaneous determination of fifteen organochlorine pesticides in soil and water. Soft ionization of atmospheric pressure gas chromatography was evaluated by comparing with traditional more energetic electron impact ionization (EI). APGC-QTOF-MS showed a sensitivity enhancement by approximately 7-305 times. The QuEChERs (Quick, Easy, Cheap, Effective, Rugged, and Safe) method was used to pretreat the soil samples and solid phase extraction (SPE) cleanup was used for water samples. Precision, accuracy and stability experiments were undertaken to evaluate the feasibility of the method. The results showed that the mean recoveries for all the pesticides from the soil samples were 70.3-118.9% with 0.4-18.3% intra-day relative standard deviations (RSD) and 1.0-15.6% inter-day RSD at 10, 50 and 500 μg/L levels, while the mean recoveries of water samples were 70.0-118.0% with 1.1-17.8% intra-day RSD and 0.5-12.2% inter-day RSD at 0.1, 0.5 and 1.0 μg/L levels. Excellent linearity (0.9931 ≦ r(2)≤ 0.9999) was obtained for each pesticides in the soil and water matrix calibration curves within the range of 0.01-1.0mg/L. The limits of detection (LOD) for each of the 15 pesticides was less than 3.00 μg/L, while the limit of quantification (LOQ) was less than 9.99 μg/L in soil and water. Furthermore, the developed method was successfully applied to monitor the targeted pesticides in real soil and water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Non-planar microfabricated gas chromatography column

DOEpatents

Lewis, Patrick R.; Wheeler, David R.

2007-09-25

A non-planar microfabricated gas chromatography column comprises a planar substrate having a plurality of through holes, a top lid and a bottom lid bonded to opposite surfaces of the planar substrate, and inlet and outlet ports for injection of a sample gas and elution of separated analytes. A plurality of such planar substrates can be aligned and stacked to provide a longer column length having a small footprint. Furthermore, two or more separate channels can enable multi-channel or multi-dimensional gas chromatography. The through holes preferably have a circular cross section and can be coated with a stationary phase material or packed with a porous packing material. Importantly, uniform stationary phase coatings can be obtained and band broadening can be minimized with the circular channels. A heating or cooling element can be disposed on at least one of the lids to enable temperature programming of the column.

Pilot study on feasibility of application of gas chromatography for the assessment of acrylamide concentration in sewage sludge.

PubMed

Włodarczyk, Elżbieta; Próba, Marta; Wolny, Lidia; Wojtal, Łukasz

2014-01-01

The aim of this study was to determine the possibility of using gas chromatography to measurement of the acrylamide concentration in sewage sludge. Acrylamide, as a toxic substance, is not indifferent to human health, but it is used in the production of plastics, dyes, adhesives, cosmetics, mortar, as well as a coagulant for water treatment, wastewater or sewage sludge conditioning. Determination of acrylamide by gas chromatography was based on standard: EPA Method 8032A "Acrylamid by gas chromatography." It consists of a bromination reaction of the compound in the presence of dibromopropendial derivative, a triple extraction with the ethyl acetate, a concentration of the eluate sample up to the 1 ml volume, and an analysis by the gas chromatography using an electron capture detector (ECD). The acrylamide concentration of was calculated according to the formula presented in the mentioned standard. All samples were performed twice (the difference between the results was not greater than 10%), and the average value of the four samples was 17.64 µg/L(-1). The presence of acrylamide in sewage sludge has been confirmed.

Pulse length of ultracold electron bunches extracted from a laser cooled gas

PubMed Central

Franssen, J. G. H.; Frankort, T. L. I.; Vredenbregt, E. J. D.; Luiten, O. J.

2017-01-01

We present measurements of the pulse length of ultracold electron bunches generated by near-threshold two-photon photoionization of a laser-cooled gas. The pulse length has been measured using a resonant 3 GHz deflecting cavity in TM110 mode. We have measured the pulse length in three ionization regimes. The first is direct two-photon photoionization using only a 480 nm femtosecond laser pulse, which results in short (∼15 ps) but hot (∼104 K) electron bunches. The second regime is just-above-threshold femtosecond photoionization employing the combination of a continuous-wave 780 nm excitation laser and a tunable 480 nm femtosecond ionization laser which results in both ultracold (∼10 K) and ultrafast (∼25 ps) electron bunches. These pulses typically contain ∼103 electrons and have a root-mean-square normalized transverse beam emittance of 1.5 ± 0.1 nm rad. The measured pulse lengths are limited by the energy spread associated with the longitudinal size of the ionization volume, as expected. The third regime is just-below-threshold ionization which produces Rydberg states which slowly ionize on microsecond time scales. PMID:28396879

Enantioselective comprehensive two-dimensional gas chromatography of lavender essential oil.

PubMed

Krupčík, Ján; Gorovenko, Roman; Špánik, Ivan; Armstrong, Daniel W; Sandra, Pat

2016-12-01

The enantiomeric composition of several chiral markers in lavender essential oil was studied by flow modulated comprehensive two-dimensional gas chromatography operated in the reverse flow mode and hyphenated to flame ionization and quadrupole mass spectrometric detection. Two capillary column series were used in this study, 2,3-di-O-ethyl-6-O-tert-butyldimethylsilyl-β-cyclodextrin or 2,3,6-tri-O-methyl-β-cyclodextrin, as the chiral column in the first dimension and α polyethylene glycol column in the second dimension. Combining the chromatographic data obtained on these column series, the enantiomeric and excess ratios for α-pinene, β-pinene, camphor, lavandulol, borneol, and terpinen-4-ol were determined. This maybe a possible route to assess the authenticity of lavender essential oil. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

IC 5181: An S0 Galaxy with Ionized Gas on Polar Orbits

NASA Astrophysics Data System (ADS)

Pizzella, A.; Morelli, L.; Corsini, E. M.; Dalla Bontá, E.; Cesetti, M.

2014-05-01

The nearby S0 galaxy IC 5181 is studied to address the origin of the ionized gas component that orbits the galaxy on polar orbit. We perform detailed photometric and spectroscopic observations measuring the surface brightness distribution of the stars (I band), ionized gas of IC 5181 (Hα narrow band), the ionized-gas and stellar kinematics along both the major and minor axis, and the corresponding line strengths of the Lick indices. We conclude that the galaxy hosts a geometrically and kinematically decoupled component of ionized gas. It is elongated along the galaxy minor axis and in orthogonal rotation with respect to the galaxy disk. The result is suggesting that the gas component is not related to the stars having an external origin. The gas was accreted by IC 5181 on polar orbits from the surrounding environment.

IONIZED GAS IN THE FIRST 10 kpc OF THE INTERSTELLAR GALACTIC HALO: METAL ION FRACTIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howk, J. Christopher; Consiglio, S. Michelle, E-mail: jhowk@nd.edu, E-mail: smconsiglio@ucla.edu

2012-11-10

We present direct measures of the ionization fractions of several sulfur ions in the Galactic warm ionized medium (WIM). We obtained high-resolution ultraviolet absorption-line spectroscopy of post-asymptotic giant branch stars in the globular clusters Messier 3 [(l, b) = (42.{sup 0}2, +78.{sup 0}7), d = 10.2 kpc, and z = 10.0 kpc] and Messier 5 [(l, b) = (3.{sup 0}9, +46.{sup 0}8), d = 7.5 kpc, and z = +5.3 kpc] with the Hubble Space Telescope and Far Ultraviolet Spectroscopic Explorer to measure, or place limits on, the column densities of S I, S II, S III, S IV, Smore » VI, and H I. These clusters also house millisecond pulsars, whose dispersion measures give an electron column density from which we infer the H II column in these directions. We find fractions of S{sup +2} in the WIM for the M 3 and M 5 sight lines x(S{sup +2}) {identical_to} N(S{sup +2})/N(S) = 0.33 {+-} 0.07 and 0.47 {+-} 0.09, respectively, with variations perhaps related to location. With negligible quantities of the higher ionization states, we conclude that S{sup +} and S{sup +2} account for all of the S in the WIM. We extend the methodology to study the ion fractions in the warm and hot ionized gas of the Milky Way, including the high ions Si{sup +3}, C{sup +3}, N{sup +4}, and O{sup +5}. The vast majority of the Galactic ionized gas is warm (T {approx} 10{sup 4} K) and photoionized (the WIM) or very hot (T > 4 Multiplication-Sign 10{sup 5} K) and collisionally ionized. The common tracer of ionized gas beyond the Milky Way, O{sup +5}, traces <1% of the total ionized gas mass of the Milky Way.« less

Shock Structure Analysis and Aerodynamics in a Weakly Ionized Gas Flow

NASA Technical Reports Server (NTRS)

Saeks, R.; Popovic, S.; Chow, A. S.

2006-01-01

The structure of a shock wave propagating through a weakly ionized gas is analyzed using an electrofluid dynamics model composed of classical conservation laws and Gauss Law. A viscosity model is included to correctly model the spatial scale of the shock structure, and quasi-neutrality is not assumed. A detailed analysis of the structure of a shock wave propagating in a weakly ionized gas is presented, together with a discussion of the physics underlying the key features of the shock structure. A model for the flow behind a shock wave propagating through a weakly ionized gas is developed and used to analyze the effect of the ionization on the aerodynamics and performance of a two-dimensional hypersonic lifting body.

Determination of amantadine in biological fluids using simultaneous derivatization and dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection.

PubMed

Farajzadeh, Mir Ali; Nouri, Nina; Alizadeh Nabil, Ali Akbar

2013-12-01

A one-step derivatization and microextraction technique for the determination of amantadine in the human plasma and urine samples is presented. An appropriate mixture of methanol (disperser solvent), 1,2-dibromoethane (extraction solvent), and butylchloroformate (derivatization agent) is rapidly injected into samples. After centrifuging, the sedimented phase is analyzed by gas chromatography-flame ionization detection (GC-FID). The kind of extraction and disperser solvents and their volumes, amount of derivatization agent and reaction/extraction time which are effective in derivatization/dispersive liquid-liquid microextraction (DLLME) procedure are optimized. Under the optimal conditions, the enrichment factor (EF) of the target analyte was obtained to be 408 and 420, and limit of detection (LOD) 4.2 and 2.7ngmL(-1), in plasma and urine respectively. The linear range is 14-5000 and 8.7-5000ng/mL for plasma and urine, respectively (squared correlation coefficient≥0.990). The relative recoveries obtained for the spiked plasma and urine samples are between 72% and 93%. Moreover, the inter- and intra-day precisions are acceptable at all spiked concentrations (relative standard deviation <7%). Finally the method was successfully applied to determine amantadine in biological samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Graphene oxide-based dispersive micro-solid phase extraction for separation and preconcentration of nicotine from biological and environmental water samples followed by gas chromatography-flame ionization detection.

PubMed

Mahpishanian, Shokouh; Sereshti, Hassan

2014-12-01

Graphene oxide (GO) has showed great potential to use as an adsorbent in sample preparation procedures. In this research, GO was used as an effective adsorbent in a simple GO-based dispersive micro-solid phase extraction (GO-D-µ-SPE) method for isolation and preconcentration of nicotine prior to gas chromatography-flame ionization detection (GC-FID). The prepared GO was characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), thermogravimetric analysis/differential thermal analysis (TGA/DTA), and ultraviolet-visible (UV-vis) absorption spectroscopy techniques. Various experimental parameters affecting the extraction recovery, including the amount of GO, extraction time, pH of the sample solution, salt concentration, and desorption conditions were investigated and optimized. Under the optimized conditions, a linear response was obtained in the concentration range of 5-2000 ng mL(-1) with a determination coefficient of 0.9987. The limit of detection (LOD) of the method at a signal to noise ratio of 3 was 1.5 ng mL(-1). The linearity was in the concentration range of 5-2000 ng mL(-1) with a determination coefficient of 0.9987. Intraday and inter-day precisions were obtained equal to 2.7% and 5.2%, respectively. The method was successfully applied to the nicotine analysis in biological and water samples with the recoveries in the range of 88.7-109.7%. Copyright © 2014 Elsevier B.V. All rights reserved.

Electron-impact-ionization dynamics of S F6

NASA Astrophysics Data System (ADS)

Bull, James N.; Lee, Jason W. L.; Vallance, Claire

2017-10-01

A detailed understanding of the dissociative electron ionization dynamics of S F6 is important in the modeling and tuning of dry-etching plasmas used in the semiconductor manufacture industry. This paper reports a crossed-beam electron ionization velocity-map imaging study on the dissociative ionization of cold S F6 molecules, providing complete, unbiased kinetic energy distributions for all significant product ions. Analysis of these distributions suggests that fragmentation following single ionization proceeds via formation of S F5 + or S F3 + ions that then dissociate in a statistical manner through loss of F atoms or F2, until most internal energy has been liberated. Similarly, formation of stable dications is consistent with initial formation of S F4 2 + ions, which then dissociate on a longer time scale. These data allow a comparison between electron ionization and photoionization dynamics, revealing similar dynamical behavior. In parallel with the ion kinetic energy distributions, the velocity-map imaging approach provides a set of partial ionization cross sections for all detected ionic fragments over an electron energy range of 50-100 eV, providing partial cross sections for S2 +, and enables the cross sections for S F4 2 + from S F+ to be resolved.

Analysis of fragrance compounds in blood samples of mice by gas chromatography, mass spectrometry, GC/FTIR and GC/AES after inhalation of sandalwood oil.

PubMed

Jirovetz, L; Buchbauer, G; Jäger, W; Woidich, A; Nikiforov, A

1992-01-01

After inhalation experiments with sandalwood oil and the pure fragrance compounds coumarin and alpha-terpineol, substances were detected and measured in the blood samples of test animals (mice) using gas chromatography/mass spectrometry (GC/MS) (MID) in connection with GC/FTIR (SWC), GC/AES (carbon and oxygen trace) and flame ionization detection/gas chromatography. Using tiglinic acid benzyl ester as the internal standard the following concentrations in serum could be found: alpha-santalol 6.1 ng/mL, beta-santalol 5.3 ng/mL and alpha-santalene 0.5 ng/mL. In separate inhalation experiments with coumarin and with alpha-terpineol the corresponding concentrations were 7.7 ng/mL and 6.9 ng/mL, respectively.

Improved Thermal Modulator for Gas Chromatography

NASA Technical Reports Server (NTRS)

Hasselbrink, Ernest Frederick, Jr.; Hunt, Patrick J.; Sacks, Richard D.

2008-01-01

An improved thermal modulator has been invented for use in a variant of gas chromatography (GC). The variant in question denoted as two-dimensional gas chromatography (2DGC) or GC-GC involves the use of three series-connected chromatographic columns, in the form of capillary tubes coated interiorly with suitable stationary phases (compounds for which different analytes exhibit different degrees of affinity). The two end columns are relatively long and are used as standard GC columns. The thermal modulator includes the middle column, which is relatively short and is not used as a standard GC column: instead, its temperature is modulated to affect timed adsorption and desorption of analyte gases between the two end columns in accordance with a 2DGC protocol.

Ultrafast gas chromatography method with direct injection for the quantitative determination of benzene, toluene, ethylbenzene, and xylenes in commercial gasoline.

PubMed

Miranda, Nahieh Toscano; Sequinel, Rodrigo; Hatanaka, Rafael Rodrigues; de Oliveira, José Eduardo; Flumignan, Danilo Luiz

2017-04-01

Benzene, toluene, ethylbenzene, and xylenes are some of the most hazardous constituents found in commercial gasoline samples; therefore, these components must be monitored to avoid toxicological problems. We propose a new routine method of ultrafast gas chromatography coupled to flame ionization detection for the direct determination of benzene, toluene, ethylbenzene, and xylenes in commercial gasoline. This method is based on external standard calibration to quantify each compound, including the validation step of the study of linearity, detection and quantification limits, precision, and accuracy. The time of analysis was less than 3.2 min, with quantitative statements regarding the separation and quantification of all compounds in commercial gasoline samples. Ultrafast gas chromatography is a promising alternative method to official analytical techniques. Government laboratories could consider using this method for quality control. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionization and current growth in N/sub 2/ at very high electric field to gas density ratios

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gylys, V.T.; Jelenkovic, B.M.; Phelps, A.V.

1989-05-01

Measurements and analyses have been made of electron impact ionization and of current growth in pulsed, low-current, prebreakdown discharges in parallel-plane geometry in N/sub 2/ at very high electric field to gas density ratios E/n and low products of the gas density n and electrode separation d. The E/n range and nd ranges were 1

The kinematics of the diffuse ionized gas in NGC 4666

NASA Astrophysics Data System (ADS)

Voigtländer, P.; Kamphuis, P.; Marcelin, M.; Bomans, D. J.; Dettmar, R.-J.

2013-06-01

Context. The global properties of the interstellar medium with processes such as infall and outflow of gas and a large scale circulation of matter and its consequences for star formation and chemical enrichment are important for the understanding of galaxy evolution. Aims: In this paper we studied the kinematics and morphology of the diffuse ionized gas (DIG) in the disk and in the halo of the star forming spiral galaxy NGC 4666 to derive information about its kinematical properties. Especially, we searched for infalling and outflowing ionized gas. Methods: We determined surface brightness, radial velocity, and velocity dispersion of the warm ionized gas via high spectral resolution (R ≈ 9000) Fabry-Pérot interferometry. This allows the determination of the global velocity field and the detection of local deviations from this velocity field. We calculated models of the DIG distribution and its kinematics for comparison with the measured data. In this way we determined fundamental parameters such as the inclination and the scale height of NGC 4666, and established the need for an additional gas component to fit our observed data. Results: We found individual areas, especially along the minor axis, with gas components reaching into the halo which we interpret as an outflowing component of the DIG. As the main result of our study, we were able to determine that the vertical structure of the DIG distribution in NGC 4666 is best modeled with two components of ionized gas, a thick and a thin disk with 0.8 kpc and 0.2 kpc scale height, respectively. Therefore, the enhanced star formation in NGC 4666 drives an outflow and also maintains a thick ionized gas layer reminiscent of the Reynold's layer in the Milky Way.

[Determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry].

PubMed

Xia, Guanghui; Shen, Weijian; Yu, Keyao; Wu, Bin; Zhang, Rui; Shen, Chongyu; Zhao, Zengyun; Bian, Xiaohong; Xu, Jiyang

2014-07-01

A method was developed for the determination of four insecticide residues in honey and royal jelly by gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The honey and royal jelly samples were treated with different preparation methods as the result of the different components. The honey sample was extracted with ethyl acetate and cleaned up with primary second amine, and the royal jelly sample was extracted with acetonitrile-water (1:1, v/v), and cleaned up with a C18 solid-phase extraction column. Finally, the extracts of the honey and royal jelly were analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode separately. External standard calibration method was used for quantification. The linearities of calibration curves of the four insecticides were good with the correlation coefficients greater than 0.99 in the range of 50-500 microg/L. The limits of the detection (LODs) of the four insecticides were in the range of 0.12- 5.0 microg/kg, and the limits of the quantification (LOQs) were in the range of 0.40-16.5 microg/kg. The recoveries of the four insecticides spiked in honey and royal jelly at three spiked levels (10, 15 and 20 microg/kg) were in the range of 78.2 -110.0%, and the relative standard deviations (RSDs) were all below 14%. The sensitivity and selectivity of this method were good with no interfering peaks. The proposed method is simple quick and effective to analyze the four insecticide residues in honey and royal jelly.

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

PubMed

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

2004-06-15

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

Highly ionized atoms in cooling gas

NASA Technical Reports Server (NTRS)

Edgar, R. J.; Chevalier, R. A.

1986-01-01

The ionization of low density gas cooling from a high temperature was calculated. The evolution during the cooling is assumed to be isochoric, isobaric, or a combination of these cases. The calculations are used to predict the column densities and ultraviolet line luminosities of highly ionized atoms in cooling gas. In a model for cooling of a hot galactic corona, it is shown that the observed value of N(N V) can be produced in the cooling gas, while the predicted value of N(Si IV) falls short of the observed value by a factor of about 5. The same model predicts fluxes of ultraviolet emission lines that are a factor of 10 lower than the claimed detections of Feldman, Brune, and Henry. Predictions are made for ultraviolet lines in cooling flows in early-type galaxies and clusters of galaxies. It is shown that the column densities of interest vary over a fairly narrow range, while the emission line luminosities are simply proportional to the mass inflow rate.

Electron impact ionization of cycloalkanes, aldehydes, and ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Dhanoj; Antony, Bobby, E-mail: bka.ism@gmail.com

The theoretical calculations of electron impact total ionization cross section for cycloalkane, aldehyde, and ketone group molecules are undertaken from ionization threshold to 2 keV. The present calculations are based on the spherical complex optical potential formalism and complex scattering potential ionization contribution method. The results of most of the targets studied compare fairly well with the recent measurements, wherever available and the cross sections for many targets are predicted for the first time. The correlation between the peak of ionization cross sections with number of target electrons and target parameters is also reported. It was found that the crossmore » sections at their maximum depend linearly with the number of target electrons and with other target parameters, confirming the consistency of the values reported here.« less

Early stages in the history of gas chromatography.

PubMed

Kolomnikov, Ivan G; Efremov, Alexander M; Tikhomirova, Tatyana I; Sorokina, Nadezhda M; Zolotov, Yury A

2018-02-16

The creation of gas chromatography is traditionally associated with the names of Nobel Prize winner Archer Martin and his colleagues Richard Synge and Anthony James. However, sometimes references to their predecessors can be found. An investigation conducted by the authors of this article not only confirmed the reliability of these references; but in fact led to the conclusion that by 1952, which is commonly believed to be the year when gas chromatography was born, many research papers had already been devoted to this method, mainly, in its gas-solid version. These papers are considered in this article. Copyright © 2018. Published by Elsevier B.V.

Separation and identification of corticosterone metabolites by liquid chromatography--electrospray ionization mass spectrometry.

PubMed

Miksík, I; Vylitová, M; Pácha, J; Deyl, Z

1999-04-16

High-performance liquid chromatography coupled to atmospheric pressure ionization-electrospray ionization mass spectrometry (API-ESI-MS) was investigated for the analysis of corticosterone metabolites; their characterization was obtained by combining the separation on Zorbax Eclipse XDB C18 column (eluted with a methanol-water-acetic acid gradient) with identification using positive ion mode API-ESI-MS and selected ion analysis. The applicability of this method was verified by monitoring the activity of steroid converting enzymes (20beta-hydroxysteroid dehydrogenase and 11beta-hydroxysteroid dehydrogenase) in avian intestines.

Alfvén ionization in an MHD-gas interactions code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, A. D.; Diver, D. A.

A numerical model of partially ionized plasmas is developed in order to capture their evolving ionization fractions as a result of Alfvén ionization (AI). The mechanism of, and the parameter regime necessary for, AI is discussed and an expression for the AI rate based on fluid parameters, from a gas-MHD model, is derived. This AI term is added to an existing MHD-gas interactions' code, and the result is a linear, 2D, two-fluid model that includes momentum transfer between charged and neutral species as well as an ionization rate that depends on the velocity fields of both fluids. The dynamics ofmore » waves propagating through such a partially ionized plasma are investigated, and it is found that AI has a significant influence on the fluid dynamics as well as both the local and global ionization fraction.« less

21 CFR 862.2250 - Gas liquid chromatography system for clinical use.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Gas liquid chromatography system for clinical use... Instruments § 862.2250 Gas liquid chromatography system for clinical use. (a) Identification. A gas liquid... pressure. The device may include accessories such as columns, gases, column supports, and liquid coating...

21 CFR 862.2250 - Gas liquid chromatography system for clinical use.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Gas liquid chromatography system for clinical use... Instruments § 862.2250 Gas liquid chromatography system for clinical use. (a) Identification. A gas liquid... pressure. The device may include accessories such as columns, gases, column supports, and liquid coating...

21 CFR 862.2250 - Gas liquid chromatography system for clinical use.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Gas liquid chromatography system for clinical use... Instruments § 862.2250 Gas liquid chromatography system for clinical use. (a) Identification. A gas liquid... pressure. The device may include accessories such as columns, gases, column supports, and liquid coating...

21 CFR 862.2250 - Gas liquid chromatography system for clinical use.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Gas liquid chromatography system for clinical use... Instruments § 862.2250 Gas liquid chromatography system for clinical use. (a) Identification. A gas liquid... pressure. The device may include accessories such as columns, gases, column supports, and liquid coating...

21 CFR 862.2250 - Gas liquid chromatography system for clinical use.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Gas liquid chromatography system for clinical use... Instruments § 862.2250 Gas liquid chromatography system for clinical use. (a) Identification. A gas liquid... pressure. The device may include accessories such as columns, gases, column supports, and liquid coating...

[Determination of residual toluene diisocyanate in sponge bra by gas chromatography].

PubMed

Wang, Aixia; Ye, Ping; Huang, Nan; Chen, Yan; Li, Xinggen

2017-06-08

A gas chromatography (GC) with internal standard method was developed for the determination of residual toluene diisocyanate (TDI) in sponge bra. The samples were extracted with ethyl acetate dehydrated, and cleaned up with 0.22 μm microfiltration membrane. The residual toluene diisocyanate was separated on a DB-624 capillary column using temperature programming. The flame ionization detector (FID) was used at 250 ℃. The inlet temperature was 180 ℃ with nitrogen as carrier gas. The linear range was 10-200 mg/L ( R 2 =0.9989) for TDI. The average recovery ranged from 80.5% to 91.6% with RSD not more than 7.9%( n =6). The limit of detection (LOD) and limit of quantification (LOQ) were 10 mg/kg and 100 mg/kg, respectively. The developed method was then utilized to analyse the 100 batches of sponge bra samples from the manufacturing enterprises, the entity shops and electric business platforms. The method is simple, time-saving and environment friendly with high sensitivity and good reproducibility, and has practical application value due to its low-cost and short-circle.

Analysis of phthalate esters in soils near an electronics manufacturing facility and from a non-industrialized area by gas purge microsyringe extraction and gas chromatography.

PubMed

Wu, Wei; Hu, Jia; Wang, Jinqi; Chen, Xuerong; Yao, Na; Tao, Jing; Zhou, Yi-Kai

2015-03-01

Here, a novel technique is described for the extraction and quantitative determination of six phthalate esters (PAEs) from soils by gas purge microsyringe extraction and gas chromatography. Recovery of PAEs ranged from 81.4% to 120.3%, and the relative standard deviation (n=6) ranged from 5.3% to 10.5%. Soil samples were collected from roadsides, farmlands, residential areas, and non-cultivated areas in a non-industrialized region, and from the same land-use types within 1 km of an electronics manufacturing facility (n=142). Total PAEs varied from 2.21 to 157.62 mg kg(-1) in non-industrialized areas and from 8.63 to 171.64 mg kg(-1) in the electronics manufacturing area. PAE concentrations in the non-industrialized area were highest in farmland, followed (in decreasing order) by roadsides, residential areas, and non-cultivated soil. In the electronics manufacturing area, PAE concentrations were highest in roadside soils, followed by residential areas, farmland, and non-cultivated soils. Concentrations of dimethyl phthalate (DMP), diethyl phthalate (DEP), and di-n-butyl phthalate (DnBP) differed significantly (P<0.01) between the industrial and non-industrialized areas. Principal component analysis indicated that the strongest explanatory factor was related to DMP and DnBP in non-industrialized soils and to butyl benzyl phthalate (BBP) and DMP in soils near the electronics manufacturing facility. Congener-specific analysis confirmed that diethylhexyl phthalate (DEHP) was a predictive indication both in the non-industrialized area (r(2)=0.944, P<0.01) and the industrialized area (r(2)=0.860, P<0.01). The higher PAE contents in soils near the electronics manufacturing facility are of concern, considering the large quantities of electronic wastes generated with ongoing industrialization. Copyright © 2014 Elsevier B.V. All rights reserved.

Comparison of mass spectrometry-based electronic nose and solid phase microextraction gas chromatography-mass spectrometry technique to assess infant formula oxidation.

PubMed

Fenaille, François; Visani, Piero; Fumeaux, René; Milo, Christian; Guy, Philippe A

2003-04-23

Two headspace techniques based on mass spectrometry detection (MS), electronic nose, and solid phase microextraction coupled to gas chromatography-mass spectrometry (SPME-GC/MS) were evaluated for their ability to differentiate various infant formula powders based on changes of their volatiles upon storage. The electronic nose gave unresolved MS fingerprints of the samples gas phases that were further submitted to principal component analysis (PCA). Such direct MS recording combined to multivariate treatment enabled a rapid differentiation of the infant formulas over a 4 week storage test. Although MS-based electronic nose advantages are its easy-to-use aspect and its meaningful data interpretation obtained with a high throughput (100 samples per 24 h), its greatest disadvantage is that the present compounds could not be identified and quantified. For these reasons, a SPME-GC/MS measurement was also investigated. This technique allowed the identification of saturated aldehydes as the main volatiles present in the headspace of infant milk powders. An isotope dilution assay was further developed to quantitate hexanal as a potential indicator of infant milk powder oxidation. Thus, hexanal content was found to vary from roughly 500 and 3500 microg/kg for relatively non-oxidized and oxidized infant formulas, respectively.

Thermal modulation for gas chromatography

NASA Technical Reports Server (NTRS)

Block, Bruce P. (Inventor); Libardoni, Mark (Inventor); Stewart, Kristine (Inventor); Sacks, Richard D. (Inventor); Hasselbrink, Ernest F. (Inventor); Waite, J. Hunter (Inventor)

2007-01-01

A thermal modulator device for gas chromatography and associated methods. The thermal modulator device includes a cooling member, an electrically conductive capillary in direct thermal contact with the cooling member, and a power supply electrically coupled to the capillary and operable for controlled resistive heating of the capillary.

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

PubMed

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

2011-08-01

The volatile compounds of pork, other meats and meat products were studied using an electronic nose and gas chromatography mass spectrometer with headspace analyzer (GCMS-HS) for halal verification. The zNose™ was successfully employed for identification and differentiation of pork and pork sausages from beef, mutton and chicken meats and sausages which were achieved using a visual odor pattern called VaporPrint™, derived from the frequency of the surface acoustic wave (SAW) detector of the electronic nose. GCMS-HS was employed to separate and analyze the headspace gasses from samples into peaks corresponding to individual compounds for the purpose of identification. Principal component analysis (PCA) was applied for data interpretation. Analysis by PCA was able to cluster and discriminate pork from other types of meats and sausages. It was shown that PCA could provide a good separation of the samples with 67% of the total variance accounted by PC1. Copyright © 2011 Elsevier Ltd. All rights reserved.

Threshold law for electron-atom impact ionization

NASA Technical Reports Server (NTRS)

Temkin, A.

1982-01-01

A derivation of the explicit form of the threshold law for electron impact ionization of atoms is presented, based on the Coulomb-dipole theory. The important generalization is made of using a dipole function whose moment is the dipole moment formed by an inner electron and the nucleus. The result is a modulated quasi-linear law for the yield of positive ions which applies to positron-atom impact ionization.

Electron-electron correlation in two-photon double ionization of He-like ions

NASA Astrophysics Data System (ADS)

Hu, S. X.

2018-01-01

Electron correlation plays a crucial role in quantum many-body physics ranging from molecular bonding and strong-field-induced multielectron ionization, to superconducting in materials. Understanding the dynamic electron correlation in the photoionization of relatively simple quantum three-body systems, such as He and He-like ions, is an important step toward manipulating complex systems through photoinduced processes. Here we have performed ab initio investigations of two-photon double ionization (TPDI) of He and He-like ions (L i+,B e2 + , and C4 +) exposed to intense attosecond x-ray pulses. Results from such fully correlated quantum calculations show weaker and weaker electron correlation effects in TPDI spectra as the ionic charge increases, which is opposite to the intuition that the absolute increase of correlation in the ground state should lead to more equal energy sharing in photoionization. These findings indicate that the final-state electron-electron correlation ultimately determines the energy sharing of the two ionized electrons in TPDI.

Transition-matrix theory for two-photon ionization of rare-gas atoms and isoelectronic ions with application to argon

NASA Astrophysics Data System (ADS)

Starace, Anthony F.; Jiang, Tsin-Fu

1987-08-01

A transition-matrix theory for two-photon ionization processes in rare-gas atoms or isoelectronic ions is presented. Uncoupled ordinary differential equations are obtained for the radial functions needed to calculate the two-photon transition amplitude. The implications of these equations are discussed in detail. In particular, the role of correlations involving virtually excited electron pairs, which are known to be essential to the description of single-photon processes, is examined for multiphoton ionization processes. Additionally, electron scattering interactions between two electron-hole pairs are introduced into our transition amplitude in the boson approximation since these have been found important in two-photon ionization of xenon by L'Huillier and Wendin [J. Phys. B 20, L37 (1987)]. Application of our theory is made to two-photon ionization of the 3p subshell of argon below the one-photon ionization threshold. Our results are compared to previous calculations of McGuire [Phys. Rev. A 24, 835 (1981)], of Moccia, Rahman, and Rizzo [J. Phys. B 16, 2737 (1983)], and of Pindzola and Kelly [Phys. Rev. A 11, 1543 (1975)]. Results are presented for both circularly and linearly polarized photons. Among our findings are, firstly, that the electron scattering interactions, which have not been included in previous calculations for argon, produce a substantial reduction in the two-photon single-ionization cross section below the one-photon ionization threshold, which is in agreement with findings of L'Huillier and Wendin for xenon. Secondly, we find that de-excitation of virtually excited electron pairs by absorption of a photon is important for describing the interaction of the atom with the photon field, as in the case of single-photon ionization processes, but that further excitation of virtually excited electron pairs by the photon field has completely negligible effects, indicating a major simplification of the theory for higher-order absorption processes.

Identification and characterization of complex bioactive oligosaccharides in white and red wine by a combination of mass spectrometry and gas chromatography.

PubMed

Bordiga, Matteo; Travaglia, Fabiano; Meyrand, Mickael; German, J Bruce; Lebrilla, Carlito B; Coïsson, Jean Daniel; Arlorio, Marco; Barile, Daniela

2012-04-11

Over forty-five complex free oligosaccharides (of which several are novel) have been isolated and chemically characterized by gas chromatography and high resolution and high mass accuracy matrix-assisted laser desorption/ionization mass spectrometry (MALDI-FTICR MS) in red and white wines, Grignolino and Chardonnay, respectively. Oligosaccharides with a degree of polymerization between 3 and 14 were separated from simple monosaccharides and disaccharides by solid-phase extraction. The concentrations of free oligosaccharides were over 100 mg/L in both red and white wines. The free oligosaccharides-characterized for the first time in the present study-include hexose-oligosaccharides, xyloglucans, and arabinogalactans and may be the natural byproduct of the degradation of cell wall polysaccharides. The coupled gas chromatography and accurate mass spectrometry approach revealed an effective method to characterize and quantify complex functional oligosaccharides in both red and white wine.

Identification and Characterization of Complex Bioactive Oligosaccharides in White and Red Wine by a Combination of Mass Spectrometry and Gas Chromatography

PubMed Central

Bordiga, Matteo; Travaglia, Fabiano; Meyrand, Mickael; German, J. Bruce; Lebrilla, Carlito B.; Coïsson, Jean Daniel; Arlorio, Marco; Barile, Daniela

2012-01-01

Over forty-five complex free oligosaccharides (of which several are novel) have been isolated and chemically characterized by gas chromatography and high resolution and high mass accuracy matrix-assisted laser desorption/ionization mass spectrometry (MALDI-FTICR MS) in red and white wines, Grignolino and Chardonnay, respectively. Oligosaccharides with a degree of polymerization between 3 and 14 were separated from simple monosaccharides and disaccharides by solid-phase extraction. The concentrations free oligosaccharides were over 100 mg/L in both red and white wines. The free oligosaccharides—characterized for the first time in the present study include hexose-oligosaccharides, xyloglucans and arabinogalactans, and may be the natural by-products of the degradation of cell wall polysaccharides. The coupled gas chromatography and accurate mass spectrometry approach revealed an effective method to characterize and quantify complex functional oligosaccharides in both red and white wine. PMID:22429017

Gauging Metallicity of Diffuse Gas under an Uncertain Ionizing Radiation Field

NASA Astrophysics Data System (ADS)

Chen, Hsiao-Wen; Johnson, Sean D.; Zahedy, Fakhri S.; Rauch, Michael; Mulchaey, John S.

2017-06-01

Gas metallicity is a key quantity used to determine the physical conditions of gaseous clouds in a wide range of astronomical environments, including interstellar and intergalactic space. In particular, considerable effort in circumgalactic medium (CGM) studies focuses on metallicity measurements because gas metallicity serves as a critical discriminator for whether the observed heavy ions in the CGM originate in chemically enriched outflows or in more chemically pristine gas accreted from the intergalactic medium. However, because the gas is ionized, a necessary first step in determining CGM metallicity is to constrain the ionization state of the gas which, in addition to gas density, depends on the ultraviolet background radiation field (UVB). While it is generally acknowledged that both the intensity and spectral slope of the UVB are uncertain, the impact of an uncertain spectral slope has not been properly addressed in the literature. This Letter shows that adopting a different spectral slope can result in an order of magnitude difference in the inferred CGM metallicity. Specifically, a harder UVB spectrum leads to a higher estimated gas metallicity for a given set of observed ionic column densities. Therefore, such systematic uncertainties must be folded into the error budget for metallicity estimates of ionized gas. An initial study shows that empirical diagnostics are available for discriminating between hard and soft ionizing spectra. Applying these diagnostics helps reduce the systematic uncertainties in CGM metallicity estimates.

Synthesis of refractory organic matter in the ionized gas phase of the solar nebula.

PubMed

Kuga, Maïa; Marty, Bernard; Marrocchi, Yves; Tissandier, Laurent

2015-06-09

In the nascent solar system, primitive organic matter was a major contributor of volatile elements to planetary bodies, and could have played a key role in the development of the biosphere. However, the origin of primitive organics is poorly understood. Most scenarios advocate cold synthesis in the interstellar medium or in the outer solar system. Here, we report the synthesis of solid organics under ionizing conditions in a plasma setup from gas mixtures (H2(O)-CO-N2-noble gases) reminiscent of the protosolar nebula composition. Ionization of the gas phase was achieved at temperatures up to 1,000 K. Synthesized solid compounds share chemical and structural features with chondritic organics, and noble gases trapped during the experiments reproduce the elemental and isotopic fractionations observed in primitive organics. These results strongly suggest that both the formation of chondritic refractory organics and the trapping of noble gases took place simultaneously in the ionized areas of the protoplanetary disk, via photon- and/or electron-driven reactions and processing. Thus, synthesis of primitive organics might not have required a cold environment and could have occurred anywhere the disk is ionized, including in its warm regions. This scenario also supports N2 photodissociation as the cause of the large nitrogen isotopic range in the solar system.

An innovative online VFA monitoring system for the anerobic process, based on headspace gas chromatography.

PubMed

Boe, Kanokwan; Batstone, Damien John; Angelidaki, Irini

2007-03-01

A new method for online measurement of volatile fatty acids (VFA) in anerobic digesters has been developed based on headspace gas chromatography (HSGC). The method applies ex situ VFA stripping with variable headspace volume and gas analysis by gas chromatography-flame ionization detection (GC-FID). In each extraction, digester sample was acidified with H(3)PO(4) and NaHSO(4), then heated to strip the VFA into the gas phase. The gas was sampled in a low friction glass syringe before injected into the GC for measurement. The system has been tested for online monitoring of a lab-scale CSTR reactor treating manure for more than 6 months and has shown good agreement with off-line analysis. The system is capable of measuring individual VFA components. This is of advantage since specific VFA components such as propionic and butyric acid can give extra information about the process status. Another important advantage of this sensor is that there is no filtration, which makes possible application in high solids environments. The system can thus be easily applied in a full-scale biogas reactor by connecting the system to the liquid circulation loop to obtain fresh sample from the reactor. Local calibration is needed but automatic calibration is also possible using standard addition method. Sampling duration is 25-40 min, depending on the washing duration, and sensor response is 10 min. This is appropriate for full-scale reactors, since dynamics within most biogas reactors are of the order of several hours.

High-resolution liquid chromatography/electrospray ionization time-of-flight mass spectrometry combined with liquid chromatography/electrospray ionization tandem mass spectrometry to identify polyphenols from grape antioxidant dietary fiber.

PubMed

Touriño, Sonia; Fuguet, Elisabet; Jáuregui, Olga; Saura-Calixto, Fulgencio; Cascante, Marta; Torres, Josep Lluís

2008-11-01

Grape antioxidant dietary fiber (GADF) is a dietary supplement that combines the benefits of both fiber and antioxidants that help prevent cancer and cardiovascular diseases. The antioxidant polyphenolic components in GADF probably help prevent cancer in the digestive tract, where they are bioavailable. Mass spectrometry coupled to liquid chromatography is a powerful tool for the analysis of complex plant derivatives such as GADF. We use a combination of MS techniques, namely liquid chromatography/electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOF-MS) and liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) on a triple quadrupole, for the identification of the polyphenolic constituents of the soluble fraction of GADF. First, we separated the mixture into four fractions which were tested for phenolic constituents using the TOF system in the full scan mode. The high sensitivity and resolution of the TOF detector over the triple quadrupole facilitate the preliminary characterization of the fractions. Then we used LC/ESI-MS/MS to identify the individual phenols through MS/MS experiments (product ion scan, neutral loss scan, precursor ion scan). Finally, most of the identities were unequivocally confirmed by accurate mass measurements on the TOF spectrometer. LC/ESI-TOF-MS combined with MS/MS correctly identifies the bioactive polyphenolic components from the soluble fraction of GADF. High-resolution TOF-MS is particularly useful for identifying the structure of compounds with the same LC/ESI-MS/MS fragmentation patterns.

Gas chromatography: Possible application of advanced instrumentation developed for solar system exploration to space station cabin atmospheres

NASA Technical Reports Server (NTRS)

Carle, G. C.

1985-01-01

Gas chromatography (GC) technology was developed for flight experiments in solar system exploration. The GC is a powerful analytical technique with simple devices separating individual components from complex mixtures to make very sensitive quantitative and qualitative measurements. It monitors samples containing mixtures of fixed gases and volatile organic molecules. The GC was used on the Viking mission in support of life detection experiments and on the Pioneer Venus Large Probe to determine the composition of the venusian atmosphere. A flight GC is under development to study the progress and extent of STS astronaut denitrogenation prior to extravehicular activity. Advanced flight GC concepts and systems for future solar system exploration are also studied. Studies include miniature ionization detectors and associated control systems capable of detecting from ppb up to 100% concentration levels. Further miniaturization is investigated using photolithography and controlled chemical etching in silicon wafers. Novel concepts such as ion mobility drift spectroscopy and multiplex gas chromatography are also developed for future flight experiments. These powerful analytical concepts and associated hardware are ideal for the monitoring of cabin atmospheres containing potentially dangerous volatile compounds.

Semi-automated 96-well solid-phase extraction and gas chromatography-negative chemical ionization tandem mass spectrometry for the trace analysis of fluprostenol in rat plasma.

PubMed

Gauw, R D; Stoffolano, P J; Kuhlenbeck, D L; Patel, V S; Garver, S M; Baker, T R; Wehmeyer, K R

2000-07-21

Semi-automated 96-well plate solid-phase extraction (SPE) was used for sample preparation of fluprostenol, a prostaglandin analog, in rat plasma prior to detection by gas chromatography-negative chemical ionization tandem mass spectrometry (GC-NCI-MS-MS). A liquid handling system was utilized for all aspects of sample handling prior to SPE including transferring of samples into a 96-well format, preparation of standards as well as addition of internal standard to standards, quality control samples and study samples. SPE was performed in a 96-well plate format using octadecylsilane packing and the effluent from the SPE was dried in a custom-made 96-well apparatus. The sample residue was derivatized sequentially with pentafluorobenzylbromide followed by N-methyl-N-trimethylsilyltrifluoroacetamide. The derivatized sample was then analyzed using GC-NCI-MS-MS. The dynamic range for the method was from 7 to 5800 pg/ml with a 0.1-ml plasma sample. The methodology was evaluated over a 4-day period and demonstrated an accuracy of 90-106% with a precision of 2.4-12.9%.

Capillary liquid chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

PubMed

Ostman, Pekka; Jäntti, Sirkku; Grigoras, Kestas; Saarela, Ville; Ketola, Raimo A; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto

2006-07-01

A miniaturized nebulizer chip for capillary liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (capillary LC-microchip APCI-MS) is presented. The APCI chip consists of two wafers, a silicon wafer and a Pyrex glass wafer. The silicon wafer has a DRIE etched through-wafer nebulizer gas inlet, an edge capillary insertion channel, a stopper, a vaporizer channel and a nozzle. The platinum heater electrode and pads for electrical connection were patterned on to the Pyrex glass wafer. The two wafers were joined by anodic bonding, creating a microchip version of an APCI-source. The sample inlet capillary from an LC column is directly connected to the vaporizer channel of the APCI chip. The etched nozzle in the microchip forms a narrow sample plume, which is ionized by an external corona needle, and the formed ions are analyzed by a mass spectrometer. The nebulizer chip enables for the first time the use of low flow rate separation techniques with APCI-MS. The performance of capillary LC-microchip APCI-MS was tested with selected neurosteroids. The capillary LC-microchip APCI-MS provides quantitative repeatability and good linearity. The limits of detection (LOD) with a signal-to-noise ratio (S/N) of 3 in MS/MS mode for the selected neurosteroids were 20-1000 fmol (10-500 nmol l(-1)). LODs (S/N = 3) with commercial macro APCI with the same compounds using the same MS were about 10 times higher. Fast heat transfer allows the use of the optimized temperature for each compound during an LC run. The microchip APCI-source provides a convenient and easy method to combine capillary LC to any API-MS equipped with an APCI source. The advantages and potentials of the microchip APCI also make it a very attractive interface in microfluidic APCI-MS.

Optimization of headspace solid-phase microextraction by means of an experimental design for the determination of methyl tert.-butyl ether in water by gas chromatography-flame ionization detection.

PubMed

Dron, Julien; Garcia, Rosa; Millán, Esmeralda

2002-07-19

A procedure for determination of methyl tert.-butyl ether (MTBE) in water by headspace solid-phase microextraction (HS-SPME) has been developed. The analysis was carried out by gas chromatography with flame ionization detection. The extraction procedure, using a 65-microm poly(dimethylsiloxane)-divinylbenzene SPME fiber, was optimized following experimental design. A fractional factorial design for screening and a central composite design for optimizing the significant variables were applied. Extraction temperature and sodium chloride concentration were significant variables, and 20 degrees C and 300 g/l were, respectively chosen for the best extraction response. With these conditions, an extraction time of 5 min was sufficient to extract MTBE. The calibration linear range for MTBE was 5-500 microg/l and the detection limit 0.45 microg/l. The relative standard deviation, for seven replicates of 250 microg/l MTBE in water, was 6.3%.

Electrophysical and optophysical properties of air ionized by a short pulse of fast electrons

NASA Astrophysics Data System (ADS)

Vagin, Iu. P.; Stal', N. L.; Khokhlov, V. D.; Chernoiarskii, A. A.

A method for solving the nonstationary kinetic equation of electron deceleration is developed which is based on the multigroup approximation. The electron distribution function in air ionized by nonstationary sources of primary electrons is determined, and the avalanche formation of secondary electrons is considered. Theoretical and experimental results are presented on the time dependence of the air luminescence intensity in two spectral intervals, one including the 391.4 nm N2(+) band and the other including the 337.1 nm N2 band, for different values of gas pressure under the effect of a short beam of electrons with energies of 100 keV.

Advanced PIC-MCC simulation for the investigation of step-ionization effect in intermediate-pressure capacitively coupled plasmas

NASA Astrophysics Data System (ADS)

Kim, Jin Seok; Hur, Min Young; Kim, Chang Ho; Kim, Ho Jun; Lee, Hae June

2018-03-01

A two-dimensional parallelized particle-in-cell simulation has been developed to simulate a capacitively coupled plasma reactor. The parallelization using graphics processing units is applied to resolve the heavy computational load. It is found that the step-ionization plays an important role in the intermediate gas pressure of a few Torr. Without the step-ionization, the average electron density decreases while the effective electron temperature increases with the increase of gas pressure at a fixed power. With the step-ionization, however, the average electron density increases while the effective electron temperature decreases with the increase of gas pressure. The cases with the step-ionization agree well with the tendency of experimental measurement. The electron energy distribution functions show that the population of electrons having intermediate energy from 4.2 to 12 eV is relaxed by the step-ionization. Also, it was observed that the power consumption by the electrons is increasing with the increase of gas pressure by the step-ionization process, while the power consumption by the ions decreases with the increase of gas pressure.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; determination of organochlorine pesticides and polychlorinated biphenyls in bottom sediment by dual capillary-column gas chromatography with electron-capture detection

USGS Publications Warehouse

Foreman, William T.; Connor, Brooke F.; Furlong, Edward T.; Vaught, Deborah G.; Merten, Leslie M.

1995-01-01

A method for the determination of 30 individual organochlorine pesticides, total toxaphene, and total polychlorinated biphenyls (PCBs) in bottom sediment is described. The method isolates the pesticides and PCBs by solvent extraction with dichlorobenzene, removes inorganic sulfur, large naturally occurring molecules, and other unwanted interferences by gel permeation chromatography, and further cleans up and class fractionates the extract using adsorption chromatography. The com- pounds then are instrumentally determined using dual capillary-column gas chromatography with electron-capture detection. Reporting limits range from 1 to 5 micrograms per kilogram for 30 individual pesticides, 50 micrograms per kilogram for total PCBs, and 200 micrograms per kilogram for total toxaphene. The method also is designed to allow the simultaneous isolation of 79 other semivolatile organic compounds from the sediment, which are separately quantified using gas chromatography with mass spectrometric detection. The method was developed in support of the U.S. Geological Survey's National Water-Quality Assessment program.

Oxidation of Carbon Nanotubes in an Ionizing Environment.

PubMed

Koh, Ai Leen; Gidcumb, Emily; Zhou, Otto; Sinclair, Robert

2016-02-10

In this work, we present systematic studies on how an illuminating electron beam which ionizes molecular gas species can influence the mechanism of carbon nanotube oxidation in an environmental transmission electron microscope (ETEM). We found that preferential attack of the nanotube tips is much more prevalent than for oxidation in a molecular gas environment. We establish the cumulative electron doses required to damage carbon nanotubes from 80 keV electron beam irradiation in gas versus in high vacuum. Our results provide guidelines for the electron doses required to study carbon nanotubes within or without a gas environment, to determine or ameliorate the influence of the imaging electron beam. This work has important implications for in situ studies as well as for the oxidation of carbon nanotubes in an ionizing environment such as that occurring during field emission.

Gauging Metallicity of Diffuse Gas under an Uncertain Ionizing Radiation Field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hsiao-Wen; Zahedy, Fakhri S.; Johnson, Sean D.

Gas metallicity is a key quantity used to determine the physical conditions of gaseous clouds in a wide range of astronomical environments, including interstellar and intergalactic space. In particular, considerable effort in circumgalactic medium (CGM) studies focuses on metallicity measurements because gas metallicity serves as a critical discriminator for whether the observed heavy ions in the CGM originate in chemically enriched outflows or in more chemically pristine gas accreted from the intergalactic medium. However, because the gas is ionized, a necessary first step in determining CGM metallicity is to constrain the ionization state of the gas which, in addition tomore » gas density, depends on the ultraviolet background radiation field (UVB). While it is generally acknowledged that both the intensity and spectral slope of the UVB are uncertain, the impact of an uncertain spectral slope has not been properly addressed in the literature. This Letter shows that adopting a different spectral slope can result in an order of magnitude difference in the inferred CGM metallicity. Specifically, a harder UVB spectrum leads to a higher estimated gas metallicity for a given set of observed ionic column densities. Therefore, such systematic uncertainties must be folded into the error budget for metallicity estimates of ionized gas. An initial study shows that empirical diagnostics are available for discriminating between hard and soft ionizing spectra. Applying these diagnostics helps reduce the systematic uncertainties in CGM metallicity estimates.« less

Gas Chromatography-Based Ethylene Measurement of Arabidopsis Seedlings.

PubMed

Yoon, Gyeong Mee; Chen, Yi-Chun

2017-01-01

Plants tightly regulate the biosynthesis of ethylene to control growth and development and respond to a wide range of biotic and abiotic stresses. To understand the molecular mechanism by which plants regulate ethylene biosynthesis as well as to identify stimuli triggering the alteration of ethylene production in plants, it is essential to have a reliable tool with which one can directly measure in vivo ethylene concentration. Gas chromatography is a routine detection technique for separation and analysis of volatile compounds with relatively high sensitivity. Gas chromatography has been widely used to measure the ethylene produced by plants, and has in turn become a valuable tool for ethylene research. Here, we describe a protocol for measuring the ethylene produced by dark-grown Arabidopsis seedlings using a gas chromatograph.

Determination of valproic acid in human plasma using dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection

PubMed Central

Fazeli-Bakhtiyari, Rana; Panahi-Azar, Vahid; Sorouraddin, Mohammad Hossein; Jouyban, Abolghasem

2015-01-01

Objective(s): Dispersive liquid-liquid microextraction coupled with gas chromatography (GC)-flame ionization detector was developed for the determination of valproic acid (VPA) in human plasma. Materials and Methods: Using a syringe, a mixture of suitable extraction solvent (40 µl chloroform) and disperser (1 ml acetone) was quickly added to 10 ml of diluted plasma sample containing VPA (pH, 1.0; concentration of NaCl, 4% (w/v)), resulting in a cloudy solution. After centrifugation (6000 rpm for 6 min), an aliquot (1 µl) of the sedimented organic phase was removed using a 1-µl GC microsyringe and injected into the GC system for analysis. One variable at a time optimization method was used to study various parameters affecting the extraction efficiency of target analyte. Then, the developed method was fully validated for its accuracy, precision, recovery, stability, and robustness. Results: Under the optimum extraction conditions, good linearity range was obtained for the calibration graph, with correlation coefficient higher than 0.998. Limit of detection and lower limit of quantitation were 3.2 and 6 μg/ml, respectively. The relative standard deviations of intra and inter-day analysis of examined compound were less than 11.5%. The relative recoveries were found in the range of 97 to 107.5%. Finally, the validated method was successfully applied to the analysis of VPA in patient sample. Conclusion: The presented method has acceptable levels of precision, accuracy and relative recovery and could be used for therapeutic drug monitoring of VPA in human plasma. PMID:26730332

Determination of anabolic steroids with gas chromatography-ion trap mass spectrometry using hydrogen as carrier gas.

PubMed

Impens, S; De Wasch, K; De Brabander, H

2001-01-01

Helium is considered to be the ideal carrier gas for gas chromatography/mass spectrometry (GC/MS) in general, and for use with an ion trap in particular. Helium is an inert gas, can be used without special precautions for security and, moreover, it is needed as a damping gas in the trap. A disadvantage of helium is the high viscosity resulting in long GC run times. In this work hydrogen was tested as an alternative carrier gas for GC in performing GC/MS analyses. A hydrogen generator was used as a safe source of hydrogen gas. It is demonstrated that hydrogen can be used as a carrier gas for the gas chromatograph in combination with helium as make-up gas for the trap. The analysis time was thus shortened and the chromatographic performance was optimized. Although hydrogen has proven useful as a carrier gas in gas chromatography coupled to standard detectors such as ECD or FID, its use is not mentioned extensively in the literature concerning gas chromatography-ion trap mass spectrometry. However, it is worth considering as a possibility because of its chromatographic advantages and its advantageous price when using a hydrogen generator. Copyright 2001 John Wiley & Sons, Ltd.

Analyte quantification with comprehensive two-dimensional gas chromatography: assessment of methods for baseline correction, peak delineation, and matrix effect elimination for real samples.

PubMed

Samanipour, Saer; Dimitriou-Christidis, Petros; Gros, Jonas; Grange, Aureline; Samuel Arey, J

2015-01-02

Comprehensive two-dimensional gas chromatography (GC×GC) is used widely to separate and measure organic chemicals in complex mixtures. However, approaches to quantify analytes in real, complex samples have not been critically assessed. We quantified 7 PAHs in a certified diesel fuel using GC×GC coupled to flame ionization detector (FID), and we quantified 11 target chlorinated hydrocarbons in a lake water extract using GC×GC with electron capture detector (μECD), further confirmed qualitatively by GC×GC with electron capture negative chemical ionization time-of-flight mass spectrometer (ENCI-TOFMS). Target analyte peak volumes were determined using several existing baseline correction algorithms and peak delineation algorithms. Analyte quantifications were conducted using external standards and also using standard additions, enabling us to diagnose matrix effects. We then applied several chemometric tests to these data. We find that the choice of baseline correction algorithm and peak delineation algorithm strongly influence the reproducibility of analyte signal, error of the calibration offset, proportionality of integrated signal response, and accuracy of quantifications. Additionally, the choice of baseline correction and the peak delineation algorithm are essential for correctly discriminating analyte signal from unresolved complex mixture signal, and this is the chief consideration for controlling matrix effects during quantification. The diagnostic approaches presented here provide guidance for analyte quantification using GC×GC. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Temperature programmable microfabricated gas chromatography column

DOEpatents

Manginell, Ronald P.; Frye-Mason, Gregory C.

2003-12-23

A temperature programmable microfabricated gas chromatography column enables more efficient chemical separation of chemical analytes in a gas mixture by the integration of a resistive heating element and temperature sensing on the microfabricated column. Additionally, means are provided to thermally isolate the heated column from their surroundings. The small heat capacity and thermal isolation of the microfabricated column improves the thermal time response and power consumption, both important factors for portable microanalytical systems.

Degradation spectra and ionization yields of electrons in gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inokuti, M.; Douthat, D.A.; Rau, A.R.P.

1975-01-01

Progress in the microscopic theory of electron degradation in gases by Platzman, Fano, and co-workers is outlined. The theory consists of (1) the cataloging of all major inelastic-collision cross sections for electrons (including secondary-electron energy distribution in a single ionizing collision) and (2) the evaluation of cumulative consequences of individual electron collisions for the electrons themselves as well as for target molecules. For assessing the data consistency and reliability and extrapolating the data to the unexplored ranges of variables (such as electron energy), a series of plots devised by Platzman are very powerful. Electron degradation spectra were obtained through numericalmore » solution of the Spencer--Fano equation for all electron energies down to the first ionization thresholds for a few examples such as He and Ne. The systematics of the solutions resulted in the recognition of approximate scaling properties of the degradation spectra for different initial electron energies and pointed to new methods of more efficient treatment. Systematics of the ionization yields and their energy dependence on the initial electron energy were also recognized. Finally, the Spencer--Fano equation for the degradation spectra and the Fowler equation for the ionization and other yields are tightly linked with each other by a set of variational principles. (52 references, 7 figures) (DLC)« less

Study of dust particle charging in weakly ionized inert gases taking into account the nonlocality of the electron energy distribution function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Filippov, A. V., E-mail: fav@triniti.ru; Dyatko, N. A.; Kostenko, A. S.

2014-11-15

The charging of dust particles in weakly ionized inert gases at atmospheric pressure has been investigated. The conditions under which the gas is ionized by an external source, a beam of fast electrons, are considered. The electron energy distribution function in argon, krypton, and xenon has been calculated for three rates of gas ionization by fast electrons: 10{sup 13}, 10{sup 14}, and 10{sup 15} cm{sup −1}. A model of dust particle charging with allowance for the nonlocal formation of the electron energy distribution function in the region of strong plasma quasi-neutrality violation around the dust particle is described. The nonlocalitymore » is taken into account in an approximation where the distribution function is a function of only the total electron energy. Comparative calculations of the dust particle charge with and without allowance for the nonlocality of the electron energy distribution function have been performed. Allowance for the nonlocality is shown to lead to a noticeable increase in the dust particle charge due to the influence of the group of hot electrons from the tail of the distribution function. It has been established that the screening constant virtually coincides with the smallest screening constant determined according to the asymptotic theory of screening with the electron transport and recombination coefficients in an unperturbed plasma.« less

Utilizing two detectors in the measurement of trichloroacetic acid in human urine by reaction headspace gas chromatography.

PubMed

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

2018-05-16

A reaction headspace gas chromatography (HS-GC) technique was investigated for quantitatively analyzing trichloroacetic acid in human urine. This method is based on the decomposition reaction of trichloroacetic acid under high-temperature conditions. The carbon dioxide and chloroform formed from the decomposition reaction can be respectively detected by the thermal conductivity detection HS-GC and flame ionization detection HS-GC. The reaction can be completed in 60 min at 90°C. This method was used to quantify 25 different human urine samples, which had a range of trichloroacetic acid from 0.52 to 3.47 mg/L. It also utilized two different detectors, the thermal conductivity detector and the flame ionization detector. The present reaction HS-GC method is accurate, reliable and well suitable for batch detection of trichloroacetic acid in human urine. Copyright © 2018 John Wiley & Sons, Ltd.

Determination of guaifenesin in human serum by capillary gas chromatography and electron capture detection.

PubMed

Sharaf, Maged H M; Stiff, Dwight D

2004-06-29

A method for the quantitation of guaifenesin in human serum has been developed and validated. The procedure involves liquid-liquid extraction of the serum sample in the presence of mephenesin as an internal standard, followed by derivatization and analysis using capillary gas chromatography (GC) and electron capture detection (ECD). Different solvents were tested for extraction of guaifenesin from serum. n-Hexane/dichloromethane (1:1, v/v) gave the highest recovery and the lowest background and was chosen as the extraction solvent. After extraction, the residue of guaifenesin was derivatized at 60 degrees C for 30 min, with trifluoroacetic acid anhydride (TFAA) in toluene in the presence of pyridine. Excess trifluoroacetic acid anhydride was removed using dilute solution of ammonium hydroxide. The method proved to be linear over the range of 25.0-1000 ng/ml. Recovery of guaifenesin from spiked samples was consistent, averaging 75.5% at 50.0 ng/ml with a range of 72.0-80.0% (N = 8 determinations) and averaging 78% at 800 ng/ml with a range of 76.0-81.0% (N = 8 determinations). The internal standard recovery was also consistent averaging 72.8% with a range of 67.0-76.0% (N = 16 determinations). Copyright 2004 Elsevier B.V.

Preparation of the spacer for narrow electrode gap configuration in ionization-based gas sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saheed, Mohamed Shuaib Mohamed; Mohamed, Norani Muti; Burhanudin, Zainal Arif

2012-09-26

Carbon nanotubes (CNTs) have started to be developed as the sensing element for ionization-based gas sensors due to the demand for improved sensitivity, selectivity, stability and other sensing properties beyond what can be offered by the conventional ones. Although these limitations have been overcome, the problems still remain with the conventional ionization-based gas sensors in that they are bulky and operating with large breakdown voltage and high temperature. Recent studies have shown that the breakdown voltage can be reduced by using nanostructured electrodes and narrow electrode gap. Nanostructured electrode in the form of aligned CNTs array with evenly distributed nanotipsmore » can enhance the linear electric field significantly. The later is attributed to the shorter conductivity path through narrow electrode gap. The paper presents the study on the design consideration in order to realize ionization based gas sensor using aligned carbon nanotubes array in an optimum sensor configuration with narrow electrode gap. Several deposition techniques were studied to deposit the spacer, the key component that can control the electrode gap. Plasma spray deposition, electron beam deposition and dry oxidation method were employed to obtain minimum film thickness around 32 {mu}m. For plasma spray method, sand blasting process is required in order to produce rough surface for strong bonding of the deposited film onto the surface. Film thickness, typically about 39 {mu}m can be obtained. For the electron beam deposition and dry oxidation, the film thickness is in the range of nanometers and thus unsuitable to produce the spacer. The deposited multilayer film consisting of copper, alumina and ferum on which CNTs array will be grown was found to be removed during the etching process. This is attributed to the high etching rate on the thin film which can be prevented by reducing the rate and having a thicker conductive copper film.« less

The Formation and Physical Origin of Highly Ionized Cooling Gas

NASA Astrophysics Data System (ADS)

Bordoloi, Rongmon; Wagner, Alexander Y.; Heckman, Timothy M.; Norman, Colin A.

2017-10-01

We present a simple model that explains the origin of warm, diffuse gas seen primarily as highly ionized absorption-line systems in the spectra of background sources. We predict the observed column densities of several highly ionized transitions such as O VI, O vii, Ne viii, N v, and Mg x, and we present a unified comparison of the model predictions with absorption lines seen in the Milky Way disk, Milky Way halo, starburst galaxies, the circumgalactic medium, and the intergalactic medium at low and high redshifts. We show that diffuse gas seen in such diverse environments can be simultaneously explained by a simple model of radiatively cooling gas. We show that most such absorption-line systems are consistent with being collisionally ionized, and we estimate the maximum-likelihood temperature of the gas in each observation. This model satisfactorily explains why O VI is regularly observed around star-forming low-z L* galaxies, and why N v is rarely seen around the same galaxies. We further present some consequences of this model in quantifying the dynamics of the cooling gas around galaxies and predict the shock velocities associated with such flows. A unique strength of this model is that while it has only one free (but physically well-constrained) parameter, it nevertheless successfully reproduces the available data on O VI absorbers in the interstellar, circumgalactic, intragroup, and intergalactic media, as well as the available data on other absorption lines from highly ionized species.

Electron Impact Ionization and Dissociative Ionization of C2H2

NASA Technical Reports Server (NTRS)

Srivastava, S. K.

1995-01-01

By utilizing a crossed electron beam collision geometry, a combination of time-of-flight (TOF) and quadrupole mass spectrometers, and the relative flow technique1 normalized values of cross sections and appearance energies (AP) were obtained for the formation of singly and multiply ionized species resulting from the ionization and dissociation of C2H2. Details ont he apparatus and technique have been published previously.2,3.

Impact of comprehensive two-dimensional gas chromatography with mass spectrometry on food analysis.

PubMed

Tranchida, Peter Q; Purcaro, Giorgia; Maimone, Mariarosa; Mondello, Luigi

2016-01-01

Comprehensive two-dimensional gas chromatography with mass spectrometry has been on the separation-science scene for about 15 years. This three-dimensional method has made a great positive impact on various fields of research, and among these that related to food analysis is certainly at the forefront. The present critical review is based on the use of comprehensive two-dimensional gas chromatography with mass spectrometry in the untargeted (general qualitative profiling and fingerprinting) and targeted analysis of food volatiles; attention is focused not only on its potential in such applications, but also on how recent advances in comprehensive two-dimensional gas chromatography with mass spectrometry will potentially be important for food analysis. Additionally, emphasis is devoted to the many instances in which straightforward gas chromatography with mass spectrometry is a sufficiently-powerful analytical tool. Finally, possible future scenarios in the comprehensive two-dimensional gas chromatography with mass spectrometry food analysis field are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The detection of dissolved gases in transformer oil by gas chromatography with helium ionization detector

NASA Astrophysics Data System (ADS)

Deng, Xian-qin; Fang, Hua; Li, Min-xian

2017-07-01

The GC-PDD with the technology of valve cutting and helium ionization detector was used to analyze the dissolved gases in ultra-high voltage(UHV) and extra-high voltage(EHV) transformer oil. The detection limit(DL) reached ppb grade, especially for the featuring gas—C2H2 and H2, whose DL could reach 5ppb and 11ppb respectively. The test reproducibility of the instrument was about 1% and the correlation coefficient of standard curve-r is greater or equal to 0.99, which showed obvious advantage compared with normal GC. In addition, the auxiliary gas of H2 was not used in this instrument, which completely improved the safety performance. Thus, the application of GC-PDD has significant meaning in warning potential malfunction inside the ultra-high voltage transformer in advance.

Synthesis of refractory organic matter in the ionized gas phase of the solar nebula

PubMed Central

Kuga, Maïa; Marty, Bernard; Marrocchi, Yves; Tissandier, Laurent

2015-01-01

In the nascent solar system, primitive organic matter was a major contributor of volatile elements to planetary bodies, and could have played a key role in the development of the biosphere. However, the origin of primitive organics is poorly understood. Most scenarios advocate cold synthesis in the interstellar medium or in the outer solar system. Here, we report the synthesis of solid organics under ionizing conditions in a plasma setup from gas mixtures (H2(O)−CO−N2−noble gases) reminiscent of the protosolar nebula composition. Ionization of the gas phase was achieved at temperatures up to 1,000 K. Synthesized solid compounds share chemical and structural features with chondritic organics, and noble gases trapped during the experiments reproduce the elemental and isotopic fractionations observed in primitive organics. These results strongly suggest that both the formation of chondritic refractory organics and the trapping of noble gases took place simultaneously in the ionized areas of the protoplanetary disk, via photon- and/or electron-driven reactions and processing. Thus, synthesis of primitive organics might not have required a cold environment and could have occurred anywhere the disk is ionized, including in its warm regions. This scenario also supports N2 photodissociation as the cause of the large nitrogen isotopic range in the solar system. PMID:26039983

Plasma channel created by ionization of gas by a surface wave

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konovalov, V. N.; Kuz’min, G. P.; Minaev, I. M., E-mail: minaev1945@mail.ru

2015-09-15

Conditions for gas ionization in the field of a slow surface wave excited by a microwave source are considered. The gas ionization rate and the plasma density distribution over the radius of the discharge tube were studied by the optical method. The experiments were conducted in a dielectric tube with a radius much smaller than the tube length, the gas pressure being ∼1–3 Torr. It is shown that the stationary distribution of the plasma density is determined by diffusion processes.

Decomposition reaction of the veterinary antibiotic ciprofloxacin using electron ionizing energy.

PubMed

Cho, Jae Young; Chung, Byung Yeoup; Lee, Kyeong-Bo; Lee, Geon-Hwi; Hwang, Seon Ah

2014-12-01

The application of electron ionizing energy for degrading veterinary antibiotic ciprofloxacin (CFX) in aqueous solution was elucidated. The degradation efficiency of CFX after irradiation with electron ionizing energy was 38% at 1 kGy, 80% at 5kGy, and 97% at 10 kGy. Total organic carbon of CFX in aqueous solution after irradiation with electron ionizing energy decreased 2% at 1 kGy, 18% at 5 kGy, and 53% at 10 kGy. The CFX degradation products after irradiation with electron ionizing energy were CFX1 ([M+H] m/z 330), CFX2 ([M+H] m/z 314), and CFX3 ([M+H] m/z 263). CFX1 had an F atom substituted with OH and CFX2 was expected to originate from CFX via loss of F or H2O. CFX3 was expected to originate from CFX via loss of the piperazynilic ring. Among the several radicals, hydrate electron (eaq(-)) is expected to play an important role in degradation of veterinary antibiotic during irradiation with electron ionizing energy. The toxicity of the degraded products formed during irradiation with electron ionizing energy was evaluated using microbes such as Escherichia coli, Pseudomonas putida, and Bacillus subtilis, and the results revealed that the toxicity decreased with irradiation. These results demonstrate that irradiation technology using electron ionizing energy is an effective was to remove veterinary antibiotics from an aquatic ecosystem. Copyright © 2014 Elsevier Ltd. All rights reserved.

Identification of Fatty Acids and Aliphatic Hydrocarbons in Sarcina lutea by Gas Chromatography and Combined Gas Chromatography-Mass Spectrometry

PubMed Central

Tornabene, T. G.; Gelpi, E.; Oró, J.

1967-01-01

The composition and nature of the fatty acids and hydrocarbons of Sarcina lutea were elucidated by gas chromatography and by combined gas chromatography-mass spectrometry. The distribution of fatty acids found in S. lutea showed two families of pairs, or dyads, of saturated monocarboxylic acids (C12–C18) with and without methyl branching. These pairs of fatty acids showed a pattern of iso and anteiso structures for C13, C15, and C17, and iso and normal structures for C12, C14, and C16. Only the C18 showed unsaturation. The distribution of hydrocarbons in the range C22–C29 showed two families of tetrads of unsaturated aliphatic hydrocarbons all showing methyl branching. Each tetrad was composed of four isomers identified as two iso olefins and two anteiso olefins. The only difference between the tetrads pertaining to different families was found in the relative gas chromatographic retention times of the last two components of each group. PMID:6039356

Thermal modulation for gas chromatography

NASA Technical Reports Server (NTRS)

Waite, J. Hunter (Inventor); Libardoni, Mark (Inventor); Stewart, Kristine (Inventor); Block, Bruce P. (Inventor); Sacks, Richard D. (Inventor); Hasselbrink, Ernest F. (Inventor)

2007-01-01

A thermal modulator device for gas chromatography and associated methods. The thermal modulator device includes a recirculating fluid cooling member, an electrically conductive capillary in direct thermal contact with the cooling member, and a power supply electrically coupled to the capillary and operable for controlled resistive heating of the capillary. The capillary can include more than one separate thermally modulated sections.

Influence of ionization on ultrafast gas-based nonlinear fiber optics.

PubMed

Chang, W; Nazarkin, A; Travers, J C; Nold, J; Hölzer, P; Joly, N Y; Russell, P St J

2011-10-10

We numerically investigate the effect of ionization on ultrashort high-energy pulses propagating in gas-filled kagomé-lattice hollow-core photonic crystal fibers by solving an established uni-directional field equation. We consider the dynamics of two distinct regimes: ionization induced blue-shift and resonant dispersive wave emission in the deep-UV. We illustrate how the system evolves between these regimes and the changing influence of ionization. Finally, we consider the effect of higher ionization stages.

Determination of Vinyl Chloride at ug/l. Level in Water by Gas Chromatography

ERIC Educational Resources Information Center

Bellar, Thomas A.; And Others

1976-01-01

A quantitative method for the determination of vinyl chloride in water is presented. Vinyl chloride is transfered to the gas phase by bubbling inert gas through the water. After concentration on silica gel or Carbosieve-B, determination is by gas chromatography. Confirmation of vinyl chloride is by gas chromatography-mass spectrometry. (Author/BT)

Atmospheric pressure gas chromatography-time-of-flight-mass spectrometry (APGC-ToF-MS) for the determination of regulated and emerging contaminants in aqueous samples after stir bar sorptive extraction (SBSE).

PubMed

Pintado-Herrera, Marina G; González-Mazo, Eduardo; Lara-Martín, Pablo A

2014-12-03

This work presents the development, optimization and validation of a multi-residue method for the simultaneous determination of 102 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and several types of pesticides in aqueous matrices. Water samples were processed using stir bar sorptive extraction (SBSE) after the optimization of several parameters: agitation time, ionic strength, presence of organic modifiers, pH, and volume of the derivatizing agent. Target compounds were extracted from the bars by liquid desorption (LD). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to time-of-flight (ToF-MS) mass spectrometry. A new ionization source, atmospheric pressure gas chromatography (APGC), was tested. The optimized protocol showed acceptable recovery percentages (50-100%) and limits of detection below 1ngL(-1) for most of the compounds. Occurrence of 21 out of 102 analytes was confirmed in several environmental aquatic matrices, including seawater, sewage effluent, river water and groundwater. Non-target compounds such as organophosphorus flame retardants were also identified in real samples by accurate mass measurement of their molecular ions using GC-APGC-ToF-MS. To the best of our knowledge, this is the first time that this technique has been applied for the analysis of contaminants in aquatic systems. By employing lower energy than the more widely used electron impact ionization (EI), AGPC provides significant advantages over EI for those substances very susceptible to high fragmentation (e.g., fragrances, pyrethroids). Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of oleamide and erucamide in polyethylene films by pressurised fluid extraction and gas chromatography.

PubMed

Garrido-López, Alvaro; Esquiu, Vanesa; Tena, María Teresa

2006-08-18

A pressurized fluid extraction (PFE) and gas chromatography-flame ionization detection (GC-FID) method is proposed to determine the slip agents in polyethylene (PE) films. The study of PFE variables was performed using a fractional factorial design (FFD) for screening and a central composite design (CCD) for optimizing the main variables obtained from the Pareto charts. The variables that were studied include temperature, static time, percentage of cyclohexane and the number of extraction cycles. The final condition selected was pure isopropanol (two times) at 105 degrees C for 16min. The recovery of spiked oleamide and erucamide was around 100%. The repeatability of the method was between 9.6% for oleamide and 8% for erucamide, expressed as relative standard deviation. Finally, the method was applied to determine oleamide and erucamide in several polyethylene films and the results were statistically equal to those obtained by pyrolysis and gas-phase chemiluminescence (CL).

The Impact of Diffuse Ionized Gas on Emission-line Ratios and Gas Metallicity Measurements

NASA Astrophysics Data System (ADS)

Zhang, Kai; Yan, Renbin; MaNGA Team

2016-01-01

Diffuse Ionized Gas (DIG) is prevalent in star-forming galaxies. Using a sample of galaxies observed by MaNGA, we demonstrate how DIG in star-forming galaxies impact the measurements of emission line ratios, hence the gas-phase metallicity measurements and the interpretation of diagnostic diagrams. We demonstrate that emission line surface brightness (SB) is a reasonably good proxy to separate HII regions from regions dominated by diffuse ionized gas. For spatially-adjacent regions or regions at the same radius, many line ratios change systematically with emission line surface brightness, reflecting a gradual increase of dominance by DIG towards low SB. DIG could significantly bias the measurement of gas metallicity and metallicity gradient. Because DIG tend to have a higher temperature than HII regions, at fixed metallicity DIG displays lower [NII]/[OII] ratios. DIG also show lower [OIII]/[OII] ratios than HII regions, due to extended partially-ionized regions that enhance all low-ionization lines ([NII], [SII], [OII], [OI]). The contamination by DIG is responsible for a substantial portion of the scatter in metallicity measurements. At different surface brightness, line ratios and line ratio gradients can differ systematically. As DIG fraction could change with radius, it can affect the metallicity gradient measurements in systematic ways. The three commonly used strong-line metallicity indicators, R23, [NII]/[OII], O3N2, are all affected in different ways. To make robust metallicity gradient measurements, one has to properly isolate HII regions and correct for DIG contamination. In line ratio diagnostic diagrams, contamination by DIG moves HII regions towards composite or LINER-like regions.

Gas and particulate phase products from the ozonolysis of acenaphthylene

NASA Astrophysics Data System (ADS)

Riva, Matthieu; Healy, Robert M.; Tomaz, Sophie; Flaud, Pierre-Marie; Perraudin, Emilie; Wenger, John C.; Villenave, Eric

2016-10-01

Polycyclic aromatic hydrocarbons (PAHs) are recognized as important secondary organic aerosol (SOA) precursors in the urban atmosphere. In this work, the gas-phase ozonolysis of acenaphthylene was investigated in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) for on-line characterization of the oxidation products in the gas and particle phases, respectively. SOA samples were also collected on filters and analyzed by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). The major gas-phase products included a range of oxygenated naphthalene derivatives such as 1,8-naphthalic anhydride, naphthalene 1,8-dicarbaldehyde and naphthaldehyde, as well as a secondary ozonide. Possible reaction mechanisms are proposed for the formation of these products and favoured pathways have been suggested. Many of these products were also found in the particle phase along with a range of oligomeric compounds. The same range of gas and particle phase products was observed in the presence and absence of excess cyclohexane, an OH scavenger, indicating that OH radical production from the ozonolysis of acenaphthylene is negligible. SOA yields in the range 23-37% were determined and indicate that acenaphthylene ozonolysis may contribute to part of the SOA observed in urban areas.

A selective and sensitive method for quantitation of lysergic acid diethylamide (LSD) in whole blood by gas chromatography-ion trap tandem mass spectrometry.

PubMed

Libong, Danielle; Bouchonnet, Stéphane; Ricordel, Ivan

2003-01-01

A gas chromatography-ion trap tandem mass spectrometry (GC-ion trap MS-MS) method for detection and quantitation of LSD in whole blood is presented. The sample preparation process, including a solid-phase extraction step with Bond Elut cartridges, was performed with 2 mL of whole blood. Eight microliters of the purified extract was injected with a cold on-column injection method. Positive chemical ionization was performed using acetonitrile as reagent gas; LSD was detected in the MS-MS mode. The chromatograms obtained from blood extracts showed the great selectivity of the method. GC-MS quantitation was performed using lysergic acid methylpropylamide as the internal standard. The response of the MS was linear for concentrations ranging from 0.02 ng/mL (detection threshold) to 10.0 ng/mL. Several parameters such as the choice of the capillary column, the choice of the internal standard and that of the ionization mode (positive CI vs. EI) were rationalized. Decomposition pathways under both ionization modes were studied. Within-day and between-day stability were evaluated.

Characterisation of odorants in roasted stem tea using gas chromatography-mass spectrometry and gas chromatography-olfactometry analysis.

PubMed

Sasaki, Tetsuya; Koshi, Erina; Take, Harumi; Michihata, Toshihide; Maruya, Masachika; Enomoto, Toshiki

2017-04-01

Roasted stem tea has a characteristic flavour, which is obtained by roasting tea stems, by-product of green tea production. This research aims to understand the characteristic odorants in roasted stem tea by comparing it to roasted leaf tea. We revealed potent odorants in commercial roasted stem tea using gas chromatography-mass spectrometry (GC-MS) and gas chromatography-olfactometry with aroma extract dilution analysis (AEDA). The difference between roasted stem and leaf tea derived from the same tea plants were investigated using GC-MS. Pyrazine compounds exhibited a roasted odour and high flavour dilution (FD) factors, as determined via AEDA. Roasted stem tea was richer in these pyrazines than roasted leaf tea. Geraniol and linalool exhibited high FD factors and a floral odour, and roasted stem tea was richer in these compounds than roasted leaf tea. These results may have a positive impact on the development of tea products. Copyright © 2016 Elsevier Ltd. All rights reserved.

Theoretical Calculations for Electron Impact Ionization of Atoms and Molecules

NASA Astrophysics Data System (ADS)

Amami, Sadek Mohamed Fituri

In the last twenty years, significant progress has been made for the theoretical treatment of electron impact ionization (e,2e) of atoms and molecules and, for some cases, very nice agreement between experiment and theory has been achieved. In particular, excellent agreement between theory and experiment and theory has been achieved for ionization of hydrogen and helium. However, agreement between experiment and theory is not nearly as good for ionization of larger atoms and molecules. In the first part of this dissertation, different theoretical approaches will be employed to study the triply differential cross section (TDCS) for low and intermediate energy electron-impact ionization of Neon and Argon for different orbital states. There is a very recent interest in studying ionization of Laser aligned atoms in order to get a better understanding about electron impact ionization of molecules. In the next part of this dissertation, results will be presented for electron-impact ionization of three laser aligned atoms, Mg, Ca, and Na. The comparison between the theory and experiment showed that our three body distorted wave (3DW) model gave excellent agreement with experiment in the scattering plane but very poor agreement perpendicular to the scattering plane. An explanation for this poor agreement out of the scattering plane has been provided by comparing our theoretical results with those of the time depended close coupling (TDCC) model and this explanation is also provided in this dissertation. Recently, significant attention has been directed towards obtaining a better under-standing of electron-impact ionization of molecules which are significantly more challenging than atoms. In the last part of this dissertation, results will be presented for electron-impact ionization of three different molecules (N2 , H2O, and CH4) which have been studied comprehensively using different theoretical approximations for different types of geometries. The published papers in

Observations of extended and counterrotating disks of ionized gas in S0 galaxies

NASA Technical Reports Server (NTRS)

Dettmar, Ralf-Juergen; Jullien-Dettmar, Marlies; Barteldrees, Andreas

1990-01-01

While many E/S0 galaxies have been found to show emission line spectra in their nuclear regions, the question of the presence and nature of extended disks of ionized gas in these galaxies has been addressed only in recent years. Typically the ionized gas is detected in the inner region on a scale of approx. 1 kpc (e.g., Phillips et al. 1986, Caldwell 1984). Here researchers present evidence that the disks of ionized gas of at least some S0 galaxies are much more extended than previously believed. In addition, with the detection of the counterrotation of gas and stars in NGC 7007 they strengthen the basis for arguments that the source of gas in S0 galaxies is external

Electronic structures of elements according to ionization energies.

PubMed

Zadeh, Dariush H

2017-11-28

The electronic structures of elements in the periodic table were analyzed using available experimental ionization energies. Two new parameters were defined to carry out the study. The first parameter-apparent nuclear charge (ANC)-quantified the overall charge of the nucleus and inner electrons observed by an outer electron during the ionization process. This parameter was utilized to define a second parameter, which presented the shielding ability of an electron against the nuclear charge. This second parameter-electron shielding effect (ESE)-provided an insight into the electronic structure of atoms. This article avoids any sort of approximation, interpolation or extrapolation. First experimental ionization energies were used to obtain the two aforementioned parameters. The second parameter (ESE) was then graphed against the electron number of each element, and was used to read the corresponding electronic structure. The ESE showed spikes/peaks at the end of each electronic shell, providing insight into when an electronic shell closes and a new one starts. The electronic structures of elements in the periodic table were mapped using this methodology. These graphs did not show complete agreement with the previously known "Aufbau" filling rule. A new filling rule was suggested based on the present observations. Finally, a new way to organize elements in the periodic table is suggested. Two earlier topics of effective nuclear charge, and shielding factor were also briefly discussed and compared numerically to demonstrate the capability of the new approach.

The Formation and Physical Origin of Highly Ionized Cooling Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bordoloi, Rongmon; Wagner, Alexander Y.; Heckman, Timothy M.

We present a simple model that explains the origin of warm, diffuse gas seen primarily as highly ionized absorption-line systems in the spectra of background sources. We predict the observed column densities of several highly ionized transitions such as O vi, O vii, Ne viii, N v, and Mg x, and we present a unified comparison of the model predictions with absorption lines seen in the Milky Way disk, Milky Way halo, starburst galaxies, the circumgalactic medium, and the intergalactic medium at low and high redshifts. We show that diffuse gas seen in such diverse environments can be simultaneously explainedmore » by a simple model of radiatively cooling gas. We show that most such absorption-line systems are consistent with being collisionally ionized, and we estimate the maximum-likelihood temperature of the gas in each observation. This model satisfactorily explains why O vi is regularly observed around star-forming low- z L* galaxies, and why N v is rarely seen around the same galaxies. We further present some consequences of this model in quantifying the dynamics of the cooling gas around galaxies and predict the shock velocities associated with such flows. A unique strength of this model is that while it has only one free (but physically well-constrained) parameter, it nevertheless successfully reproduces the available data on O vi absorbers in the interstellar, circumgalactic, intragroup, and intergalactic media, as well as the available data on other absorption lines from highly ionized species.« less

Dissociative Ionization of Benzene by Electron Impact

NASA Technical Reports Server (NTRS)

Huo, Winifred; Dateo, Christopher; Kwak, Dochan (Technical Monitor)

2002-01-01

We report a theoretical study of the dissociative ionization (DI) of benzene from the low-lying ionization channels. Our approach makes use of the fact that electron motion is much faster than nuclear motion and DI is treated as a two-step process. The first step is electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model. For the unimolecular dissociation step, we study the steepest descent reaction path to the minimum of the ion potential energy surface. The path is used to analyze the probability of unimolecular dissociation and to determine the product distributions. Our analysis of the dissociation products and the thresholds of the productions are compared with the result dissociative photoionization measurements of Feng et al. The partial oscillator strengths from Feng et al. are then used in the iBED cross section calculations.

Electron gyroharmonic effects in ionization and electron acceleration during high-frequency pumping in the ionosphere.

PubMed

Gustavsson, B; Leyser, T B; Kosch, M; Rietveld, M T; Steen, A; Brändström, B U E; Aso, T

2006-11-10

Optical emissions and incoherent scatter radar data obtained during high-frequency electromagnetic pumping of the ionospheric plasma from the ground give data on electron energization in an energy range from 2 to 100 eV. Optical emissions at 4278 A from N2+ that require electrons with energies above the 18 eV ionization energy give the first images ever of pump-induced ionization of the thermosphere. The intensity at 4278 A is asymmetric around the ionospheric electron gyroharmonic, being stronger above the gyroresonance. This contrasts with emissions at 6300 A from O(1D) and of electron temperature enhancements, which have minima at the gyroharmonic but have no apparent asymmetry. This direct evidence of pump-induced ionization contradicts previous indirect evidence, which indicated that ionization is most efficiently produced when the pump frequency was below the gyroharmonic.

Electron-Atom Ionization Calculations using Propagating Exterior Complex Scaling

NASA Astrophysics Data System (ADS)

Bartlett, Philip

2007-10-01

The exterior complex scaling method (Science 286 (1999) 2474), pioneered by Rescigno, McCurdy and coworkers, provided highly accurate ab initio solutions for electron-hydrogen collisions by directly solving the time-independent Schr"odinger equation in coordinate space. An extension of this method, propagating exterior complex scaling (PECS), was developed by Bartlett and Stelbovics (J. Phys. B 37 (2004) L69, J. Phys. B 39 (2006) R379) and has been demonstrated to provide computationally efficient and accurate calculations of ionization and scattering cross sections over a large range of energies below, above and near the ionization threshold. An overview of the PECS method for three-body collisions and the computational advantages of its propagation and iterative coupling techniques will be presented along with results of: (1) near-threshold ionization of electron-hydrogen collisions and the Wannier threshold laws, (2) scattering cross section resonances below the ionization threshold, and (3) total and differential cross sections for electron collisions with excited targets and hydrogenic ions from low through to high energies. Recently, the PECS method has been extended to solve four-body collisions using time-independent methods in coordinate space and has initially been applied to the s-wave model for electron-helium collisions. A description of the extensions made to the PECS method to facilitate these significantly more computationally demanding calculations will be given, and results will be presented for elastic, single-excitation, double-excitation, single-ionization and double-ionization collisions.

Polymer Analysis by Liquid Chromatography/Electrospray Ionization Time-of-Flight Mass Spectrometry.

PubMed

Nielen, M W; Buijtenhuijs, F A

1999-05-01

Hyphenation of liquid chromatography (LC) techniques with electrospray ionization (ESI) orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (MS) provides both MS-based structural information and LC-based quantitative data in polymer analysis. In one experimental setup, three different LC modes are interfaced with MS:  size-exclusion chromatography (SEC/MS), gradient polymer elution chromatography (GPEC/MS), and liquid chromatography at the critical point of adsorption (LCCC/MS). In SEC/MS, both absolute mass calibration of the SEC column based on the polymer itself and determination of monomers and end groups from the mass spectra are achieved. GPEC/MS shows detailed chemical heterogeneity of the polymer and the chemical composition distribution within oligomer groups. In LCCC/MS, the retention behavior is primarily governed by chemical heterogeneities, such as different end group functionalities, and quantitative end group calculations can be easily made. The potential of these methods and the benefit of time-of-flight analyzers in polymer analysis are discussed using SEC/MS of a polydisperse poly(methyl methacrylate) sample, GPEC/MS of dipropoxylated bisphenol A/adipic acid polyester resin, LCCC/MS of alkylated poly(ethylene glycol), and LCCC/MS of terephthalic acid/neopentyl glycol polyester resin.

Determination of free amino compounds in betalainic fruits and vegetables by gas chromatography with flame ionization and mass spectrometric detection.

PubMed

Kugler, Florian; Graneis, Stephan; Schreiter, Pat P-Y; Stintzing, Florian C; Carle, Reinhold

2006-06-14

Amino acids and amines are the precursors of betalains. Therefore, the profiles of free amino compounds in juices obtained from cactus pears [Opuntia ficus-indica (L.) Mill. cv. Bianca, cv. Gialla, and cv. Rossa], pitaya fruits [Selenicereus megalanthus (K. Schumann ex Vaupel) Moran, Hylocereus polyrhizus (Weber) Britton & Rose, and Hylocereus undatus (Haworth) Britton & Rose], and in extracts from differently colored Swiss chard [Beta vulgaris L. ssp. cicla (L.) Alef. cv. Bright Lights] petioles and red and yellow beets (B. vulgaris L. ssp. vulgaris var. conditiva Alef. cv. Burpee's Golden) were investigated for the first time. Amino compounds were derivatized with propyl chloroformate. While gas chromatography (GC) with mass spectrometry was used for peak assignment, GC flame ionization detection was applied for quantification of individual compounds. Whereas proline was the major free amino compound of cactus pear and pitaya fruit juices, glutamine dominated in Swiss chard stems and beets, respectively. Interestingly, extremely high concentrations of dopamine were detected in Swiss chard stems and beets. Furthermore, the cleavage of betaxanthins caused by derivatization in alkaline reaction solutions is demonstrated for the first time. Amino acids and amines thus released might increase the actual free amino compound contents of the respective sample. To evaluate the contribution of betaxanthin cleavage to total amino acid and amine concentration, isolated betaxanthins were derivatized according to the "EZ:faast" method prior to quantification of the respective amino compounds released. On a molar basis, betaxanthin contribution to overall amino compound contents was always below 6.4%.

Development and Validation of a Method for Alcohol Analysis in Brain Tissue by Headspace Gas Chromatography with Flame Ionization Detector

PubMed Central

Chun, Hao-Jung; Poklis, Justin L.; Poklis, Alphonse; Wolf, Carl E.

2016-01-01

Ethanol is the most widely used and abused drug. While blood is the preferred specimen for analysis, tissue specimens such as brain serve as alternative specimens for alcohol analysis in post-mortem cases where blood is unavailable or contaminated. A method was developed using headspace gas chromatography with flame ionization detection (HS-GC-FID) for the detection and quantification of ethanol, acetone, isopropanol, methanol and n-propanol in brain tissue specimens. Unfixed volatile-free brain tissue specimens were obtained from the Department of Pathology at Virginia Commonwealth University. Calibrators and controls were prepared from 4-fold diluted homogenates of these brain tissue specimens, and were analyzed using t-butanol as the internal standard. The chromatographic separation was performed with a Restek BAC2 column. A linear calibration was generated for all analytes (mean r2 > 0.9992) with the limits of detection and quantification of 100–110 mg/kg. Matrix effect from the brain tissue was determined by comparing the slopes of matrix prepared calibration curves with those of aqueous calibration curves; no significant differences were observed for ethanol, acetone, isopropanol, methanol and n-propanol. The bias and the CVs for all volatile controls were ≤10%. The method was also evaluated for carryover, selectivity, interferences, bench-top stability and freeze-thaw stability. The HS-GC-FID method was determined to be reliable and robust for the analysis of ethanol, acetone, isopropanol, methanol and n-propanol concentrations in brain tissue, effectively expanding the specimen options for post-mortem alcohol analysis. PMID:27488829

Vacuum ultraviolet detector for gas chromatography.

PubMed

Schug, Kevin A; Sawicki, Ian; Carlton, Doug D; Fan, Hui; McNair, Harold M; Nimmo, John P; Kroll, Peter; Smuts, Jonathan; Walsh, Phillip; Harrison, Dale

2014-08-19

Analytical performance characteristics of a new vacuum ultraviolet (VUV) detector for gas chromatography (GC) are reported. GC-VUV was applied to hydrocarbons, fixed gases, polyaromatic hydrocarbons, fatty acids, pesticides, drugs, and estrogens. Applications were chosen to feature the sensitivity and universal detection capabilities of the VUV detector, especially for cases where mass spectrometry performance has been limited. Virtually all chemical species absorb and have unique gas phase absorption cross sections in the approximately 120-240 nm wavelength range monitored. Spectra are presented, along with the ability to use software for deconvolution of overlapping signals. Some comparisons with experimental synchrotron data and computed theoretical spectra show good agreement, although more work is needed on appropriate computational methods to match the simultaneous broadband electronic and vibronic excitation initiated by the deuterium lamp. Quantitative analysis is governed by Beer-Lambert Law relationships. Mass on-column detection limits reported for representatives of different classes of analytes ranged from 15 (benzene) to 246 pg (water). Linear range measured at peak absorption for benzene was 3-4 orders of magnitude. Importantly, where absorption cross sections are known for analytes, the VUV detector is capable of absolute determination (without calibration) of the number of molecules present in the flow cell in the absence of chemical interferences. This study sets the stage for application of GC-VUV technology across a wide breadth of research areas.

Using chromatography – desorption method of manufacturing gas mixtures for analytical instruments calibration

NASA Astrophysics Data System (ADS)

Platonov, I. A.; Kolesnichenko, I. N.; Lange, P. K.

2018-05-01

In this paper, the chromatography desorption method of obtaining gas mixtures of known compositions stable for a time sufficient to calibrate analytical instruments is considered. The comparative analysis results of the preparation accuracy of gas mixtures with volatile organic compounds using diffusion, polyabarbotage and chromatography desorption methods are presented. It is shown that the application of chromatography desorption devices allows one to obtain gas mixtures that are stable for 10...60 hours in a dynamic condition. These gas mixtures contain volatile aliphatic and aromatic hydrocarbons with a concentration error of no more than 7%. It is shown that it is expedient to use such gas mixtures for analytical instruments calibration (chromatographs, spectrophotometers, etc.)

Application of gas chromatography to analysis of spirit-based alcoholic beverages.

PubMed

Wiśniewska, Paulina; Śliwińska, Magdalena; Dymerski, Tomasz; Wardencki, Waldemar; Namieśnik, Jacek

2015-01-01

Spirit-based beverages are alcoholic drinks; their production processes are dependent on the type and origin of raw materials. The composition of this complex matrix is difficult to analyze, and scientists commonly choose gas chromatography techniques for this reason. With a wide selection of extraction methods and detectors it is possible to provide qualitative and quantitative analysis for many chemical compounds with various functional groups. This article describes different types of gas chromatography techniques and their most commonly used associated extraction techniques (e.g., LLE, SPME, SPE, SFE, and SBME) and detectors (MS, TOFMS, FID, ECD, NPD, AED, O or EPD). Additionally, brief characteristics of internationally popular spirit-based beverages and application of gas chromatography to the analysis of selected alcoholic drinks are presented.

Interrelated structures of the transport shock and collisional relaxation layer in a multitemperature, multilevel ionized gas

NASA Technical Reports Server (NTRS)

Vinolo, A. R.; Clarke, J. H.

1973-01-01

The gas dynamic structures of the transport shock and the downstream collisional relaxation layer are evaluated for partially ionized monatomic gases. Elastic and inelastic collisional nonequilibrium effects are taken into consideration. In the microscopic model of the atom, three electronic levels are accounted for. By using an asymptotic technique, the shock morphology is found on a continuum flow basis. This procedure gives two distinct layers in which the nonequilibrium effects to be considered are different. A transport shock appears as the inner solution to an outer collisional relaxation layer. The results show four main interesting points: (1) on structuring the transport shock, ionization and excitation rates must be included in the formulation, since the flow is not frozen with respect to the population of the different electronic levels; (2) an electron temperature precursor appears at the beginning of the transport shock; (3) the collisional layer is rationally reduced to quadrature for special initial conditions, which (4) are obtained from new Rankine-Hugoniot relations for the inner shock.

Quality classification of Spanish olive oils by untargeted gas chromatography coupled to hybrid quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization and metabolomics-based statistical approach.

PubMed

Sales, C; Cervera, M I; Gil, R; Portolés, T; Pitarch, E; Beltran, J

2017-02-01

The novel atmospheric pressure chemical ionization (APCI) source has been used in combination with gas chromatography (GC) coupled to hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) for determination of volatile components of olive oil, enhancing its potential for classification of olive oil samples according to their quality using a metabolomics-based approach. The full-spectrum acquisition has allowed the detection of volatile organic compounds (VOCs) in olive oil samples, including Extra Virgin, Virgin and Lampante qualities. A dynamic headspace extraction with cartridge solvent elution was applied. The metabolomics strategy consisted of three different steps: a full mass spectral alignment of GC-MS data using MzMine 2.0, a multivariate analysis using Ez-Info and the creation of the statistical model with combinations of responses for molecular fragments. The model was finally validated using blind samples, obtaining an accuracy in oil classification of 70%, taking the official established method, "PANEL TEST", as reference. Copyright © 2016 Elsevier Ltd. All rights reserved.

ELECTRON IONIZATION FREQUENCY IN HYDROGEN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cottingham, W.B.; Buchsbaum, S.J.

1963-05-01

The frequency of ionization by electrons in hydrogen was measured during pulsed microwave breakdown in a waveguide. Optical radiation emanating from the plasma was used to determine the temporal rate of growth of electron density. Values of the ionization frequency are presented as a function of E/sub e//p/sub o/ for 36 < E/sub e//p/sub o/ < 200 v/cm-mm Hg. The measurements constitute an extension of the work of Madan, Gordon, Buchsbaum, and Brown who measured this coefficient up to an E/sub e//p/sub o/ of 40 v/cm-mm Hg by microwave cavity techniques. Comparison is made with previous d-c measurements of Rosemore » and with the theory of Allis and Brown. Good agreement is obtained with the measurements of Rose but not with the theory of Allis and Brown extended to high E/sub e//p/ sub o/, nor with the previous microwave measurements of Madan et al. (auth)« less

Lyman-continuum leakage as dominant source of diffuse ionized gas in the Antennae galaxy

NASA Astrophysics Data System (ADS)

Weilbacher, Peter M.; Monreal-Ibero, Ana; Verhamme, Anne; Sandin, Christer; Steinmetz, Matthias; Kollatschny, Wolfram; Krajnović, Davor; Kamann, Sebastian; Roth, Martin M.; Erroz-Ferrer, Santiago; Marino, Raffaella Anna; Maseda, Michael V.; Wendt, Martin; Bacon, Roland; Dreizler, Stefan; Richard, Johan; Wisotzki, Lutz

2018-04-01

The Antennae galaxy (NGC 4038/39) is the closest major interacting galaxy system and is therefore often studied as a merger prototype. We present the first comprehensive integral field spectroscopic dataset of this system, observed with the MUSE instrument at the ESO VLT. We cover the two regions in this system which exhibit recent star formation: the central galaxy interaction and a region near the tip of the southern tidal tail. In these fields, we detect HII regions and diffuse ionized gas to unprecedented depth. About 15% of the ionized gas was undetected by previous observing campaigns. This newly detected faint ionized gas is visible everywhere around the central merger, and shows filamentary structure. We estimate diffuse gas fractions of about 60% in the central field and 10% in the southern region. We are able to show that the southern region contains a significantly different population of HII regions, showing fainter luminosities. By comparing HII region luminosities with the HST catalog of young star clusters in the central field, we estimate that there is enough Lyman-continuum leakage in the merger to explain the amount of diffuse ionized gas that we detect. We compare the Lyman-continuum escape fraction of each HII region against emission line ratios that are sensitive to the ionization parameter. While we find no systematic trend between these properties, the most extreme line ratios seem to be strong indicators of density bounded ionization. Extrapolating the Lyman-continuum escape fractions to the southern region, we conclude that simply from the comparison of the young stellar populations to the ionized gas there is no need to invoke other ionization mechanisms than Lyman-continuum leaking HII regions for the diffuse ionized gas in the Antennae. FITS images and Table of HII regions are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/611/A95 and at http://muse-vlt.eu/science/antennae/

The interaction of intense, ultra-short microwave beams with the plasma generated by gas ionization

NASA Astrophysics Data System (ADS)

Shafir, G.; Cao, Y.; Bliokh, Y.; Leopold, J. G.; Levko, D.; Rostov, V.; Gad, R.; Fisher, A.; Bernshtam, V.; Krasik, Ya. E.

2018-03-01

Results of the non-linear interaction of an extremely short (0.6 ns) high power (˜500 MW) X-band focused microwave beam with the plasma generated by gas ionization are presented. Within certain gas pressure ranges, specific to the gas type, the plasma density is considerably lower around the microwave beam axis than at its periphery, thus forming guiding channel through which the beam self-focuses. Outside these pressure ranges, either diffuse or streamer-like plasma is observed. We also observe high energy electrons (˜15 keV), accelerated by the very high-power microwaves. A simplified analytical model of this complicated dynamical system and particle-in-cell numerical simulations confirm the experimental results.

Resonant- and avalanche-ionization amplification of laser-induced plasma in air

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yue; Zhang, Zhili, E-mail: zzhang24@utk.edu; Jiang, Naibo

2014-10-14

Amplification of laser-induced plasma in air is demonstrated utilizing resonant laser ionization and avalanche ionization. Molecular oxygen in air is ionized by a low-energy laser pulse employing (2 + 1) resonance-enhanced multi-photon ionization (REMPI) to generate seed electrons. Subsequent avalanche ionization of molecular oxygen and nitrogen significantly amplifies the laser-induced plasma. In this plasma-amplification effect, three-body attachments to molecular oxygen dominate the electron-generation and -loss processes, while either nitrogen or argon acts as the third body with low electron affinity. Contour maps of the electron density within the plasma obtained in O₂/N₂ and O₂/Ar gas mixtures are provided to showmore » relative degrees of plasma amplification with respect to gas pressure and to verify that the seed electrons generated by O₂ 2 + 1 REMPI are selectively amplified by avalanche ionization of molecular nitrogen in a relatively low-pressure condition (≤100 Torr). Such plasma amplification occurring in air could be useful in aerospace applications at high altitude.« less

[Analytical method and comparison for static and dynamic headspace gas chromatography of anisole in water].

PubMed

Zhang, Yan; Qian, Jie-feng; Liu, Lan-xia; Zhao, Hui-qin

2013-01-01

To establish and compare the method of static headspace gas chromatography hydrogen flame detector (static headspace method) and purge and trap gas chromatography-mass spectrometry (dynamic headspace method) of anisole in water. Nitrogen gas was used as carrier gas in the static headspace method, 5 g NaCl as matrix modifier was added into 10 ml water. The sample was balanced with high speed vibration at 75°C for 30 min, and anisole was detected by gas chromatography and quantified with external standard. Helium was used as carrier gas in dynamic headspace method, 5.0 ml water and 0.004 mg/L internal standard fluorobenzene was purged into the purge and trap apparatus. After purging, trapping and desorption, anisole was detected by the gas chromatography-mass spectrograph, confirmed by the retention time and comparison of mass-spectrogram in spectrum library and quantified with internal standard. The repeatability and sensitivity of assay were evaluated. A good linear range for anisole was observed in static headspace gas chromatography and dynamic headspace gas chromatography-mass spectrometry, within the range of 10 - 500 µg/L and 0.5 - 60.0 µg/L respectively. The linear regression equation was Y = 782.150X + 1.3446 and Y = 0.0358X - 0.0209 respectively, both the correlation coefficient ≥ 0.999. The detection limit (LOD) were 0.002 µg/L and 0.110 µg/L, the lower limit of quantitation (LOQ) were 0.006 µg/L and 0.350 µg/L, the relative standard deviation (RSD) were 1.8% - 2.3% and 2.0% - 3.4%, and the spiking recovery were 93% - 101% and 96% - 101% respectively. The methods of static headspace gas chromatography and dynamic headspace gas chromatography-mass spectrometry are simple and can measure anisole in water quickly, sensitively and accurately.

Less common applications of monoliths III. Gas chromatography

PubMed Central

Svec, Frantisek; Kurganov, Alexander A.

2008-01-01

Porous polymer monoliths emerged about two decades ago. Despite this short time, they are finding applications in a variety of fields. In addition to the most common and certainly best known use of this new category of porous media as stationary phases in liquid chromatography, monolithic materials also found their applications in other areas. This review article focuses on monoliths in capillaries designed for separations in gas chromatography. PMID:17645884

Method development for the analysis of N-nitrosodimethylamine and other N-nitrosamines in drinking water at low nanogram/liter concentrations using solid-phase extraction and gas chromatography with chemical ionization tandem mass spectrometry.

PubMed

Munch, Jean W; Bassett, Margarita V

2006-01-01

N-nitrosodimethylamine (NDMA) is a probable human carcinogen of concern that has been identified as a drinking water contaminant. U.S. Environmental Protection Agency Method 521 has been developed for the analysis of NDMA and 6 additional N-nitrosamines in drinking water at low ng/L concentrations. The method uses solid-phase extraction with coconut charcoal as the sorbent and dichloromethane as the eluent to concentrate 0.50 L water samples to 1 mL. The extracts are analyzed by gas chromatography-chemical ionization tandem mass spectrometry using large-volume injection. Method performance was evaluated in 2 laboratories. Typical analyte recoveries of 87-104% were demonstrated for fortified reagent water samples, and recoveries of 77-106% were demonstrated for fortified drinking water samples. All relative standard deviations on replicate analyses were < 11%.

Diagnosis of gastroenterological diseases by metabolome analysis using gas chromatography-mass spectrometry.

PubMed

Yoshida, Masaru; Hatano, Naoya; Nishiumi, Shin; Irino, Yasuhiro; Izumi, Yoshihiro; Takenawa, Tadaomi; Azuma, Takeshi

2012-01-01

Recently, metabolome analysis has been increasingly applied to biomarker detection and disease diagnosis in medical studies. Metabolome analysis is a strategy for studying the characteristics and interactions of low molecular weight metabolites under a specific set of conditions and is performed using mass spectrometry and nuclear magnetic resonance spectroscopy. There is a strong possibility that changes in metabolite levels reflect the functional status of a cell because alterations in their levels occur downstream of DNA, RNA, and protein. Therefore, the metabolite profile of a cell is more likely to represent the current status of a cell than DNA, RNA, or protein. Thus, owing to the rapid development of mass spectrometry analytical techniques metabolome analysis is becoming an important experimental method in life sciences including the medical field. Here, we describe metabolome analysis using liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry (GC-MS), capillary electrophoresis-mass spectrometry, and matrix assisted laser desorption ionization-mass spectrometry. Then, the findings of studies about GC-MS-based metabolome analysis of gastroenterological diseases are summarized, and our research results are also introduced. Finally, we discuss the realization of disease diagnosis by metabolome analysis. The development of metabolome analysis using mass spectrometry will aid the discovery of novel biomarkers, hopefully leading to the early detection of various diseases.

Ultratrace detector for hand-held gas chromatography

DOEpatents

Andresen, Brian D.; Miller, Fred S.

1999-01-01

An ultratrace detector system for hand-held gas chromatography having high sensitivity, for example, to emissions generated during production of weapons, biological compounds, drugs, etc. The detector system is insensitive to water, air, helium, argon, oxygen, and C0.sub.2. The detector system is basically composed of a hand-held capillary gas chromatography (GC), an insulated heated redox-chamber, a detection chamber, and a vapor trap. For example, the detector system may use gas phase redox reactions and spectral absorption of mercury vapor. The gas chromatograph initially separates compounds that percolate through a bed of heated mercuric oxide (HgO) in a silica--or other metal--aerogel material which acts as an insulator. Compounds easily oxidized by HgO liberate atomic mercury that subsequently pass through a detection chamber which includes a detector cell, such as quartz, that is illuminated with a 254 nm ultra-violet (UV) mercury discharge lamp which generates the exact mercury absorption bands that are used to detect the liberated mercury atoms. Atomic mercury strongly absorbs 254 nm energy is therefore a specific signal for reducing compounds eluting from the capillary GC, whereafter the atomic mercury is trapped for example, in a silicon-aerogel trap.

Microplume model of spatial-yield spectra. [applying to electron gas degradation in molecular nitrogen gas

NASA Technical Reports Server (NTRS)

Green, A. E. S.; Singhal, R. P.

1979-01-01

An analytic representation for the spatial (radial and longitudinal) yield spectra is developed in terms of a model containing three simple 'microplumes'. The model is applied to electron energy degradation in molecular nitrogen gas for 0.1 to 5 keV incident electrons. From the nature of the cross section input to this model it is expected that the scaled spatial yield spectra for other gases will be quite similar. The model indicates that each excitation, ionization, etc. plume should have its individual spatial and energy dependence. Extensions and aeronomical and radiological applications of the model are discussed.

Simultaneous determination of carisoprodol and acetaminophen in an attempted suicide by liquid chromatography-mass spectrometry with positive electrospray ionization.

PubMed

Matsumoto, Tomohiro; Sano, Toshiyuki; Matsuoka, Toshiyasu; Aoki, Minoru; Maeno, Yoshitaka; Nagao, Masataka

2003-03-01

An adult female ingested a considerable quantity of carisoprodol/acetaminophen tablets, which are not commercially available in Japan, in an attempt to commit suicide. Generally, because of lack of the appreciable ultraviolet absorbance or fluorescence, carisoprodol and its major metabolite meprobamate are determined by gas chromatography or gas chromatography-mass spectrometry. Complicated derivatization is, however, necessary to that methodology. Thus, we investigated the derivatization-free, highly sensitive, and simultaneous determination of carisoprodol, meprobamate, and acetaminophen by means of liquid chromatography-mass spectrometry (LC-MS) with positive electrospray ionization. A semi-micro ODS column was used. Ammonium acetate solution (10mM) and acetonitrile were used as mobile phase at a flow rate of 150 microL/min using gradient elution. MS parameters were as follows: capillary voltage, 3.5 kV; cone voltage, +30 V; extractor voltage, 5 kV; and ion source temperature, 100 degrees C. Urine samples pretreated by Oasis HLB cartridge, or plasma samples deproteinized by adding ice-cold acetonitrile were analyzed by LC-MS. The limits of quantitation for each compound were as follows: 0.50 ng/mL for carisoprodol; 10 ng/mL for acetaminophen; and 1.0 ng/mL for meprobamate. In the present case, carisoprodol and acetaminophen were the only drugs detected. Meprobamate was also found as the metabolite of carisoprodol in both urine and plasma. The plasma levels of carisoprodol, acetaminophen, and meprobamate on arrival were 29.5, 245, and 46.7 microg/mL, respectively. These levels were extremely high compared with therapeutic plasma concentrations. Despite the high plasma concentrations of these drugs, which correspond to fatal levels, the patient survived.

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

PubMed

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.

Ionization rate from the electron precipitation during August 2011 storm

NASA Astrophysics Data System (ADS)

Huang, Y.; Huang, C. Y.; Su, Y.

2013-12-01

We apply a parameterization by Fang et al. [2010] (Fang2010) to the complex energy spectra measured by DMSP F16 satellites to calculate the ionization rate from electron precipitation during a moderate storm on August 6th, 2011. The DMSP electron flux measurements show that there is clear enhancement of electron fluxes in the polar cap. The mean energy in the polar cap is mostly above 100 eV, while the mean energy of auroral zone is above 1 keV. F16 also captures a strong Poynting flux enhancement in the polar cap. The electron impact ionization rates using thermospheric densities and temperatures from NRLMSISE-00, TIE-GCM and GITM show clear enhancement at F-region altitudes in the polar cap region due to the low-energy electrons precipitated. Using the default empirical formulations of electron impact ionization in GCMs, TIE-GCM and GITM do not capture the F-region ionization shown in the results of Fang2010 parameterization. Fang, X, C. E. Randall, D. Lummerzheim, W. Wang, G. Lu, S. C. Solomon, and R. A. Frahm (2010), Geophys. Res. Lett., 37, L22106, doi:10.1029/2010GL045406.

Prediction of response factors for gas chromatography with flame ionization detection: Algorithm improvement, extension to silylated compounds, and application to the quantification of metabolites

PubMed Central

de Saint Laumer, Jean‐Yves; Leocata, Sabine; Tissot, Emeline; Baroux, Lucie; Kampf, David M.; Merle, Philippe; Boschung, Alain; Seyfried, Markus

2015-01-01

We previously showed that the relative response factors of volatile compounds were predictable from either combustion enthalpies or their molecular formulae only 1. We now extend this prediction to silylated derivatives by adding an increment in the ab initio calculation of combustion enthalpies. The accuracy of the experimental relative response factors database was also improved and its population increased to 490 values. In particular, more brominated compounds were measured, and their prediction accuracy was improved by adding a correction factor in the algorithm. The correlation coefficient between predicted and measured values increased from 0.936 to 0.972, leading to a mean prediction accuracy of ± 6%. Thus, 93% of the relative response factors values were predicted with an accuracy of better than ± 10%. The capabilities of the extended algorithm are exemplified by (i) the quick and accurate quantification of hydroxylated metabolites resulting from a biodegradation test after silylation and prediction of their relative response factors, without having the reference substances available; and (ii) the rapid purity determinations of volatile compounds. This study confirms that Gas chromatography with a flame ionization detector and using predicted relative response factors is one of the few techniques that enables quantification of volatile compounds without calibrating the instrument with the pure reference substance. PMID:26179324

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization.

PubMed

Neustetter, M; Jabbour Al Maalouf, E; Limão-Vieira, P; Denifl, S

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO)6) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)6 clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)n (+) (0 ≤ n ≤ 6) and W2(CO)n (+) (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)n (+) (0 ≤ n ≤ 3) and W2C(CO)n (+) (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.

Epoxidized soy bean oil migrating from the gaskets of lids into food packed in glass jars. Analysis by on-line liquid chromatography-gas chromatography.

PubMed

Fankhauser-Noti, Anja; Fiselier, Katell; Biedermann-Brem, Sandra; Grob, Koni

2005-08-05

The migration of epoxidized soy bean oil (ESBO) from the gasket in the lids of glass jars into foods, particularly those rich in edible oil, often far exceeds the legal limit (60 mg/kg). ESBO was determined through a methyl ester isomer of diepoxy linoleic acid. Transesterification occurred directly in the homogenized food. From the extracted methyl esters, the diepoxy components were isolated by normal-phase LC and transferred on-line to gas chromatography with flame ionization detection using the on-column interface in the concurrent solvent evaporation mode. The method involves verification elements to ensure the reliability of the results for every sample analyzed. The detection limit is 2-5 mg/kg, depending on the food. Uncertainty of the procedure is below 10%.

Ablation from High Velocity Clouds: A Source for Low Velocity Ionized Gas

NASA Astrophysics Data System (ADS)

Shelton, Robin L.; Henley, D. B.; Kwak, K.

2012-05-01

High velocity clouds shed material as they move through the Galaxy. This material mixes with the Galactic interstellar medium, resulting in plasma whose temperature and ionization levels are intermediate between those of the cloud and those of the Galaxy. As time passes, the mixed material slows to the velocity of the ambient gas. This raises the possibility that initially warm (T 10^3 K), poorly ionized clouds moving through hot (T 10^6 K), very highly ionized ambient gas could lead to mixed gas that harbors significant numbers of high ions (O+5, N+4, and C+3) and thus helps to explain the large numbers of low-velocity high ions seen on high latitude lines of sight through the Galactic halo. We have used a series of detailed FLASH simulations in order to track the hydrodynamics of warm clouds embedded in hot Galactic halo gas. These simulations tracked the ablated material as it mixed and slowed to low velocities. By following the ionization levels of the gas in a time-dependent fashion, we determined that the mixed material is rich in O+5, N+4, and C+3 ions and continues to contain these ions for some time after slowing to low velocities. Combining our simulational results with estimates of the high velocity cloud infall rate leads to the finding that the mixed gas can account for 1/3 of the normal-velocity O+5 column density found on high latitude lines of sight. It accounts for lesser fractions of the N+4 and C+3 column densities. We will discuss our high velocity cloud results as part of a composite halo model that also includes cooling Galactic fountain gas, isolated supernova remnants, and ionizing photons.

Electron- and proton-induced ionization of pyrimidine

DOE PAGES

Champion, Christophe; Quinto, Michele; Weck, Philippe F

2015-03-27

This present work describes a quantum-mechanically based model of the electron- and proton-induced ionization of isolated pyrimidine molecules. The impact energies range from the target ionization threshold up to ~1 keV for electrons and from 10 keV up to 10 MeV for protons. The cross-section calculations are performed within the 1st Born approximation in which the ejected electron is described by a Coulomb wave whereas the incident and the scattered projectiles are both described by plane waves. The pyrimidine target is described using the Gaussian 09 software package. Furthermore, our theoretical predictions obtained are in good agreement with experimental absolutemore » total cross sections, while large discrepancies are observed between existing semi-empirical models and the present calculations.« less

Highly-ionized metals as probes of the circumburst gas in the natal regions of gamma-ray bursts

NASA Astrophysics Data System (ADS)

Heintz, K. E.; Watson, D.; Jakobsson, P.; Fynbo, J. P. U.; Bolmer, J.; Arabsalmani, M.; Cano, Z.; Covino, S.; D'Elia, V.; Gomboc, A.; Japelj, J.; Kaper, L.; Krogager, J.-K.; Pugliese, G.; Sánchez-Ramírez, R.; Selsing, J.; Sparre, M.; Tanvir, N. R.; Thöne, C. C.; de Ugarte Postigo, A.; Vergani, S. D.

2018-06-01

We present here a survey of high-ionization absorption lines in the afterglow spectra of long-duration gamma-ray bursts (GRBs) obtained with the VLT/X-shooter spectrograph. Our main goal is to investigate the circumburst medium in the natal regions of GRBs. Our primary focus is on the N V λλ 1238,1242 line transitions, but we also discuss other high-ionization lines such as O VI, C IV and Si IV. We find no correlation between the column density of N V and the neutral gas properties such as metallicity, H I column density and dust depletion, however the relative velocity of N V, typically a blueshift with respect to the neutral gas, is found to be correlated with the column density of H I. This may be explained if the N V gas is part of an H II region hosting the GRB, where the region's expansion is confined by dense, neutral gas in the GRB's host galaxy. We find tentative evidence (at 2σ significance) that the X-ray derived column density, NH, X, may be correlated with the column density of N V, which would indicate that both measurements are sensitive to the column density of the gas located in the vicinity of the GRB. We investigate the scenario where N V (and also O VI) is produced by recombination after the corresponding atoms have been stripped entirely of their electrons by the initial prompt emission, in contrast to previous models where highly-ionized gas is produced by photoionization from the GRB afterglow.

Photoionization and electron-impact ionization of Ar5+

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, J.C.; Lu, M.; Esteves, D.

2007-02-27

Absolute cross sections for photoionization andelectron-impact Photionization of Ar5+ have been measuredusing twodifferent interacting-beams setups. The spectra consist of measurementsof the yield of products dueto single ionization as a function ofelectron or photon energy. In addition, absolute photoionization andelectron-impact ionization cross sections were measured to normalize themeasured Ar6+ product-ion yield spectra. In the energy range from 90 to111 eV, both electron-impact ionization and photoionization of Ar5+aredominated by indirect 3s subshell excitation-autoionization. In theenergy range from 270 to 285 eV, resonances due to 2p-3dexcitation-autoionization are prominent in the photoionization spectrum.In the range from 225 to 335 eV, an enhancement due tomore » 2p-nl (n>2>excitations are evident in the electron-impactionization cross section.The electron and photon impact data show some features due to excitationof the same intermediate autoionizing states.« less

Theory of electron-impact ionization of atoms

NASA Astrophysics Data System (ADS)

Kadyrov, A. S.; Mukhamedzhanov, A. M.; Stelbovics, A. T.; Bray, I.

2004-12-01

The existing formulations of electron-impact ionization of a hydrogenic target suffer from a number of formal problems including an ambiguous and phase-divergent definition of the ionization amplitude. An alternative formulation of the theory is given. An integral representation for the ionization amplitude which is free of ambiguity and divergence problems is derived and is shown to have four alternative, but equivalent, forms well suited for practical calculations. The extension to amplitudes of all possible scattering processes taking place in an arbitrary three-body system follows. A well-defined conventional post form of the breakup amplitude valid for arbitrary potentials including the long-range Coulomb interaction is given. Practical approaches are based on partial-wave expansions, so the formulation is also recast in terms of partial waves and partial-wave expansions of the asymptotic wave functions are presented. In particular, expansions of the asymptotic forms of the total scattering wave function, developed from both the initial and the final state, for electron-impact ionization of hydrogen are given. Finally, the utility of the present formulation is demonstrated on some well-known model problems.

Characterization of Secondary Organic Aerosol Precursors Using Two-Dimensional Gas-Chromatography

NASA Astrophysics Data System (ADS)

Roskamp, M.; Lou, W.; Pankow, J. F.; Harley, P. C.; Turnipseed, A.; Barsanti, K. C.

2012-12-01

The oxidation of volatile organic compounds (VOCs) plays a role in both regional and global air quality. However, field and laboratory research indicate that the body of knowledge around the identities, quantities and oxidation processes of these compounds in the ambient atmosphere is still incomplete (e.g., Goldstein & Galbally, 2007; Robinson et al., 2009). VOCs emitted to the atmosphere largely are of biogenic origin (Guenther et al., 2006), and many studies of ambient secondary organic aerosol (SOA) suggest that SOA is largely of biogenic origin (albeit closely connected to anthropogenic activities, e.g., de Gouw and Jimenez, 2009). Accurate modeling of SOA levels and properties will require a more complete understanding of biogenic VOCs (BOCs) and their atmospheric oxidation products. For example, satellite measurements indicate that biogenic VOC emissions are two to three times greater than levels currently included in models (Heald et al., 2010). Two-dimensional gas chromatography (GC×GC) is a powerful analytical technique that shows much promise in advancing the state-of-knowledge regarding BVOCs and their role in SOA formation. In this work, samples were collected during BEACHON-RoMBAS (Bio-hydro-atmosphere Interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study) in July and August of 2011. The field site was a Ponderosa Pine forest near Woodland, CO, inside the Manitou Experimental Forest, which is operated by the US Forest Service. The area is characteristic of the central Rocky Mountains and trace gas monitoring indicates that little anthropogenic pollution is transported from the nearby urban areas (Kim et al. 2010 and references therein). Ambient and enclosure samples were collected on ATD (adsorption/thermal desorption) cartridges and analyzed for BVOCs using two-dimensional gas chromatography (GC×GC) with time of flight mass spectrometry (TOFMS) and flame ionized detection (FID). Measurements of

Ionization Cross Sections and Dissociation Channels of DNA Bases by Electron Collisions

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Dateo, Christopher E.; Fletcher, Graham D.

2004-01-01

Free secondary electrons are the most abundant secondary species in ionizing radiation. Their role in DNA damage, both direct and indirect, is an active area of research. While indirect damage by free radicals, particularly by the hydroxyl radical generated by electron collision with water. is relatively well studied, damage by direct electron collision with DNA is less well understood. Only recently Boudaiffa et al. demonstrated that electrons at energies well below ionization thresholds can induce substantial yields of single- and double-strand breaks in DNA by a resonant, dissociative attachment process. This study attracted renewed interest in electron collisions with DNA, especially in the low energy region. At higher energies ionization becomes important. While Monte Carlo track simulations of radiation damage always include ionization, the probability of dissociative ionization, i.e., simultaneous ionization and dissociation, is ignored. Just like dissociative attachment, dissociative ionization may be an important contributor to double-strand breaks since the radicals and ions produced by dissociative ionization, located in the vicinity of the DNA coil, can readily interact with other parts of the DNA. Using the improved binary-encounter dipole (iBED) formulation, we calculated the ionization cross sections of the four DNA bases, adenine, cytosine, guanine, and thymine, by electrons at energies from threshold to 1 KeV. The present calculation gives cross sections approximately 20% lower than the results by Bemhardt and Paretzke using the Deutsch-Mark and Binary-Encounter-Bethe (BEB) formalisms. The difference is most likely due to the lack of a shielding term in the dipole potential used in the Deutsch-Mark and BEB formalisms. The dissociation channels of ionization for the bases are currently being studied.

Simultaneous determination of eighteen nitro-polyaromatic hydrocarbons in PM2.5 by atmospheric pressure gas chromatography-tandem mass spectrometry.

PubMed

Zhang, Yanhao; Li, Ruijin; Fang, Jing; Wang, Chen; Cai, Zongwei

2018-05-01

A new atmospheric pressure gas chromatography-tandem mass spectrometry (APGC-MS/MS) was developed to simultaneously separate, identify and quantify 18 nitro-polyaromatic hydrocarbons (NPAHs) in air fine particulate matter (PM 2.5 ). Compared with traditional negative chemical ionization (NCI) or electron impact ionization (EI)-MS/MS methods, APGC-MS/MS equipped with an atmospheric pressure chemical ionization (APCI) source provided better sensitivity and selectivity for NPAHs analysis in PM 2.5 .18 NPAHs were completely separated, and satisfactory linear response (R 2  > 0.99), low instrumental detection limits (0.20-2.18 pg mL -1 ) and method detection limits (0.001-0.015 pg m -3 ) were achieved. Due to the reliable performance of the instrument, only minimal sample pretreatment is needed. It ensured the satisfactory method recovery (70%-120%) and qualified repeatability (RSD: 1.1%-17.2%), which met the requirement of trace analysis of NAPHs in the real environmental PM 2.5 . Using the developed method, the actual PM 2.5 samples collected from Taiyuan, China in both summer and winter were analyzed, and 17 NPAHs but 2-nitrofluorene were detected and quantified. According to the obtained NAPH concentration results, the generation mechanism of NPAHs in PM 2.5 and the effects on NPAHs formation caused by some ambient air pollutants were preliminarily discussed: secondary photochemical reaction might be the dominant source of NPAHs in PM 2.5 collected from Taiyuan in both summer and winter; ambient air pollutants (NO 2 , SO 2 , CO) had more contribution on the NPAHs secondary formation of PM 2.5 in winter. Copyright © 2018 Elsevier Ltd. All rights reserved.

In-gas-cell laser ionization studies of plutonium isotopes at IGISOL

NASA Astrophysics Data System (ADS)

Pohjalainen, I.; Moore, I. D.; Kron, T.; Raeder, S.; Sonnenschein, V.; Tomita, H.; Trautmann, N.; Voss, A.; Wendt, K.

2016-06-01

In-gas-cell resonance laser ionization has been performed on long-lived isotopes of Pu at the IGISOL facility, Jyväskylä. This initiates a new programme of research towards high-resolution optical spectroscopy of heavy actinide elements which can be produced in sufficient quantities at research reactors and transported to facilities elsewhere. In this work a new gas cell has been constructed for fast extraction of laser-ionized elements. Samples of 238-240,242Pu and 244Pu have been evaporated from Ta filaments, laser ionized, mass separated and delivered to the collinear laser spectroscopy station. Here we report on the performance of the gas cell through studies of the mass spectra obtained in helium and argon, before and after the radiofrequency quadrupole cooler-buncher. This provides valuable insight into the gas phase chemistry exhibited by Pu, which has been additionally supported by measurements of ion time profiles. The resulting monoatomic yields are sufficient for collinear laser spectroscopy. A gamma-ray spectroscopic analysis of the Pu samples shows a good agreement with the assay provided by the Mainz Nuclear Chemistry department.

[Simultaneous determination of cocaine and its metabolite ecgonine methyl ester in human blood using microwave extraction-gas chromatography].

PubMed

Wang, Xiaobo; Ye, Nengsheng; Wang, Jifen; Gu, Xuexin

2010-07-01

A method was developed for the simultaneous determination of cocaine (COC) and its metabolite ecgonine methyl ester (EME) in human blood using gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detection (GC-FID). The blood sample was prepared by microwave extraction (MWE). The optimal parameters of MWE were as follows: 6 mL of chloroform-isopropanol (9: 1, v/v) mixture as extraction solvent, the pH value of the sample was adjusted at 10.0 with 0.05 mol/L Na2CO3-NaHCO3 buffer, the extraction was performed at 40 degrees C for 6 min. The COC and EME in the extract were qualified using GC-MS and quantitated using GC-FID. The average recoveries of COC and EME were from 79.91% to 99.85%, the relative standard deviations were less than 3.10%, and the limits of detection (LOD) were 60 and 40 mg/L, respectively. In the method COC and EME were detected without derivatization. The method is rapid, accurate and sensitive, and can be used for the simultaneous determination of COC and EME in blood samples.

Low-energy electron-impact single ionization of helium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Colgan, J.; Pindzola, M. S.; Childers, G.

2006-04-15

A study is made of low-energy electron-impact single ionization of ground-state helium. The time-dependent close-coupling method is used to calculate total integral, single differential, double differential, and triple differential ionization cross sections for impact electron energies ranging from 32 to 45 eV. For all quantities, the calculated cross sections are found to be in very good agreement with experiment, and for the triple differential cross sections, good agreement is also found with calculations made using the convergent close-coupling technique.

Electron-electron correlation in two-photon double ionization of He-like ions [Counterintuitive electron correlation in two-photon double ionization of He-like ions

DOE PAGES

Hu, S. X.

2018-01-18

Electron correlation plays a crucial role in quantum many-body physics ranging from molecular bonding, strong-field–induced multi-electron ionization, to superconducting in materials. Understanding the dynamic electron correlation in the photoionization of relatively simple quantum three-body systems, such as He and He-like ions, is an important step toward manipulating complex systems through photo-induced processes. Here we have performed ab initio investigations of two-photon double ionization (TPDI) of He and He-like ions [Li +, Be 2+, and C 4+] exposed to intense attosecond x-ray pulses. Results from such fully correlated quantum calculations show weaker and weaker electron correlation effects in TPDI spectra asmore » the ionic charge increases, which is counterintuitive to the belief that the strongly correlated ground state and the strong Coulomb field of He-like ions should lead to more equal-energy sharing in photoionization. Lastly, these findings indicate that the final-state electron–electron correlation ultimately determines their energy sharing in TPDI.« less

Electron-electron correlation in two-photon double ionization of He-like ions [Counterintuitive electron correlation in two-photon double ionization of He-like ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, S. X.

Electron correlation plays a crucial role in quantum many-body physics ranging from molecular bonding, strong-field–induced multi-electron ionization, to superconducting in materials. Understanding the dynamic electron correlation in the photoionization of relatively simple quantum three-body systems, such as He and He-like ions, is an important step toward manipulating complex systems through photo-induced processes. Here we have performed ab initio investigations of two-photon double ionization (TPDI) of He and He-like ions [Li +, Be 2+, and C 4+] exposed to intense attosecond x-ray pulses. Results from such fully correlated quantum calculations show weaker and weaker electron correlation effects in TPDI spectra asmore » the ionic charge increases, which is counterintuitive to the belief that the strongly correlated ground state and the strong Coulomb field of He-like ions should lead to more equal-energy sharing in photoionization. Lastly, these findings indicate that the final-state electron–electron correlation ultimately determines their energy sharing in TPDI.« less

DIRECT-DEPOSITION INFRARED SPECTROMETRY WITH GAS AND SUPERCRITICAL FLUID CHROMATOGRAPHY

EPA Science Inventory

A direct-deposition Fourier transform infrared (FT-IR) system has been evaluated for applicability to gas chromatography (GC) and supercritical fluid chromatography (SFC) of environmental analytes. A 100-um i.d. fused-silica transfer line was used for GC, and a 50-um transfer lin...

Multidimensional gas chromatography in combination with accurate mass, tandem mass spectrometry, and element-specific detection for identification of sulfur compounds in tobacco smoke.

PubMed

Ochiai, Nobuo; Mitsui, Kazuhisa; Sasamoto, Kikuo; Yoshimura, Yuta; David, Frank; Sandra, Pat

2014-09-05

A method is developed for identification of sulfur compounds in tobacco smoke extract. The method is based on large volume injection (LVI) of 10μL of tobacco smoke extract followed by selectable one-dimensional ((1)D) or two-dimensional ((2)D) gas chromatography (GC) coupled to a hybrid quadrupole time-of-flight mass spectrometer (Q-TOF-MS) using electron ionization (EI) and positive chemical ionization (PCI), with parallel sulfur chemiluminescence detection (SCD). In order to identify each individual sulfur compound, sequential heart-cuts of 28 sulfur fractions from (1)D GC to (2)D GC were performed with the three MS detection modes (SCD/EI-TOF-MS, SCD/PCI-TOF-MS, and SCD/PCI-Q-TOF-MS). Thirty sulfur compounds were positively identified by MS library search, linear retention indices (LRI), molecular mass determination using PCI accurate mass spectra, formula calculation using EI and PCI accurate mass spectra, and structure elucidation using collision activated dissociation (CAD) of the protonated molecule. Additionally, 11 molecular formulas were obtained for unknown sulfur compounds. The determined values of the identified and unknown sulfur compounds were in the range of 10-740ngmg total particulate matter (TPM) (RSD: 1.2-12%, n=3). Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Update of on-line coupled liquid chromatography - gas chromatography for the analysis of mineral oil hydrocarbons in foods and cosmetics.

PubMed

Biedermann, Maurus; Munoz, Celine; Grob, Koni

2017-10-27

On-line coupled high performance liquid chromatography-gas chromatography-flame ionization detection (HPLC-GC-FID) is the most widely used method for the analysis of mineral oil hydrocarbons in food, food contact materials, tissues and cosmetics. With comprehensive two-dimensional gas chromatography (GCxGC), a tool became available for better establishing the elution sequence of the various types of hydrocarbons from the HPLC column used for isolating the mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The performance of a heavily used HPLC column with reduced retention for MOAH was investigated to improve the robustness of the method. Updates are recommended that render the MOSH/MOAH separation less dependent of the state of the HPLC column and more correct in cases of highly refined mineral oil products of high molecular mass. Cyclohexyl cyclohexane (Cycy), used as internal standard, turned out to be eluted slightly after cholestane (Cho); apparently the size exclusion effect predominates the extra retention by ring number on the 60Å pore size silica gel. Hence, Cycy can be used to determine the end of the MOSH fraction. Long chain alkyl benzenes were eluted earlier than tri-tert. butyl benzene (Tbb). It is proposed to start the MOAH transfer immediately after the MOSH fraction and use a gradient causing breakthrough of dichloromethane (visible in the UV chromatogram) at a time suitable to elute perylene (Per) at the end of the fraction. In this way, a decrease in retention power of the HPLC column can be tolerated without adjustment of the MOAH fraction until some MOAH start being eluted into the MOSH fraction. This critical point can be checked either with di(2-ethylhexyl) benzene (DEHB) as a marker or the HPLC-UV chromatogram. Finally, based on new findings in rats and human tissues, it is recommended to integrate the MOSH and MOAH up to the retention time of the n-alkane C40. Copyright © 2017 Elsevier B.V. All rights

Gas chromatography fractionation platform featuring parallel flame-ionization detection and continuous high-resolution analyte collection in 384-well plates.

PubMed

Jonker, Willem; Clarijs, Bas; de Witte, Susannah L; van Velzen, Martin; de Koning, Sjaak; Schaap, Jaap; Somsen, Govert W; Kool, Jeroen

2016-09-02

Gas chromatography (GC) is a superior separation technique for many compounds. However, fractionation of a GC eluate for analyte isolation and/or post-column off-line analysis is not straightforward, and existing platforms are limited in the number of fractions that can be collected. Moreover, aerosol formation may cause serious analyte losses. Previously, our group has developed a platform that resolved these limitations of GC fractionation by post-column infusion of a trap solvent prior to continuous small-volume fraction collection in a 96-wells plate (Pieke et al., 2013 [17]). Still, this GC fractionation set-up lacked a chemical detector for the on-line recording of chromatograms, and the introduction of trap solvent resulted in extensive peak broadening for late-eluting compounds. This paper reports advancements to the fractionation platform allowing flame ionization detection (FID) parallel to high-resolution collection of a full GC chromatograms in up to 384 nanofractions of 7s each. To this end, a post-column split was incorporated which directs part of the eluate towards FID. Furthermore, a solvent heating device was developed for stable delivery of preheated/vaporized trap solvent, which significantly reduced band broadening by post-column infusion. In order to achieve optimal analyte trapping, several solvents were tested at different flow rates. The repeatability of the optimized GC fraction collection process was assessed demonstrating the possibility of up-concentration of isolated analytes by repetitive analyses of the same sample. The feasibility of the improved GC fractionation platform for bioactivity screening of toxic compounds was studied by the analysis of a mixture of test pesticides, which after fractionation were subjected to a post-column acetylcholinesterase (AChE) assay. Fractions showing AChE inhibition could be unambiguously correlated with peaks from the parallel-recorded FID chromatogram. Copyright © 2016 Elsevier B.V. All rights

Application of liquid chromatography-electrospray ionization mass spectrometry for study of steroid-converting enzymes.

PubMed

Miksík, Ivan; Mikulíková, Katerina; Pácha, Jirí; Kucka, Marek; Deyl, Zdenek

2004-02-05

A high-performance liquid chromatography-atmospheric pressure ionization-electrospray ionization mass spectrometry (HPLC-API-ESI-MS) method was developed for the analysis of steroids in a study of steroid-converting enzymes. Separations ware done on a Zorbax Eclipse XDB-C18 column (eluted with a linear methanol-water-acetic acid gradient) and identification of the steroids involved was done by API-ESI-MS using positive ion mode and extracted ion analysis. The applicability of the present method for studying steroid metabolism was proven in assaying two steroid-converting enzymes (20beta-hydroxysteroid dehydrogenase and 11beta-hydroxysteroid dehydrogenase) in various biological samples (rat and chicken intestine, chicken oviduct).

Soil moisture by extraction and gas chromatography

NASA Technical Reports Server (NTRS)

Merek, E. L.; Carle, G. C.

1973-01-01

To determine moisture content of soils rapidly and conveniently extract moisture with methanol and determine water content of methanol extract by gas chromatography. Moisture content of sample is calculated from weight of water and methanol in aliquot and weight of methanol added to sample.

Electron beam method and apparatus for obtaining uniform discharges in electrically pumped gas lasers

DOEpatents

Fenstermacher, Charles A.; Boyer, Keith

1986-01-01

A method and apparatus for obtaining uniform, high-energy, large-volume electrical discharges in the lasing medium of a gas laser whereby a high-energy electron beam is used as an external ionization source to ionize substantially the entire volume of the lasing medium which is then readily pumped by means of an applied potential less than the breakdown voltage of the medium. The method and apparatus are particularly useful in CO.sub.2 laser systems.

Determining degree of roasting in cocoa beans by artificial neural network (ANN)-based electronic nose system and gas chromatography/mass spectrometry (GC/MS).

PubMed

Tan, Juzhong; Kerr, William L

2018-08-01

Roasting is a critical step in chocolate processing, where moisture content is decreased and unique flavors and texture are developed. The determination of the degree of roasting in cocoa beans is important to ensure the quality of chocolate. Determining the degree of roasting relies on human specialists or sophisticated chemical analyses that are inaccessible to small manufacturers and farmers. In this study, an electronic nose system was constructed consisting of an array of gas sensors and used to detect volatiles emanating from cocoa beans roasted for 0, 20, 30 and 40 min. The several signals were used to train a three-layer artificial neural network (ANN). Headspace samples were also analyzed by gas chromatography/mass spectrometry (GC/MS), with 23 select volatiles used to train a separate ANN. Both ANNs were used to predict the degree of roasting of cocoa beans. The electronic nose had a prediction accuracy of 94.4% using signals from sensors TGS 813, 826, 822, 830, 830, 2620, 2602 and 2610. In comparison, the GC/MS predicted the degree of roasting with an accuracy of 95.8%. The electronic nose system is able to predict the extent of roasting, as well as a more sophisticated approach using GC/MS. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Bound-Electron Nonlinearity Beyond the Ionization Threshold.

PubMed

Wahlstrand, J K; Zahedpour, S; Bahl, A; Kolesik, M; Milchberg, H M

2018-05-04

We present absolute space- and time-resolved measurements of the ultrafast laser-driven nonlinear polarizability in argon, krypton, xenon, nitrogen, and oxygen up to ionization fractions of a few percent. These measurements enable determination of the strongly nonperturbative bound-electron nonlinear polarizability well beyond the ionization threshold, where it is found to remain approximately quadratic in the laser field, a result normally expected at much lower intensities where perturbation theory applies.

Bound-Electron Nonlinearity Beyond the Ionization Threshold

NASA Astrophysics Data System (ADS)

Wahlstrand, J. K.; Zahedpour, S.; Bahl, A.; Kolesik, M.; Milchberg, H. M.

2018-05-01

We present absolute space- and time-resolved measurements of the ultrafast laser-driven nonlinear polarizability in argon, krypton, xenon, nitrogen, and oxygen up to ionization fractions of a few percent. These measurements enable determination of the strongly nonperturbative bound-electron nonlinear polarizability well beyond the ionization threshold, where it is found to remain approximately quadratic in the laser field, a result normally expected at much lower intensities where perturbation theory applies.

Communication: Electron ionization of DNA bases.

PubMed

Rahman, M A; Krishnakumar, E

2016-04-28

No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve the existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space.

Thermospray ionization liquid chromatography-mass spectrometry and chemical ionization gas chromatography- mass spectrometry of hexazinone metabolites in soil and vegetation extracts

Treesearch

Joseph B. Fischer; Jerry L. Michael

1995-01-01

We have used thermospray LC-MS to confirm three highly polar metabolites (A, B. and G) of the herbicide hexazinone [3-cyclohexyl-6-(dimethylamino)-l-methyl-1,3,5-triazine-2,4(1H,3H)-dione]. and chemical ionization GC-MS to confirm two other metabolites (D and E) in extracts of soil and vegetation from a forest in the Central Alabama Piedmont. Selected-ion monitoring (...

Demonstration of self-truncated ionization injection for GeV electron beams

PubMed Central

Mirzaie, M.; Li, S.; Zeng, M.; Hafz, N. A. M.; Chen, M.; Li, G. Y.; Zhu, Q. J.; Liao, H.; Sokollik, T.; Liu, F.; Ma, Y. Y.; Chen, L.M.; Sheng, Z. M.; Zhang, J.

2015-01-01

Ionization-induced injection mechanism was introduced in 2010 to reduce the laser intensity threshold for controllable electron trapping in laser wakefield accelerators (LWFA). However, usually it generates electron beams with continuous energy spectra. Subsequently, a dual-stage target separating the injection and acceleration processes was regarded as essential to achieve narrow energy-spread electron beams by ionization injection. Recently, we numerically proposed a self-truncation scenario of the ionization injection process based upon overshooting of the laser-focusing in plasma which can reduce the electron injection length down to a few hundred micrometers, leading to accelerated beams with extremely low energy-spread in a single-stage. Here, using 100 TW-class laser pulses we report experimental observations of this injection scenario in centimeter-long plasma leading to the generation of narrow energy-spread GeV electron beams, demonstrating its robustness and scalability. Compared with the self-injection and dual-stage schemes, the self-truncated ionization injection generates higher-quality electron beams at lower intensities and densities, and is therefore promising for practical applications. PMID:26423136

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neustetter, M.; Jabbour Al Maalouf, E.; Denifl, S., E-mail: Stephan.Denifl@uibk.ac.at, E-mail: plimaovieira@fct.unl.pt

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO){sub 6}) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO){sub 6} clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO){sub n}{sup +} (0 ≤ n ≤ 6) and W{sub 2}(CO){sub n}{sup +} (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO){sub n}{sup +} (0 ≤more » n ≤ 3) and W{sub 2}C(CO){sub n}{sup +} (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.« less

Analysis of chlorophenoxy acid herbicides in water by large-volume on-line derivatization and gas chromatography-mass spectrometry.

PubMed

Ding, W H; Liu, C H; Yeh, S P

2000-10-27

This work presents a modified method to analyze chlorophenoxy acid herbicides in water samples. The herbicides 2,4-D (2,4-dichlorophenoxyacetic acid). Silvex (2,4,5-trichlorophenoxypropionic acid) and 2,4,5-T (2,4,5-trichlorophenoxyacetic acid) were used to evaluate the method. The method involves extraction of samples by a graphitized carbon black cartridge, and on-line derivatization in the GC injection port using a large-volume (10-20 microl) direct sample introduction (DSI) device with tetraalkylammonium salts. The analytes were then identified and quantitated by ion-trap gas chromatography-mass spectrometry. The large-volume DSI injection-port derivatization technique provides sensitivity, fast and reproducible results for chlorophenoxy acid herbicides residues, to quantitation at 0.1 to 0.2 microg/l in 500-ml water samples. An enhanced characteristic mass chromatogram of molecular ions of butylated chlorophenoxy acid herbicides with a significant chlorine isotope pattern by electron impact ionization MS allows us to determine herbicides residues at trace levels in aqueous samples. Recovery of the herbicide residues in spiked various water samples ranged from 70 to 99% while RSDs ranged from 1 to 13%.

S1 certification of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in a candidate certified reference material (organochlorine pesticides in tea) by isotope dilution gas chromatography-mass spectrometry.

PubMed

Sin, Della Wai-Mei; Wong, Yee-Lok; Cheng, Eddie Chung-Chin; Lo, Man-Fung; Ho, Clare; Mok, Chuen-Shing; Wong, Siu-Kay

2015-04-01

This paper presents the certification of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in a candidate tea certified reference material (code: GLHK-11-03) according to the requirements of the ISO Guide 30 series. Certification of GLHK-11-03 was based on an analytical method purposely developed for the accurate measurement of the mass fraction of the target analytes in the material. An isotope dilution mass spectrometry (IDMS) method involving determination by (i) gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS) and (ii) gas chromatography-electron ionization-high-resolution mass spectrometry (GC-EI-HRMS) techniques was employed. The performance of the described method was demonstrated through participation in the key comparison CCQM-K95 "Mid-Polarity Analytes in Food Matrix: Mid-Polarity Pesticides in Tea" organized by the Consultative Committee for Amount of Substance-Metrology in Chemistry in 2012, where the study material was the same as the certified reference material (CRM). The values reported by using the developed method were in good agreement with the key comparison reference value (KCRV) assigned for beta-endosulfan (727 ± 14 μg kg(-1)) and endosulfan sulfate (505 ± 11 μg kg(-1)), where the degree of equivalence (DoE) values were 0.41 and 0.40, respectively. The certified values of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in dry mass fraction in GLHK-11-03 were 350, 730, and 502 μg kg(-1), respectively, and the respective expanded uncertainties, due to sample inhomogeneity, long-term and short-term stability, and variability in the characterization procedure, were 27 μg kg(-1) (7.8 %), 48 μg kg(-1) (6.6 %), and 33 μg kg(-1) (6.6 %).

Headspace Gas Chromatography Method for Studies of Reaction and Permeation of Volatile Agents with Solid Materials

DTIC Science & Technology

2015-01-01

HEADSPACE GAS CHROMATOGRAPHY METHOD FOR STUDIES OF REACTION AND PERMEATION OF...TITLE AND SUBTITLE Headspace Gas Chromatography Method for Studies of Reaction and Permeation of Volatile Agents with Solid Materials 5a...method is described for measuring the reactivity and permeability of fabrics, films, and other solid materials. Headspace gas chromatography (GC)

Electron-Impact Excitation and Ionization in Air

DTIC Science & Technology

2009-09-01

average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron...information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and...physics-based model of nonequilibrium chemistry and radiation in hypersonic flow, it is timely to investigate and update the electron collision cross

Mixed Stationary Liquid Phases for Gas-Liquid Chromatography.

ERIC Educational Resources Information Center

Koury, Albert M.; Parcher, Jon F.

1979-01-01

Describes a laboratory technique for use in an undergraduate instrumental analysis course that, using the interpretation of window diagrams, prepares a mixed liquid phase column for gas-liquid chromatography. A detailed procedure is provided. (BT)

Prototype of an Interface for Hyphenating Distillation with Gas Chromatography and Mass Spectrometry

PubMed Central

Tang, Ya-Ru; Yang, Hui-Hsien; Urban, Pawel L.

2017-01-01

Chemical analysis of complex matrices—containing hundreds of compounds—is challenging. Two-dimensional separation techniques provide an efficient way to reduce complexity of mixtures analyzed by mass spectrometry (MS). For example, gasoline is a mixture of numerous compounds, which can be fractionated by distillation techniques. However, coupling conventional distillation with other separations as well as MS is not straightforward. We have established an automatic system for online coupling of simple microscale distillation with gas chromatography (GC) and electron ionization MS. The developed system incorporates an interface between the distillation condenser and the injector of a fused silica capillary GC column. Development of this multidimensional separation (distillation-GC-MS) was preceded by a series of preliminary off-line experiments. In the developed technique, the components with different boiling points are fractionated and instantly analyzed by GC-MS. The obtained data sets illustrate dynamics of the distillation process. An important advantage of the distillation-GC-MS technique is that raw samples can directly be analyzed without removal of the non-volatile matrix residues that could contaminate the GC injection port and the column. Distilling the samples immediately before the injection to the GC column may reduce possible matrix effects—especially in the early phase of separation, when molecules with different volatilities co-migrate. It can also reduce losses of highly volatile components (during fraction collection and transfer). The two separation steps are partly orthogonal, what can slightly increase selectivity of the entire analysis. PMID:28337400

Effect of injection-gas concentration on the electron beam quality from a laser-plasma accelerator

NASA Astrophysics Data System (ADS)

Mirzaie, Mohammad; Zhang, Guobo; Li, Song; Gao, Kai; Li, Guangyu; Ain, Quratul; Hafz, Nasr A. M.

2018-04-01

By using 25-45 TW ultra-short (30 fs) laser pulses, we report on the effect of the injection gas concentration on the quality of electron beams generated by a laser-driven plasma wakefield acceleration employing the ionization-injection. For a plasma formed from helium-nitrogen gas mixture and depending on the concentration of the nitrogen gas, we could distinguish a clear trend for the quality of the generated electron beams in terms of their peak energy, energy-spread, divergence angle, and beam charge. The results clearly showed that the lower the nitrogen concentration, the better the quality (higher peak energy, smaller energy spread, and smaller emittance) of the generated electron beams. The results are in reasonable agreement with two-dimensional particle-in-cell simulations.

Highly informative multiclass profiling of lipids by ultra-high performance liquid chromatography - Low resolution (quadrupole) mass spectrometry by using electrospray ionization and atmospheric pressure chemical ionization interfaces.

PubMed

Beccaria, Marco; Inferrera, Veronica; Rigano, Francesca; Gorynski, Krzysztof; Purcaro, Giorgia; Pawliszyn, Janusz; Dugo, Paola; Mondello, Luigi

2017-08-04

A simple, fast, and versatile method, using an ultra-high performance liquid chromatography system coupled with a low resolution (single quadrupole) mass spectrometer was optimized to perform multiclass lipid profiling of human plasma. Particular attention was made to develop a method suitable for both electrospray ionization and atmospheric pressure chemical ionization interfaces (sequentially in positive- and negative-ion mode), without any modification of the chromatographic conditions (mobile phase, flow-rate, gradient, etc.). Emphasis was given to the extrapolation of the structural information based on the fragmentation pattern obtained using atmospheric pressure chemical ionization interface, under each different ionization condition, highlighting the complementary information obtained using the electrospray ionization interface, of support for related molecule ions identification. Furthermore, mass spectra of phosphatidylserine and phosphatidylinositol obtained using the atmospheric pressure chemical ionization interface are reported and discussed for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron self-injection due to a plasma density downramp and gas ionization in a plasma wakefield accelerator in the blowout regime

NASA Astrophysics Data System (ADS)

Yi, S. A.; D'Avignon, E. C.; Khudik, V.; Shvets, G.

2010-11-01

We study self-injection into a plasma wakefield accelerator (PWFA) in the blowout regime analytically and through particle-in-cell (PIC) simulations. We propose a new injection mechanism into a plasma wakefield accelerator, where growth of the blowout region is enabled through a slow decrease in background plasma density along the direction of propagation. Deepening of the potential well due to this growth causes a reduction of electron Hamiltonian in the co-moving frame. This reduction depends on the shape of the blowout region, its growth rate, and impact parameter of the electron. When the reduction is greater than mc^2 [1,2], the electron becomes trapped inside the bubble. We demonstrate this effect using analytic expressions for the bubble potentials [3], and estimate plasma density gradients, and beam charge and size required for injection. We also apply the injection criterion to electron trapping through gas ionization. This work is supported by the US DOE grants DE-FG02-04ER41321 and DE-FG02-07ER54945. [1] S. Kalmykov, S.A. Yi, V. Khudik, and G. Shvets, Phys. Rev. Lett. 103, 135004 (2009). [2] S.A. Yi, V. Khudik, S. Kalmykov, and G. Shvets, Plasma Phys. Contr. Fus., in press. [3] W. Lu, C. Huang, M. Zhou, M. Tzoufras et al., Phys. Plasmas 13, 056709 (2006).

Attosecond Electron Correlation Dynamics in Double Ionization of Benzene Probed with Two-Electron Angular Streaking

NASA Astrophysics Data System (ADS)

Winney, Alexander H.; Lee, Suk Kyoung; Lin, Yun Fei; Liao, Qing; Adhikari, Pradip; Basnayake, Gihan; Schlegel, H. Bernhard; Li, Wen

2017-09-01

With a novel three-dimensional electron-electron coincidence imaging technique and two-electron angular streaking method, we show that the emission time delay between two electrons can be measured from tens of attoseconds to more than 1 fs. Surprisingly, in benzene, the double ionization rate decays as the time delay between the first and second electron emission increases during the first 500 as. This is further supported by the decay of the Coulomb repulsion in the direction perpendicular to the laser polarization. This result reveals that laser-induced electron correlation plays a major role in strong field double ionization of benzene driven by a nearly circularly polarized field.

Non-targeted analysis of electronics waste by comprehensive two-dimensional gas chromatography combined with high-resolution mass spectrometry: Using accurate mass information and mass defect analysis to explore the data.

PubMed

Ubukata, Masaaki; Jobst, Karl J; Reiner, Eric J; Reichenbach, Stephen E; Tao, Qingping; Hang, Jiliang; Wu, Zhanpin; Dane, A John; Cody, Robert B

2015-05-22

Comprehensive two-dimensional gas chromatography (GC×GC) and high-resolution mass spectrometry (HRMS) offer the best possible separation of their respective techniques. Recent commercialization of combined GC×GC-HRMS systems offers new possibilities for the analysis of complex mixtures. However, such experiments yield enormous data sets that require new informatics tools to facilitate the interpretation of the rich information content. This study reports on the analysis of dust obtained from an electronics recycling facility by using GC×GC in combination with a new high-resolution time-of-flight (TOF) mass spectrometer. New software tools for (non-traditional) Kendrick mass defect analysis were developed in this research and greatly aided in the identification of compounds containing chlorine and bromine, elements that feature in most persistent organic pollutants (POPs). In essence, the mass defect plot serves as a visual aid from which halogenated compounds are recognizable on the basis of their mass defect and isotope patterns. Mass chromatograms were generated based on specific ions identified in the plots as well as region of the plot predominantly occupied by halogenated contaminants. Tentative identification was aided by database searches, complementary electron-capture negative ionization experiments and elemental composition determinations from the exact mass data. These included known and emerging flame retardants, such as polybrominated diphenyl ethers (PBDEs), hexabromobenzene, tetrabromo bisphenol A and tris (1-chloro-2-propyl) phosphate (TCPP), as well as other legacy contaminants such as polychlorinated biphenyls (PCBs) and polychlorinated terphenyls (PCTs). Copyright © 2015 Elsevier B.V. All rights reserved.

ENVIRONMENTAL APPLICATION OF GAS CHROMATOGRAPHY/ATOMIC EMISSION DETECTION

EPA Science Inventory

A gas chromatography/atomic emission detector (GC/AED) system has been evaluated for its applicability to environmental analysis. Detection limits, elemental response factors, and regression analysis data were determined for 58 semivolatile environmental contaminants. Detection l...

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

PubMed

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.

Soft Argon-Propane Dielectric Barrier Discharge Ionization.

PubMed

Schütz, Alexander; Lara-Ortega, Felipe J; Klute, Felix David; Brandt, Sebastian; Schilling, Michael; Michels, Antje; Veza, Damir; Horvatic, Vlasta; García-Reyes, Juan F; Franzke, Joachim

2018-03-06

Dielectric barrier discharges (DBDs) have been used as soft ionization sources (DBDI) for organic mass spectrometry (DBDI-MS) for approximately ten years. Helium-based DBDI is often used because of its good ionization efficiency, low ignition voltage, and homogeneous plasma conditions. Argon needs much higher ignition voltages than helium when the same discharge geometry is used. A filamentary plasma, which is not suitable for soft ionization, may be produced instead of a homogeneous plasma. This difference results in N 2 , present in helium and argon as an impurity, being Penning-ionized by helium but not by metastable argon atoms. In this study, a mixture of argon and propane (C 3 H 8 ) was used as an ignition aid to decrease the ignition and working voltages, because propane can be Penning-ionized by argon metastables. This approach leads to homogeneous argon-based DBDI. Furthermore, operating DBDI in an open environment assumes that many uncharged analyte molecules do not interact with the reactant ions. To overcome this disadvantage, we present a novel approach, where the analyte is introduced in an enclosed system through the discharge capillary itself. This nonambient DBDI-MS arrangement is presented and characterized and could advance the novel connection of DBDI with analytical separation techniques such as gas chromatography (GC) and high-pressure liquid chromatography (HPLC) in the near future.

Communication: Electron ionization of DNA bases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rahman, M. A.; Krishnakumar, E., E-mail: ekkumar@tifr.res.in

2016-04-28

No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve themore » existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space.« less

Statistical analysis of fragmentation patterns of electron ionization mass spectra of enolized-trimethylsilylated anabolic androgenic steroids

NASA Astrophysics Data System (ADS)

Fragkaki, A. G.; Angelis, Y. S.; Tsantili-Kakoulidou, A.; Koupparis, M.; Georgakopoulos, C.

2009-08-01

Anabolic androgenic steroids (AAS) are included in the List of prohibited substances of the World Anti-Doping Agency (WADA) as substances abused to enhance athletic performance. Gas chromatography coupled to mass spectrometry (GC-MS) plays an important role in doping control analyses identifying AAS as their enolized-trimethylsilyl (TMS)-derivatives using the electron ionization (EI) mode. This paper explores the suitability of complementary GC-MS mass spectra and statistical analysis (principal component analysis, PCA and partial least squares-discriminant analysis, PLS-DA) to differentiate AAS as a function of their structural and conformational features expressed by their fragment ions. The results obtained showed that the application of PCA yielded a classification among the AAS molecules which became more apparent after applying PLS-DA to the dataset. The application of PLS-DA yielded a clear separation among the AAS molecules which were, thus, classified as: 1-ene-3-keto, 3-hydroxyl with saturated A-ring, 1-ene-3-hydroxyl, 4-ene-3-keto, 1,4-diene-3-keto and 3-keto with saturated A-ring anabolic steroids. The study of this paper also presents structurally diagnostic fragment ions and dissociation routes providing evidence for the presence of unknown AAS or chemically modified molecules known as designer steroids.

Tracing kinematic (mis)alignments in CALIFA merging galaxies. Stellar and ionized gas kinematic orientations at every merger stage

NASA Astrophysics Data System (ADS)

Barrera-Ballesteros, J. K.; García-Lorenzo, B.; Falcón-Barroso, J.; van de Ven, G.; Lyubenova, M.; Wild, V.; Méndez-Abreu, J.; Sánchez, S. F.; Marquez, I.; Masegosa, J.; Monreal-Ibero, A.; Ziegler, B.; del Olmo, A.; Verdes-Montenegro, L.; García-Benito, R.; Husemann, B.; Mast, D.; Kehrig, C.; Iglesias-Paramo, J.; Marino, R. A.; Aguerri, J. A. L.; Walcher, C. J.; Vílchez, J. M.; Bomans, D. J.; Cortijo-Ferrero, C.; González Delgado, R. M.; Bland-Hawthorn, J.; McIntosh, D. H.; Bekeraitė, S.

2015-10-01

We present spatially resolved stellar and/or ionized gas kinematic properties for a sample of 103 interacting galaxies, tracing all merger stages: close companions, pairs with morphological signatures of interaction, and coalesced merger remnants. In order to distinguish kinematic properties caused by a merger event from those driven by internal processes, we compare our galaxies with a control sample of 80 non-interacting galaxies. We measure for both the stellar and the ionized gas components the major (projected) kinematic position angles (PAkin, approaching and receding) directly from the velocity distributions with no assumptions on the internal motions. This method also allow us to derive the deviations of the kinematic PAs from a straight line (δPAkin). We find that around half of the interacting objects show morpho-kinematic PA misalignments that cannot be found in the control sample. In particular, we observe those misalignments in galaxies with morphological signatures of interaction. On the other hand, thelevel of alignment between the approaching and receding sides for both samples is similar, with most of the galaxies displaying small misalignments. Radial deviations of the kinematic PA orientation from a straight line in the stellar component measured by δPAkin are large for both samples. However, for a large fraction of interacting galaxies the ionized gas δPAkin is larger than the typical values derived from isolated galaxies (48%), indicating that this parameter is a good indicator to trace the impact of interaction and mergers in the internal motions of galaxies. By comparing the stellar and ionized gas kinematic PA, we find that 42% (28/66) of the interacting galaxies have misalignments larger than 16°, compared to 10% from the control sample. Our results show the impact of interactions in the motion of stellar and ionized gas as well as the wide the variety of their spatially resolved kinematic distributions. This study also provides a local

Some recent developments in headspace gas chromatography

Treesearch

J.Y. Zhu; X.-S. Chai

2005-01-01

In this study, recent developments in headspace gas chromatography (HSGC) are briefly reviewed. Several novel HSGC techniques developed recently are presented in detail. These techniques were developed using the unique characteristics of the headspace sampling process implemented in commercial HSGC systems and therefore can be easily applied in laboratory and...

Determination of short chain carboxylic acids in vegetable oils and fats using ion exclusion chromatography electrospray ionization mass spectrometry.

PubMed

Viidanoja, Jyrki

2015-02-27

A new method for quantification of short chain C1-C6 carboxylic acids in vegetable oils and fats by employing Liquid Chromatography Mass Spectrometry (LC-MS) has been developed. The method requires minor sample preparation and applies non-conventional Electrospray Ionization (ESI) liquid phase chemistry. Samples are first dissolved in chloroform and then extracted using water that has been spiked with stable isotope labeled internal standards that are used for signal normalization and absolute quantification of selected acids. The analytes are separated using Ion Exclusion Chromatography (IEC) and detected with Electrospray Ionization Mass Spectrometry (ESI-MS) as deprotonated molecules. Prior to ionization the eluent that contains hydrochloric acid is modified post-column to ensure good ionization efficiency of the analytes. The averaged within run precision and between run precision were generally lower than 8%. The accuracy was between 85 and 115% for most of the analytes. The Lower Limit of Quantification (LLOQ) ranged from 0.006 to 7mg/kg. It is shown that this method offers good selectivity in cases where UV detection fails to produce reliable results. Copyright © 2015 Elsevier B.V. All rights reserved.

Electron impact ionization dynamics of para-benzoquinone

NASA Astrophysics Data System (ADS)

Jones, D. B.; Ali, E.; Ning, C. G.; Colgan, J.; Ingólfsson, O.; Madison, D. H.; Brunger, M. J.

2016-10-01

Triple differential cross sections (TDCSs) for the electron impact ionization of the unresolved combination of the 4 highest occupied molecular orbitals (4b3g, 5b2u, 1b1g, and 2b3u) of para-benzoquinone are reported. These were obtained in an asymmetric coplanar geometry with the scattered electron being observed at the angles -7.5°, -10.0°, -12.5° and -15.0°. The experimental cross sections are compared to theoretical calculations performed at the molecular 3-body distorted wave level, with a marginal level of agreement between them being found. The character of the ionized orbitals, through calculated momentum profiles, provides some qualitative interpretation for the measured angular distributions of the TDCS.

Easy ambient sonic-spray ionization mass spectrometry combined with thin-layer chromatography.

PubMed

Haddad, Renato; Milagre, Humberto M S; Catharino, Rodrigo Ramos; Eberlin, Marcos N

2008-04-15

On-spot detection and analyte characterization on thin-layer chromatography (TLC) plates is performed via ambient desorption/ionization and (tandem) mass spectrometry detection, that is, via easy ambient sonic spray ionization mass spectrometry (EASI-MS). As proof-of-principle cases, mixtures of semipolar nitrogenated compounds as well as pharmaceutical drugs and vegetable oils have been tested. The technique has also been applied to monitor a chemical reaction of synthetic importance. EASI is the simplest and gentlest ambient ionization technique currently available, assisted solely by N2 (or air). It uses no voltages, no electrical discharges; no UV or laser beams, and no high temperature and is most easily implemented in all API mass spectrometers. TLC is also the simplest, fastest, and most easily performed chromatographic technique. TLC plus EASI-MS therefore provide a simple and advantageous combination of chromatographic separation and sensitive detection of the TLC spots as well as on-spot MS or MS/MS characterization. The favorable characteristics of TLC-EASI-MS indicate advantageous applications in several areas such as drug and oil analysis, phytochemistry and synthetic chemistry, forensics via reliable counterfeit detection, and quality control.

Electron Impact Ionization: A New Parameterization for 100 eV to 1 MeV Electrons

NASA Technical Reports Server (NTRS)

Fang, Xiaohua; Randall, Cora E.; Lummerzheim, Dirk; Solomon, Stanley C.; Mills, Michael J.; Marsh, Daniel; Jackman, Charles H.; Wang, Wenbin; Lu, Gang

2008-01-01

Low, medium and high energy electrons can penetrate to the thermosphere (90-400 km; 55-240 miles) and mesosphere (50-90 km; 30-55 miles). These precipitating electrons ionize that region of the atmosphere, creating positively charged atoms and molecules and knocking off other negatively charged electrons. The precipitating electrons also create nitrogen-containing compounds along with other constituents. Since the electron precipitation amounts change within minutes, it is necessary to have a rapid method of computing the ionization and production of nitrogen-containing compounds for inclusion in computationally-demanding global models. A new methodology has been developed, which has parameterized a more detailed model computation of the ionizing impact of precipitating electrons over the very large range of 100 eV up to 1,000,000 eV. This new parameterization method is more accurate than a previous parameterization scheme, when compared with the more detailed model computation. Global models at the National Center for Atmospheric Research will use this new parameterization method in the near future.

Electron kinetics dependence on gas pressure in laser-induced oxygen plasma experiment: Theoretical analysis

NASA Astrophysics Data System (ADS)

Gamal, Yosr E. E.-D.; Abdellatif, Galila

2017-08-01

A study is performed to investigate the dependency of threshold intensity on gas pressure observed in the measurements of the breakdown of molecular oxygen that carried out by Phuoc (2000) [1]. In this experiment, the breakdown was induced by 532 nm laser radiation of pulse width 5.5 ns and spot size of 8.5 μm, in oxygen over a wide pressure range (190-3000 Torr). The analysis aimed to explore the electron kinetic reliance on gas pressure for the separate contribution of each of the gain and loss processes encountered in this study. The investigation is based on an electron cascade model applied previously in Gamal and Omar (2001) [2] and Gaabour et al. (2013) [3]. This model solves numerically a differential equation designates the time evolution of the electron energy distribution, and a set of rate equations that describe the change of excited states population. The numerical examination of the electron energy distribution function and its parameters revealed that photo-ionization of the excited molecules plays a significant role in enhancing the electron density growth rate over the whole tested gas pressure range. This process is off set by diffusion of electrons out of the focal volume in the low-pressure regime. At atmospheric pressure electron, collisional processes dominate and act mainly to populate the excited states. Hence photo-ionization becomes efficient and compete with the encountered loss processes (electron diffusion, vibrational excitation of the ground state molecules as well as two body attachments). At high pressures ( 3000 Torr) three body attachments are found to be the primary cause of losses which deplete the electron density and hence results in the slow decrease of the threshold intensity.

Enhanced Ionization of Embedded Clusters by Electron-Transfer-Mediated Decay in Helium Nanodroplets.

PubMed

LaForge, A C; Stumpf, V; Gokhberg, K; von Vangerow, J; Stienkemeier, F; Kryzhevoi, N V; O'Keeffe, P; Ciavardini, A; Krishnan, S R; Coreno, M; Prince, K C; Richter, R; Moshammer, R; Pfeifer, T; Cederbaum, L S; Mudrich, M

2016-05-20

We report the observation of electron-transfer-mediated decay (ETMD) involving magnesium (Mg) clusters embedded in helium (He) nanodroplets. ETMD is initiated by the ionization of He followed by removal of two electrons from the Mg clusters of which one is transferred to the He ion while the other electron is emitted into the continuum. The process is shown to be the dominant ionization mechanism for embedded clusters for photon energies above the ionization potential of He. For Mg clusters larger than five atoms we observe stable doubly ionized clusters. Thus, ETMD provides an efficient pathway to the formation of doubly ionized cold species in doped nanodroplets.

Quantitative structure-retention relationship studies using immobilized artificial membrane chromatography I: amended linear solvation energy relationships with the introduction of a molecular electronic factor.

PubMed

Li, Jie; Sun, Jin; Cui, Shengmiao; He, Zhonggui

2006-11-03

Linear solvation energy relationships (LSERs) amended by the introduction of a molecular electronic factor were employed to establish quantitative structure-retention relationships using immobilized artificial membrane (IAM) chromatography, in particular ionizable solutes. The chromatographic indices, log k(IAM), were determined by HPLC on an IAM.PC.DD2 column for 53 structurally diverse compounds, including neutral, acidic and basic compounds. Unlike neutral compounds, the IAM chromatographic retention of ionizable compounds was affected by their molecular charge state. When the mean net charge per molecule (delta) was introduced into the amended LSER as the sixth variable, the LSER regression coefficient was significantly improved for the test set including ionizable solutes. The delta coefficients of acidic and basic compounds were quite different indicating that the molecular electronic factor had a markedly different impact on the retention of acidic and basic compounds on IAM column. Ionization of acidic compounds containing a carboxylic group tended to impair their retention on IAM, while the ionization of basic compounds did not have such a marked effect. In addition, the extra-interaction with the polar head of phospholipids might cause a certain change in the retention of basic compounds. A comparison of calculated and experimental retention indices suggested that the semi-empirical LSER amended by the addition of a molecular electronic factor was able to reproduce adequately the experimental retention factors of the structurally diverse solutes investigated.

Isomer and Fluorination Effects among Fluorine Substituted Hydrocarbon C3/C4 Molecules in Electron Impact Ionization

NASA Astrophysics Data System (ADS)

Patel, U. R.; Joshipura, K. N.

2015-05-01

Electron collision processes are very important in both man-made and natural plasmas, for determining the energy balances and transport properties of electrons. Electron -molecule scattering leading to ionization represents one of the most fundamental processes in collision physics. In the gas phase, the total efficiency of the process is described by the absolute total electron impact ionization cross section. Carbon based materials are some of the widely used materials for a divertor plate and magnetically confined fusion devices. In the ``ITER,'' it is very important for steady state operation to have an estimate of the lifetime of carbon plasma facing components. Apart from fusion plasma relevance, the present theoretical study is very important in modeling and controlling other electron assisted processes in many areas. Hydrocarbons play an important role for plasma diagnostics as impurities in the Tokamak fusion divertor, as seed gases for the production of radicals and ions in low temperature plasma processing. Fluorine substituted hydrocarbons (perfluorocarbons) are important as reactants in plasma assisted fabrication processes. In the present work, we have calculated total ionization cross sections Qion for C3/C4 Hydrocarbon isomers by electron impact, and comparisons are made mutually to observe isomer effect. Comparisons are also made by substituting H atom by F atom and revealing fluorination effect. The present calculations are quite significant owing to the lack of experimental data, with just an isolated previous theoretical work in some cases.

A Modified Kinematic Model of Neutral and Ionized Gas in Galactic Center

NASA Astrophysics Data System (ADS)

Krishnarao, Dhanesh; Benjamin, Robert A.; Haffner, L. Matthew

2018-01-01

Gas near the center of the Milky Way is very complex across all phases (cold, warm, neutral, ionized, atomic, molecular, etc.) and shows strong observational evidence for warping, lopsided orientations and strongly non-circular kinematics. Historically, the kinematic complexities were modeled with many discrete features involved with expulsive phenomena near Galactic Center. However, much of the observed emission can be explained with a single unified and smooth density structure when geometrical and perspective effects are accounted for. Here we present a new model for a tilted, elliptical disk of gas within the inner 2 kpc of Galactic center based on the series of models following Burton & Liszt (1978 - 1992, Papers I- V). Machine learning techniques such as the Histogram of Oriented Gradients image correlation statistic are used to optimize the geometry and kinematics of neutral and ionized gas in 3D observational space (position,position, velocity). The model successfully predicts emission from neutral gas as seen by HI (Hi4Pi) and explains anomalous ionized gas features in H-Alpha emission (Wisconsin H-Alpha Mapper) and UV absorption lines (Hubble Space Telescope - Space Telescope Imaging Spectrograph). The modeled distribution of this tilted gas disk along with its kinematics of elliptical x1 orbits can reveal new insight about the Galactic Bar, star formation, and high-velocity gas near Galactic Center and its relation with the Fermi Bubble.

Few-cycle attosecond pulse chirp effects on asymmetries in ionized electron momentum distributions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng Liangyou; Tan Fang; Gong Qihuang

2009-07-15

The momentum distributions of electrons ionized from H atoms by chirped few-cycle attosecond pulses are investigated by numerically solving the time-dependent Schroedinger equation. The central carrier frequency of the pulse is chosen to be 25 eV, which is well above the ionization threshold. The asymmetry (or difference) in the yield of electrons ionized along and opposite to the direction of linear laser polarization is found to be very sensitive to the pulse chirp (for pulses with fixed carrier-envelope phase), both for a fixed electron energy and for the energy-integrated yield. In particular, the larger the pulse chirp, the larger themore » number of times the asymmetry changes sign as a function of ionized electron energy. For a fixed chirp, the ionized electron asymmetry is found to be sensitive also to the carrier-envelope phase of the few-cycle pulse.« less

Turbulence in the ionized gas of the Orion nebula

NASA Astrophysics Data System (ADS)

Arthur, S. J.; Medina, S.-N. X.; Henney, W. J.

2016-12-01

In order to study the nature, origin, and impact of turbulent velocity fluctuations in the ionized gas of the Orion nebula, we apply a variety of statistical techniques to observed velocity cubes. The cubes are derived from high resolving power (R ≈ 40 000) longslit spectroscopy of optical emission lines that span a range of ionizations. From velocity channel analysis (VCA), we find that the slope of the velocity power spectrum is consistent with predictions of Kolmogorov theory between scales of 8 and 22 arcsec (0.02 to 0.05 pc). The outer scale, which is the dominant scale of density fluctuations in the nebula, approximately coincides with the autocorrelation length of the velocity fluctuations that we determine from the second-order velocity structure function. We propose that this is the principal driving scale of the turbulence, which originates in the autocorrelation length of dense cores in the Orion molecular filament. By combining analysis of the non-thermal linewidths with the systematic trends of velocity centroid versus ionization, we find that the global champagne flow and smaller scale turbulence each contribute in equal measure to the total velocity dispersion, with respective root-mean-square widths of 4-5 km s-1. The turbulence is subsonic and can account for only one half of the derived variance in ionized density, with the remaining variance provided by density gradients in photoevaporation flows from globules and filaments. Intercomparison with results from simulations implies that the ionized gas is confined to a thick shell and does not fill the interior of the nebula.

Optical ionization detector

DOEpatents

Wuest, C.R.; Lowry, M.E.

1994-03-29

An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium. 3 figures.

Optical ionization detector

DOEpatents

Wuest, Craig R.; Lowry, Mark E.

1994-01-01

An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium.

Thermionic gas switch

DOEpatents

Hatch, George L.; Brummond, William A.; Barrus, Donald M.

1986-01-01

A temperature responsive thermionic gas switch having folded electron emitting surfaces. An ionizable gas is located between the emitter and an interior surface of a collector, coaxial with the emitter. In response to the temperature exceeding a predetermined level, sufficient electrons are derived from the emitter to cause the gas in the gap between the emitter and collector to become ionized, whereby a very large increase in current in the gap occurs. Due to the folded emitter surface area of the switch, increasing the "on/off" current ratio and adjusting the "on" current capacity is accomplished.

Numerical models for the diffuse ionized gas in galaxies. I. Synthetic spectra of thermally excited gas with turbulent magnetic reconnection as energy source

NASA Astrophysics Data System (ADS)

Hoffmann, T. L.; Lieb, S.; Pauldrach, A. W. A.; Lesch, H.; Hultzsch, P. J. N.; Birk, G. T.

2012-08-01

Aims: The aim of this work is to verify whether turbulent magnetic reconnection can provide the additional energy input required to explain the up to now only poorly understood ionization mechanism of the diffuse ionized gas (DIG) in galaxies and its observed emission line spectra. Methods: We use a detailed non-LTE radiative transfer code that does not make use of the usual restrictive gaseous nebula approximations to compute synthetic spectra for gas at low densities. Excitation of the gas is via an additional heating term in the energy balance as well as by photoionization. Numerical values for this heating term are derived from three-dimensional resistive magnetohydrodynamic two-fluid plasma-neutral-gas simulations to compute energy dissipation rates for the DIG under typical conditions. Results: Our simulations show that magnetic reconnection can liberate enough energy to by itself fully or partially ionize the gas. However, synthetic spectra from purely thermally excited gas are incompatible with the observed spectra; a photoionization source must additionally be present to establish the correct (observed) ionization balance in the gas.

Electron- and proton-induced ionization of pyrimidine

NASA Astrophysics Data System (ADS)

Champion, Christophe; Quinto, Michele A.; Weck, Philippe F.

2015-05-01

The present work describes a quantum-mechanically based model of the electron- and proton-induced ionization of isolated pyrimidine molecules. The impact energies range from the target ionization threshold up to ~1 keV for electrons and from 10 keV up to 10 MeV for protons. The cross-section calculations are performed within the 1st Born approximation in which the ejected electron is described by a Coulomb wave whereas the incident and the scattered projectiles are both described by plane waves. The pyrimidine target is described using the Gaussian 09 software package. The theoretical predictions obtained are in good agreement with experimental absolute total cross sections, while large discrepancies are observed between existing semi-empirical models and the present calculations. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

Properties of a weakly ionized NO gas sensor based on multi-walled carbon nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jingyuan; Zhang, Yong, E-mail: zhyong@mail.xjtu.edu.cn; Pan, Zhigang

2015-08-31

Nitric oxide NO is one of the major targets for environmental monitoring, but the existing NO sensors are limited by their low sensitivity and narrow test range. Here, a NO gas sensor employing multiwalled carbon nanotubes (MWCNTs) was fabricated, and its properties in NO–N{sub 2} mixture were investigated from both emission and ionization. The current I{sub e} passing through the nanotubes cathode was found to decrease with increasing NO concentration and increase linearly in different slopes with the extracting voltage U{sub e}. It is shown that the Schottky barrier of the MWCNTs calculated by I{sub e} increased with NO concentrationmore » due to the adsorption of NO gas, which restrained the electron emission and consequently weakened the ionization. The positive ion currents I{sub c} passing through the collecting electrode at different voltages of U{sub e} were found to monotonically decrease with increasing NO concentration, which was induced by both of the reduced electron emission and the consumption of the two excited metastable states N{sub 2}(A{sup 3}∑{sub u}{sup +}) and N{sub 2}(a′{sup 1}∑{sub u}{sup −}) by NO. The sensor exhibited high sensitivity at the low temperature of 30 °C. The calculated conductivity was found to be able to take place of I{sub c} for NO detection in a wide voltage range of 80–150 V U{sub e}.« less

Screening of environmental contaminants in honey bee wax comb using gas chromatography-high-resolution time-of-flight mass spectrometry.

PubMed

Gómez-Ramos, M M; García-Valcárcel, A I; Tadeo, J L; Fernández-Alba, A R; Hernando, M D

2016-03-01

This study reports an analytical approach intended to be used for investigation of non-targeted environmental contaminants and to characterize the organic pollution pattern of bee wax comb samples. The method comprises a generic extraction followed by detection with gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-TOF-MS), operated in electron impact ionization (EI) mode. The screening approach for the investigation of non-targeted contaminants consisted of initial peak detection by deconvolution and matching the first-stage mass spectra EI-MS(1) with a nominal mass spectral library. To gain further confidence in the structural characterization of the contaminants under investigation, the molecular formula of representative ions (molecular ion when present in the EI spectrum) and, for at least other two fragment ions, was provided for those with an accurate mass scoring (mass error < 5 ppm). This methodology was applied for screening environmental contaminants in 50 samples of bee wax comb. This approach has allowed the tentative identification of some GC-amenable contaminants belonging to different chemical groups, among them, phthalates and polycyclic aromatic hydrocarbons (PAHs), along with residues of veterinary treatments used in apiculture.

Chelate-modified polymers for atmospheric gas chromatography

NASA Technical Reports Server (NTRS)

Christensen, W. W.; Mayer, L. A.; Woeller, F. H. (Inventor)

1980-01-01

Chromatographic materials were developed to serve as the stationary phase of columns used in the separation of atmospheric gases. These materials consist of a crosslinked porous polymer matrix, e.g., a divinylbenzene polymer, into which has been embedded an inorganic complexed ion such as N,N'-ethylene-bis-(acetylacetoniminato)-cobalt (2). Organic nitrogenous bases, such as pyridine, may be incorporated into the chelate polymer complexes to increase their chromatographic utility. With such materials, the process of gas chromatography is greatly simplified, especially in terms of time and quantity of material needed for a gas separation.

Investigation of the profile of phenolic compounds in the leaves and stems of Pandiaka heudelotii using gas chromatography coupled with flame ionization detector.

PubMed

Ifeanacho, Mercy O; Ikewuchi, Catherine C; Ikewuchi, Jude C

2017-05-01

The profile of phenolic compounds in the leaves and stems of Pandiaka heudelotii was investigated using gas chromatography coupled with flame ionization detector. The leaves and stems had high flavonoids and benzoic acid derivatives content, and moderate levels of lignans and hydroxycinnamates. Twenty-eight known flavonoids were detected, which consisted mainly of kaempferol (41.93% in leaves and 47.97% in stems), (+)-catechin (17.12% in leaves and 16.11% in stems), quercetin (13.83% in leaves and 9.39% in stems), luteolin (7.34% in leaves and 7.71% in stems), and artemetin (6.53% in leaves and 4.83% in stems). Of the six known hydroxycinnamates detected, chlorogenic acid (80.79% in leaves and 87.56% in stems) and caffeic acid (18.98% in leaves and 12.30% in stems) were the most abundant, while arctigenin (77.81% in leaves and 83.40% in stems) and retusin (13.82% in leaves and 10.59% in stems) were the most abundant of the nine known lignans detected. Twelve known benzoic acid derivatives were detected, consisting mainly of ellagic acid (65.44% in leaves and 72.89% in stems), p-hydroxybenzoic acid (25.10% in leaves and 18.95% in stems), and vanillic acid (8.80% in leaves and 7.30% in stems). The rich phytochemical profile of the leaves and stems is an indication of their ability to serve as sources of nutraceuticals.

Extraction and preconcentration of residual solvents in pharmaceuticals using dynamic headspace-liquid phase microextraction and their determination by gas chromatography-flame ionization detection.

PubMed

Farajzadeh, Mir Ali; Dehghani, Hamideh; Yadeghari, Adeleh; Khoshmaram, Leila

2017-02-01

The present study describes a microextraction and determination method for analyzing residual solvents in pharmaceutical products using dynamic headspace-liquid phase microextraction technique followed by gas chromatography-flame ionization detection. In this method dimethyl sulfoxide (μL level) placed into a GC liner-shaped extraction vessel is used as a collection/extraction solvent. Then the liner is exposed to the headspace of a vial containing the sample solution. The effect of different parameters influencing the microextraction procedure including collection/extraction solvent type and its volume, ionic strength, extraction time, extraction temperature and concentration of NaOH solution used in dissolving the studied pharmaceuticals are investigated and optimized. Under the optimum extraction conditions, the method showed wide linear ranges between 0.5 and 5000 mg L -1 . The other analytical parameters were obtained in the following ranges: enrichment factors 240-327, extraction recoveries 72-98% and limits of detection 0.1-0.8 mg L -1 in solution and 0.6-3.2 μg g -1 in solid. Relative standard deviations for the extraction of 100 mg L -1 of each analyte were obtained in the ranges of 4-7 and 5-8% for intra-day (n = 6) and inter-day (n = 4) respectively. Finally the target analytes were determined in different samples such as erythromycin, azithromycin, cefalexin, amoxicillin and co-amoxiclav by the proposed method. Copyright © 2016 John Wiley & Sons, Ltd.

Direct determination of acrylamide in potato chips by using headspace solid-phase microextraction coupled with gas chromatography-flame ionization detection.

PubMed

Ghiasvand, Ali Reza; Hajipour, Somayeh

2016-01-01

Acrylamide is a potentially toxic and carcinogenic substance present in many high-consumption foods. Recently, this matter has been placed in category of "reasonably anticipated to be a human carcinogen" by National Toxicology Program (NTP). Therefore, simple and cost-effective determination of acrylamide in food samples has attracted intense interest. The most reported techniques for this purpose are GC-MS and LC-MS, which are very expensive and available in few laboratories. In this research, for the first time, a rapid, easy and low-cost method is introduced for sensitive and precise determination of acrylamide in foodstuffs, using gas chromatography-flame ionization detection (GC-FID) system after its direct trapping in the upper atmosphere of samples by headspace solid-phase microextraction (HS-SPME). The effects of main experimental variables were studied and the optimized parameters were obtained as the type of fiber, carboxen/divinylbenzene/polydimethylsiloxane (CAR/DVB/PDMS); extraction time, 30 min; extraction temperature, 60°C; moisture content, 10 µL water per 1g of sample; desorption time, 2 min; and desorption temperature, 230°C. The linear calibration graph was obtained in the range of 0.77-50 µg g(-1), with regression coefficient of 0.998. The detection and quantification limits of the proposed method were 0.22 and 0.77 µg g(-1), respectively. The recoveries, for different food samples, were 79.6-95.7%. The repeatability of measurements, expressed as relative standard deviation (RSD), were found to be 4.1-8.0% (n=9). The proposed HS-SPME-GC-FID method was successfully carried out for quantifying of trace levels of acrylamide in some processed food products (chips and French fries), sold in open local markets. Copyright © 2015 Elsevier B.V. All rights reserved.

Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum.

PubMed

Geng, Dawei; Jogsten, Ingrid Ericson; Dunstan, Jody; Hagberg, Jessika; Wang, Thanh; Ruzzin, Jerome; Rabasa-Lhoret, Rémi; van Bavel, Bert

2016-07-01

A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r(2))>0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4pg/μL) and CS 3 (4pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of field ionization effect on the divergence of laser-driven fast electrons

NASA Astrophysics Data System (ADS)

Lang, Y.; Yang, X. H.; Xu, H.; Jin, Z.; Zhuo, H. B.

2018-07-01

The effect of field ionization on the divergence of fast electrons (E k ≥ 50 keV), driven by ultrashort-ultraintense laser pulse interaction with plasma, is studied by using 2D3V particle-in-cell simulations. It is found that, due to temperature anisotropy of the fast electrons in the ionizing target, strong fluctuant magnetic fields in the preplasma region is generated through Weibel instability. In turn, the field induces an enhancement of the hot electron divergence for the target with ionization process. Meanwhile, compared with the target without an ionization process, larger divergence of hot electrons can also be seen in the ionizing target with laser intensity varying from 5 × 1019 W/cm2 to 5 × 1020 W/cm2 and the divergence is weakly dependent on target materials for a fixed profile of preplasma. The results here are useful for the application of laser-driven fast electron beams.

Treatment of Electronic Energy Level Transition and Ionization Following the Particle-Based Chemistry Model

NASA Technical Reports Server (NTRS)

Liechty, Derek S.; Lewis, Mark

2010-01-01

A new method of treating electronic energy level transitions as well as linking ionization to electronic energy levels is proposed following the particle-based chemistry model of Bird. Although the use of electronic energy levels and ionization reactions in DSMC are not new ideas, the current method of selecting what level to transition to, how to reproduce transition rates, and the linking of the electronic energy levels to ionization are, to the author s knowledge, novel concepts. The resulting equilibrium temperatures are shown to remain constant, and the electronic energy level distributions are shown to reproduce the Boltzmann distribution. The electronic energy level transition rates and ionization rates due to electron impacts are shown to reproduce theoretical and measured rates. The rates due to heavy particle impacts, while not as favorable as the electron impact rates, compare favorably to values from the literature. Thus, these new extensions to the particle-based chemistry model of Bird provide an accurate method for predicting electronic energy level transition and ionization rates in gases.

Cascade Model of Ionization Multiplication of Electrons in Glow Discharge Plasma

NASA Astrophysics Data System (ADS)

Romanenko, V. A.; Solodky, S. A.; Kudryavtsev, A. A.; Suleymanov, I. A.

1996-10-01

For determination of EDF in non-uniform fields a Monte-Carlo simulation(Tran Ngoc An et al., J.Phys.D: Appl. Phys. 10, 2317 (1977))^,(J.P. Boeuf et al., Phys.D: Appl.Phys. 15, 2169 (1982)) is applied. As alternative multi-beam cascade model(H.B. Valentini, Contrib.Plasma Phys. 27, 331 (1987)) is offered. Our model eliminates defects of that model and enables to determine EDF of low pressure plasma in non-uniform fields. A cascade model (with EDF dividing in monoenergetic electron groups) for arbitrary electric potential profile was used. Modeling was carried out for electron forward scattering only, constant electron mean free path; ionization was considered only. The equation system was solved for the region with kinetic energies more than ionization energy. The boundary conditions (on ionization energy curve) take into account electron transitions from higher-lying level in the less than ionization energy region and secondary electron production. The problem solution in analytical functions was obtained. The insertion of additional processes does not make significant difficulties. EDF and electrokinetical parameters in helium from numerical calculations are well agreed with above-mentioned authors. Work was carried out under RFFI (project N 96-02-18417) support.

CHARACTERIZATION OF DANSYLATED CYSTEINE, GLUTATHIONE DISULFIDE, CYSTEINE AND CYSTINE BY NARROW BORE LIQUID CHROMATOGRAPHY/ELECTROSPRAY IONIZATION MASS SPECTROMETRY

EPA Science Inventory

A method using reversed phase high performance liquid chromatography/electrospray ionization-mass spectrometric (RP-LC/ESI-MS) method has been developed to confirm the identity of dansylated derivatives of cysteine and glutathione, and their respective dimers. Cysteine, GSH, CSSC...

Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

2016-11-01

Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

Complete solution of electronic excitation and ionization in electron-hydrogen molecule scattering

DOE PAGES

Zammit, Mark C.; Savage, Jeremy S.; Fursa, Dmitry V.; ...

2016-06-08

The convergent close-coupling method has been used to solve the electron-hydrogen molecule scattering problem in the fixed-nuclei approximation. Excellent agreement with experiment is found for the grand total, elastic, electronic-excitation, and total ionization cross sections from the very low to the very high energies. This shows that for the electronic degrees of freedom the method provides a complete treatment of electron scattering on molecules as it does for atoms.

Dust trap formation in a non-self-sustained discharge with external gas ionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Filippov, A. V., E-mail: fav@triniti.ru; Babichev, V. N.; Pal’, A. F.

2015-11-15

Results from numerical studies of a non-self-sustained gas discharge containing micrometer dust grains are presented. The non-self-sustained discharge (NSSD) was controlled by a stationary fast electron beam. The numerical model of an NSSD is based on the diffusion drift approximation for electrons and ions and self-consistently takes into account the influence of the dust component on the electron and ion densities. The dust component is described by the balance equation for the number of dust grains and the equation of motion for dust grains with allowance for the Stokes force, gravity force, and electric force in the cathode sheath. Themore » interaction between dust grains is described in the self-consistent field approximation. The height of dust grain levitation over the cathode is determined and compared with experimental results. It is established that, at a given gas ionization rate and given applied voltage, there is a critical dust grain size above which the levitation condition in the cathode sheath cannot be satisfied. Simulations performed for the dust component consisting of dust grains of two different sizes shows that such grains levitate at different heights, i.e., size separation of dust drains levitating in the cathode sheath of an NSSD takes place.« less

Identification of clinical isolates of mycobacteria with gas-liquid chromatography: a 10-month follow-up study.

PubMed Central

Tisdall, P A; DeYoung, D R; Roberts, G D; Anhalt, J P

1982-01-01

Identification of routine mycobacterial isolates by gas-liquid chromatography profile analysis was performed on 335 strains received at the Mayo Clinic over a 10-month period. Comparison of identification by gas-liquid chromatography versus conventional biochemical profiles was made. The two methods agreed on the identification of 320 isolates, with gas-liquid chromatography profiling making eight errors and biochemical profiling making four errors. In three cases, discrepancies could not be resolved. PMID:6811612

Determination of volatile marker compounds in raw ham using headspace-trap gas chromatography.

PubMed

Bosse Née Danz, Ramona; Wirth, Melanie; Konstanz, Annette; Becker, Thomas; Weiss, Jochen; Gibis, Monika

2017-03-15

A simple, reliable and automated method was developed and optimized for qualification and quantification of aroma-relevant volatile marker compounds of North European raw ham using a headspace (HS)-Trap gas chromatography-mass spectrometry (GC-MS) and GC-flame ionization detector (FID) analysis. A total of 38 volatile compounds were detected with this HS-Trap GC-MS method amongst which the largest groups were ketones (12), alcohols (8), hydrocarbons (7), aldehydes (6) and esters (3). The HS-Trap GC-FID method was optimized for the parameters: thermostatting time and temperature, vial and desorption pressure, number of extraction cycles and salt addition. A validation for 13 volatile marker compounds with limits of detection in ng/g was carried out. The optimized method can serve as alternative to conventional headspace and solid phase micro extraction methods and allows users to determine volatile compounds in raw hams making it of interest to industrial and academic meat scientists. Copyright © 2016 Elsevier Ltd. All rights reserved.

Closed-loop pulsed helium ionization detector

DOEpatents

Ramsey, Roswitha S.; Todd, Richard A.

1987-01-01

A helium ionization detector for gas chromatography is operated in a constant current, pulse-modulated mode by configuring the detector, electrometer and a high voltage pulser in a closed-loop control system. The detector current is maintained at a fixed level by varying the frequency of fixed-width, high-voltage bias pulses applied to the detector. An output signal proportional to the pulse frequency is produced which is indicative of the charge collected for a detected species.

Ion Densities in the Nightside Ionosphere of Mars: Effects of Electron Impact Ionization

NASA Astrophysics Data System (ADS)

Girazian, Z.; Mahaffy, P.; Lillis, R. J.; Benna, M.; Elrod, M.; Fowler, C. M.; Mitchell, D. L.

2017-11-01

We use observations from the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission to show how superthermal electron fluxes and crustal magnetic fields affect ion densities in the nightside ionosphere of Mars. We find that due to electron impact ionization, high electron fluxes significantly increase the CO2+, O+, and O2+ densities below 200 km but only modestly increase the NO+ density. High electron fluxes also produce distinct peaks in the CO2+, O+, and O2+ altitude profiles. We also find that superthermal electron fluxes are smaller near strong crustal magnetic fields. Consequently, nightside ion densities are also smaller near strong crustal fields because they decay without being replenished by electron impact ionization. Furthermore, the NO+/O2+ ratio is enhanced near strong crustal fields because, in the absence of electron impact ionization, O2+ is converted into NO+ and not replenished. Our results show that electron impact ionization is a significant source of CO2+, O+, and O2+ in the nightside ionosphere of Mars.

Short rise time intense electron beam generator

DOEpatents

Olson, Craig L.

1987-01-01

A generator for producing an intense relativistic electron beam having a subnanosecond current rise time includes a conventional generator of intense relativistic electrons feeding into a short electrically conductive drift tube including a cavity containing a working gas at a low enough pressure to prevent the input beam from significantly ionizing the working gas. Ionizing means such as a laser simultaneously ionize the entire volume of working gas in the cavity to generate an output beam having a rise time less than one nanosecond.

Short rise time intense electron beam generator

DOEpatents

Olson, C.L.

1984-03-16

A generator for producing an intense relativisitc electron beam having a subnanosecond current rise time includes a conventional generator of intense relativistic electrons feeding into a short electrically conductive drift tube including a cavity containing a working gas at a low enough pressure to prevent the input beam from significantly ionizing the working gas. Ionizing means such as a laser simultaneously ionize the entire volume of working gas in the cavity to generate an output beam having a rise time less than one nanosecond.

Properties of the highly ionized disk and halo gas toward two distant high-latitude stars

NASA Technical Reports Server (NTRS)

Savage, Blair D.; Sembach, K. R.

1994-01-01

Goddard High Resolution Spectrograph (GHRS) intermediate -resolution observations of S III, Si III, Al III, Si IV, C IV, and N V absorption along the sight lines to HD 18100 (l = 217.9 deg, b = -62.7, d = 3.1 kpc, z = -2.8 kpc) and HD 100340 (l = 258.9 deg, b = +61.2 deg, d = 5.3 kpc, z = 4.6 kpc) are presented. These small science aperture spectra have resolutions ranging from 11 to 20 km/s full width at half maximum (FWHM) and S/N from 30 to 65 per diode substep. Strong absorption by moderately and highly ionized gas is seen in each direction. The absorption in the direction of the south Galactic polar region (HD 18100) is kinematically simple, while the absorption in the direction of north Galactic polar region (HD 100304) is kinematically complex. In each case the absorption by the highly ionized gas lies within the velocity range of absorption by neutral and weakly ionized gas. Along each sight line, the velocity dispersion determined from the unsaturated absorption lines increases with the energy required to create each ion. The logarithmic column densities for Al III, Si IV, C IV, and N V are log N(atoms/sq cm = 12.71, 13.10, 13.58, and 12.75 toward HD 18100 and log N = 12.88, 13.31, 13.83, and 13.04 toward HD 100340. Average ionic ratios among these species are very similar along the two sight lines. Differences in profile shape between the absorption for AL II, Si IV, C IV, and N V provide additional support for the claim of Savage, Sembach, & Cardelli (1994) that there exists two types of highly ionized gas in the interstellar medium. One type of highly ionized gas is responsible for the structured Si IV absorption and part of the C IV absorption. In this gas N(C IV)/N(Si IV) approximately 3.0 and N(C IV)/N(N V) greater than 6. The absorption by this gas seems to be associated with some type of self-regulating interface or mixing layer between the warm and hot interstellar medium. The other type of highly ionized gas is responsible for most of the N V

Ultra-high performance supercritical fluid chromatography hyphenated to atmospheric pressure chemical ionization high resolution mass spectrometry for the characterization of fast pyrolysis bio-oils.

PubMed

Crepier, Julien; Le Masle, Agnès; Charon, Nadège; Albrieux, Florian; Duchene, Pascal; Heinisch, Sabine

2018-06-01

Extensive characterization of complex mixtures requires the combination of powerful analytical techniques. A Supercritical Fluid Chromatography (SFC) method was previously developed, for the specific case of fast pyrolysis bio oils, as an alternative to gas chromatography (GC and GC × GC) or liquid chromatography (LC and LC × LC), both separation methods being generally used prior to mass spectrometry (MS) for the characterization of such complex matrices. In this study we investigated the potential of SFC hyphenated to high resolution mass spectrometry (SFC-HRMS) for this characterization using Negative ion Atmospheric Pressure Chemical ionization ((-)APCI) for the ionization source. The interface between SFC and (-)APCI/HRMS was optimized from a mix of model compounds with the objective of maximizing the signal to noise ratio. The main studied parameters included both make-up flow-rate and make-up composition. A methodology for the treatment of APCI/HRMS data is proposed. This latter allowed for the identification of molecular formulae. Both SFC-APCI/HRMS method and data processing method were applied to a mixture of 36 model compounds, first analyzed alone and then spiked in a bio-oil. In both cases, 19 compounds could be detected. Among them 9 could be detected in a fast pyrolysis bio-oil by targeted analysis. The whole procedure was applied to the characterization of a bio-oil using helpful representations such as mass-plots, van Krevelen diagrams and heteroatom class distributions. Finally the results were compared with those obtained with a Fourier Transform ion-cyclotron resonance mass spectrometer (FT-ICR/MS). Copyright © 2018 Elsevier B.V. All rights reserved.

Identifying and Determining Halocarbons in Water Using Headspace Gas Chromatography.

DTIC Science & Technology

1981-10-01

chromatography Halogenated hydrocarbons , / Wastewater 26. T -ACT C’Cth.I .- ,,ee .- ,ncee, ,Id ntify y block number) --/,*Since the discovery that...USING HEADSPACE GAS CHROMATOGRAPHY Daniel C. Leggett INTRODUCTION Chlorination is a well-established method of disinfecting water for drinking and of... disinfecting municipal wastewater prior to disposal. The recent discovery that persistent chloro-organic molecules are formed in this processi 5 has

Development of a highly-sensitive Penning ionization electron spectrometer using the magnetic bottle effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ota, Masahiro; Ishiguro, Yuki; Nakajima, Yutaro

2016-02-01

This paper reports on a highly-sensitive retarding-type electron spectrometer for a continuous source of electrons, in which the electron collection efficiency is increased by utilizing the magnetic bottle effect. This study demonstrates an application to Penning ionization electron spectroscopy using collisional ionization with metastable He*(2{sup 3}S) atoms. Technical details and performances of the instrument are presented. This spectrometer can be used for studies of functional molecules and assemblies, and exterior electron densities are expected to be selectively observed by the Penning ionization.

Silica-based ionogels: nanoconfined ionic liquid-rich fibers for headspace solid-phase microextraction coupled with gas chromatography-barrier discharge ionization detection.

PubMed

Pena-Pereira, Francisco; Marcinkowski, Lukasz; Kloskowski, Adam; Namieśnik, Jacek

2014-12-02

In this work, hybrid silica-based materials with immobilized ionic liquids (ILs) were prepared by sol-gel technology and evaluated as solid-phase microextraction (SPME) fiber coatings. High loadings of the IL 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide ([C4MIM][TFSI]) were confined within the hybrid network. Coatings composition and morphology were evaluated using scanning electron microscopy and energy dispersive X-ray spectrometry. The obtained ionogel SPME fibers exhibited high extractability for aromatic volatile compounds, yielding good sensitivity and precision when combined with a gas chromatograph with barrier ionization discharge (GC-BID) detection. A central composite design was used for assessing the effect of experimental parameters on the extraction process. Under optimized conditions, the proposed ionogel SPME fiber coatings enabled the achievement of excellent enrichment factors (up to 7400). The limits of detection (LODs) were found in the range 0.03-1.27 μg L(-1), whereas the repeatability and fiber-to-fiber reproducibility were 5.6% and 12.0% on average, respectively. Water samples were analyzed by the proposed methodology, showing recovery values in the range of 88.7-113.9%. The results obtained in this work suggest that ionogels can be promising coating materials for future applications of SPME and related sample preparation techniques.

Quantification of Triacylglycerol Molecular Species in Edible Fats and Oils by Gas Chromatography-Flame Ionization Detector Using Correction Factors.

PubMed

Yoshinaga, Kazuaki; Obi, Junji; Nagai, Toshiharu; Iioka, Hiroyuki; Yoshida, Akihiko; Beppu, Fumiaki; Gotoh, Naohiro

2017-03-01

In the present study, the resolution parameters and correction factors (CFs) of triacylglycerol (TAG) standards were estimated by gas chromatography-flame ionization detector (GC-FID) to achieve the precise quantification of the TAG composition in edible fats and oils. Forty seven TAG standards comprising capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, and/or linolenic acid were analyzed, and the CFs of these TAGs were obtained against tripentadecanoyl glycerol as the internal standard. The capillary column was Ultra ALLOY + -65 (30 m × 0.25 mm i.d., 0.10 μm thickness) and the column temperature was programmed to rise from 250°C to 360°C at 4°C/min and then hold for 25 min. The limit of detection (LOD) and limit of quantification (LOQ) values of the TAG standards were > 0.10 mg and > 0.32 mg per 100 mg fat and oil, respectively, except for LnLnLn, and the LOD and LOQ values of LnLnLn were 0.55 mg and 1.84 mg per 100 mg fat and oil, respectively. The CFs of TAG standards decreased with increasing total acyl carbon number and degree of desaturation of TAG molecules. Also, there were no remarkable differences in the CFs between TAG positional isomers such as 1-palmitoyl-2-oleoyl-3-stearoyl-rac-glycerol, 1-stearoyl-2-palmitoyl-3-oleoyl-rac-glycerol, and 1-palmitoyl-2-stearoyl-3-oleoyl-rac-glycerol, which cannot be separated by GC-FID. Furthermore, this method was able to predict the CFs of heterogeneous (AAB- and ABC-type) TAGs from the CFs of homogenous (AAA-, BBB-, and CCC-type) TAGs. In addition, the TAG composition in cocoa butter, palm oil, and canola oil was determined using CFs, and the results were found to be in good agreement with those reported in the literature. Therefore, the GC-FID method using CFs can be successfully used for the quantification of TAG molecular species in natural fats and oils.

Interstellar matter in Shapley-Ames elliptical galaxies. II. The distribution of dust and ionized gas

NASA Astrophysics Data System (ADS)

Goudfrooij, P.; Hansen, L.; Jorgensen, H. E.; Norgaard-Nielsen, H. U.

1994-06-01

We present results of deep optical CCD imaging for a complete, optical magnitude-limited sample of 56 elliptical galaxies from the RSA catalog. For each galaxy we have obtained broad-band images (in B, V, and I) and narrow-band images using interference filters isolating the Hα+[NII] emission lines to derive the amount and morphology of dust and ionized gas. Detailed consideration of systematic errors due to effects of sky background subtraction and removal of stellar continuum light from the narrow-band images is described. The flux calibration of the narrow-band images is performed by deconvolving actually measured spectral energy distributions with the filter transmission curves. We also present optical long-slit spectroscopy to determine the [NII]/Hα intensity ratio of the ionized gas. Dust lanes and/or patches have been detected in 23 galaxies (41%) from this sample using both colour-index images and division by purely elliptical model images. We achieved a detection limit for dust absorption of A_B_~0.02. Accounting for selection effects, the true fraction of elliptical galaxies containing dust is estimated to be of order 80%. This detection rate is comparable to that of the IRAS satellite, and significantly larger than results of previous optical studies. Ionized gas has been detected in 32 galaxies (57%). The spectroscopic data confirm the presence and distribution of ionized gas as seen in the direct imaging. All elliptical galaxies in our sample in which a number of emission lines is detected show very similar emission-line intensity ratios, which are typical of LINER nuclei. The amounts of detectable dust and ionized gas are generally small--of order 10^4^-10^5^Msun_ of dust and 10^3^-10^4^Msun_ of ionized gas. The dust and ionized gas show a wide variety of distributions-extended along either the apparent major axis, or the minor axis, or a skewed axis, indicating that triaxiality is in general required as a galaxy figure. In some cases (NGC 1275, NGC

Chemotaxonomic differentiation of legionellae by detection and characterization of aminodideoxyhexoses and other unique sugars using gas chromatography-mass spectrometry.

PubMed Central

Fox, A; Rogers, J C; Fox, K F; Schnitzer, G; Morgan, S L; Brown, A; Aono, R

1990-01-01

Legionellae have been differentiated previously by analyzing their carbohydrate contents by gas chromatography with flame ionization detection. In the present study, total ion mode gas chromatography-mass spectrometry (GC-MS) was used to detect a number of unusual sugars, including one that is structurally related to O-methyldideoxyheptoses. Increased sensitivity and selectivity for carbohydrate detection was achieved by selected ion-monitoring GC-MS. Two of the uncommon sugars previously discovered in the legionellae (X1 and X2) were identified as quinovosamine and fucosamine, respectively. Legionella pneumophila contained rhamnose and quinovosamine but not the quinovosamine isomer fucosamine. Tatlockia micdadei and Legionella maceachernii contained large amounts of rhamnose, fucose, and fucosamine but not quinovosamine. These two species were the only legionellae studied that contained another unusual sugar that is referred to as X3, pending determination of its structure. Fluoribacter dumoffi, Fluoribacter bozemanae, and Legionella anisa were varied in their carbohydrate contents, both within and between species, but could be distinguished from L. pneumophila and the T. micdadei and L. maceachernii group. Fluoribacter gormanii was unique among the legionellae in that it lacked both quinovosamine and fucosamine. Legionella jordanis contained other unusual carbohydrates in addition to quinovosamine. GC-MS may have wide application in the differentiation of bacterial species. PMID:2324276

Enantioselective determination of triazole fungicide simeconazole in vegetables, fruits, and cereals using modified QuEChERS (quick, easy, cheap, effective, rugged and safe) coupled to gas chromatography/tandem mass spectrometry.

PubMed

Li, Jing; Dong, Fengshou; Xu, Jun; Liu, Xingang; Li, Yuanbo; Shan, Weili; Zheng, Yongquan

2011-09-19

A rapid and effective method for enantioselective determination of simeconazole enantiomers in food products (cucumber, tomato, apple, pear, wheat and rice) has been developed. The enantiomers were resolved by capillary gas chromatography (GC) using a commercial chiral column (BGB-172) and a temperature program from 150°C (held for 1 min) and then raised at 10°C min(-1) to 240°C (held for 10 min). This enantioselective gas chromatographic separation was combined with a clean-up/enrichment procedure based on the modification of QuEChERS (quick, easy, cheap, effective, rugged and safe) method. Co-extractives were removed with graphitized carbon black/primary secondary amine (GCB/PSA) solid-phase extraction (SPE) cartridges using acetonitrile:toluene (3:1, v/v) as eluent. Gas chromatography/ion trap mass spectrometry (GC-ITMS) with electron ionization (EI) was then used for qualitative and quantitative determination of the simeconazole enantiomers. Two precursor-to-product ion transitions (m/z 121-101 and 195-153) with the best signal intensity were chosen to build the multiple-reaction monitoring (MRM) acquisition method. The limits of detection for each enantiomer of simeconazole in six food products ranged between 0.4 and 0.9 μg kg(-1), which were much lower than maximum residue levels (MRLs) established by Japan. The methodology was successfully applied for the enantioselective analysis of simeconazole enantiomers in real samples, indicating its efficacy in investigating the environmental stereochemistry of simeconazole in food matrix. Copyright © 2011 Elsevier B.V. All rights reserved.

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

PubMed

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.

Size-exclusion chromatography for the determination of the boiling point distribution of high-boiling petroleum fractions.

PubMed

Boczkaj, Grzegorz; Przyjazny, Andrzej; Kamiński, Marian

2015-03-01

The paper describes a new procedure for the determination of boiling point distribution of high-boiling petroleum fractions using size-exclusion chromatography with refractive index detection. Thus far, the determination of boiling range distribution by chromatography has been accomplished using simulated distillation with gas chromatography with flame ionization detection. This study revealed that in spite of substantial differences in the separation mechanism and the detection mode, the size-exclusion chromatography technique yields similar results for the determination of boiling point distribution compared with simulated distillation and novel empty column gas chromatography. The developed procedure using size-exclusion chromatography has a substantial applicability, especially for the determination of exact final boiling point values for high-boiling mixtures, for which a standard high-temperature simulated distillation would have to be used. In this case, the precision of final boiling point determination is low due to the high final temperatures of the gas chromatograph oven and an insufficient thermal stability of both the gas chromatography stationary phase and the sample. Additionally, the use of high-performance liquid chromatography detectors more sensitive than refractive index detection allows a lower detection limit for high-molar-mass aromatic compounds, and thus increases the sensitivity of final boiling point determination. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing the chemical selectivity in discovery-based analysis with tandem ionization time-of-flight mass spectrometry detection for comprehensive two-dimensional gas chromatography.

PubMed

Freye, Chris E; Moore, Nicholas R; Synovec, Robert E

2018-02-16

The complementary information provided by tandem ionization time-of-flight mass spectrometry (TI-TOFMS) is investigated for comparative discovery-based analysis, when coupled with comprehensive two-dimensional gas chromatography (GC × GC). The TI conditions implemented were a hard ionization energy (70 eV) concurrently collected with a soft ionization energy (14 eV). Tile-based Fisher ratio (F-ratio) analysis is used to analyze diesel fuel spiked with twelve analytes at a nominal concentration of 50 ppm. F-ratio analysis is a supervised discovery-based technique that compares two different sample classes, in this case spiked and unspiked diesel, to reduce the complex GC × GC-TI-TOFMS data into a hit list of class distinguishing analyte features. Hit lists of the 70 eV and 14 eV data sets, and the single hit list produced when the two data sets are fused together, are all investigated. For the 70 eV hit list, eleven of the twelve analytes were found in the top thirteen hits. For the 14 eV hit list, nine of the twelve analytes were found in the top nine hits, with the other three analytes either not found or well down the hit list. As expected, the F-ratios per m/z used to calculate each average F-ratio per hit were generally smaller fragment ions for the 70 eV data set, while the larger fragment ions were emphasized in the 14 eV data set, supporting the notion that complementary information was provided. The discovery rate was improved when F-ratio analysis was performed on the fused data sets resulted in eleven of the twelve analytes being at the top of the single hit list. Using PARAFAC, analytes that were "discovered" were deconvoluted in order to obtain their identification via match values (MV). Location of the analytes and the "F-ratio spectra" obtained from F-ratio analysis were used to guide the deconvolution. Eight of the twelve analytes where successfully deconvoluted and identified using the in-house library for the 70�

Phase-dependent above-barrier ionization of excited-state electrons.

PubMed

Yang, Weifeng; Song, Xiaohong; Chen, Zhangjin

2012-05-21

The carrier-envelope phase (CEP)-dependent above-barrier ionization (ABI) has been investigated in order to probe the bound-state electron dynamics. It is found that when the system is initially prepared in the excited state, the ionization yield asymmetry between left and right sides can occur both in low-energy and high-energy parts of the photoelectron spectra. Moreover, in electron momentum map, a new interference effect along the direction perpendicular to the laser polarization is found. We show that this interference is related to the competition among different excited states. The interference effect is dependent on CEPs of few-cycle probe pulses, which can be used to trace the superposition information and control the electron wave packet of low excited states.

Axial thermal gradients in microchip gas chromatography.

PubMed

Wang, Anzi; Hynynen, Sampo; Hawkins, Aaron R; Tolley, Samuel E; Tolley, H Dennis; Lee, Milton L

2014-12-29

Fabrication technologies for microelectromechanical systems (MEMS) allow miniaturization of conventional benchtop gas chromatography (GC) to portable, palm-sized microfabricated GC (μGC) devices, which are suitable for on-site chemical analysis and remote sensing. The separation performance of μGC systems, however, has not been on par with conventional GC. Column efficiency, peak symmetry and resolution are often compromised by column defects and non-ideal injections. The relatively low performance of μGC devices has impeded their further commercialization and broader application. In this work, the separation performance of μGC columns was improved by incorporating thermal gradient gas chromatography (TGGC). The analysis time was ∼20% shorter for TGGC separations compared to conventional temperature-programmed GC (TPGC) when a wide sample band was introduced into the column. Up to 50% reduction in peak tailing was observed for polar analytes, which improved their resolution. The signal-to-noise ratios (S/N) of late-eluting peaks were increased by 3-4 fold. The unique focusing effect of TGGC overcomes many of the previous shortcomings inherent in μGC analyses. Copyright © 2014 Elsevier B.V. All rights reserved.

Quantum control via a genetic algorithm of the field ionization pathway of a Rydberg electron

NASA Astrophysics Data System (ADS)

Gregoric, Vincent C.; Kang, Xinyue; Liu, Zhimin Cheryl; Rowley, Zoe A.; Carroll, Thomas J.; Noel, Michael W.

2017-08-01

Quantum control of the pathway along which a Rydberg electron field ionizes is experimentally and computationally demonstrated. Selective field ionization is typically done with a slowly rising electric field pulse. The (1/n*)4 scaling of the classical ionization threshold leads to a rough mapping between arrival time of the electron signal and principal quantum number of the Rydberg electron. This is complicated by the many avoided level crossings that the electron must traverse on the way to ionization, which in general leads to broadening of the time-resolved field ionization signal. In order to control the ionization pathway, thus directing the signal to the desired arrival time, a perturbing electric field produced by an arbitrary wave-form generator is added to a slowly rising electric field. A genetic algorithm evolves the perturbing field in an effort to achieve the target time-resolved field ionization signal.

Simultaneous determination of chlorinated organic compounds from environmental samples using gas chromatography coupled with a micro electron capture detector and micro-plasma atomic emission detector

NASA Astrophysics Data System (ADS)

Quan, Xie; Chen, Shuo; Platzer, Bernhard; Chen, Jingwen; Gfrerer, Marion

2002-01-01

Water and sediment samples were screened simultaneously for the presence of polychlorinated organic compounds using gas chromatography (GC) coupled with an micro electron capture detector (μ-ECD) and a newly developed helium plasma based on a micro-atomic emission detector (μ-AED). The GC column effluent was split 15:85 between two detectors. In this way, two chromatograms, one obtained by μ-ECD and another by μ-AED, were recorded simultaneously. α-, β-hexachlorocyclohexane and p, p'-DDE were detected. RSDs of the monitoring results from the two detection methods were <20% for the three compounds. A detection limit of 8.5 pg and at least 3 orders of magnitude of linear range for μ-AED was observed.

Achieving high peak capacity production for gas chromatography and comprehensive two-dimensional gas chromatography by minimizing off-column peak broadening.

PubMed

Wilson, Ryan B; Siegler, W Christopher; Hoggard, Jamin C; Fitz, Brian D; Nadeau, Jeremy S; Synovec, Robert E

2011-05-27

By taking into consideration band broadening theory and using those results to select experimental conditions, and also by reducing the injection pulse width, peak capacity production (i.e., peak capacity per separation time) is substantially improved for one dimensional (1D-GC) and comprehensive two dimensional (GC×GC) gas chromatography. A theoretical framework for determining the optimal linear gas velocity (the linear gas velocity producing the minimum H), from experimental parameters provides an in-depth understanding of the potential for GC separations in the absence of extra-column band broadening. The extra-column band broadening is referred to herein as off-column band broadening since it is additional band broadening not due to the on-column separation processes. The theory provides the basis to experimentally evaluate and improve temperature programmed 1D-GC separations, but in order to do so with a commercial 1D-GC instrument platform, off-column band broadening from injection and detection needed to be significantly reduced. Specifically for injection, a resistively heated transfer line is coupled to a high-speed diaphragm valve to provide a suitable injection pulse width (referred to herein as modified injection). Additionally, flame ionization detection (FID) was modified to provide a data collection rate of 5kHz. The use of long, relatively narrow open tubular capillary columns and a 40°C/min programming rate were explored for 1D-GC, specifically a 40m, 180μm i.d. capillary column operated at or above the optimal average linear gas velocity. Injection using standard auto-injection with a 1:400 split resulted in an average peak width of ∼1.5s, hence a peak capacity production of 40peaks/min. In contrast, use of modified injection produced ∼500ms peak widths for 1D-GC, i.e., a peak capacity production of 120peaks/min (a 3-fold improvement over standard auto-injection). Implementation of modified injection resulted in retention time, peak width

Observation of two-center interference effects for electron impact ionization of N2

NASA Astrophysics Data System (ADS)

Chaluvadi, Hari; Nur Ozer, Zehra; Dogan, Mevlut; Ning, Chuangang; Colgan, James; Madison, Don

2015-08-01

In 1966, Cohen and Fano (1966 Phys. Rev. 150 30) suggested that one should be able to observe the equivalent of Young’s double slit interference if the double slits were replaced by a diatomic molecule. This suggestion inspired many experimental and theoretical studies searching for double slit interference effects both for photon and particle ionization of diatomic molecules. These effects turned out to be so small for particle ionization that this work proceeded slowly and evidence for interference effects were only found by looking at cross section ratios. Most of the early particle work concentrated on double differential cross sections for heavy particle scattering and the first evidence for two-center interference for electron-impact triple differential cross section (TDCS) did not appear until 2006 for ionization of H2. Subsequent work has now firmly established that two-center interference effects can be seen in the TDCS for electron-impact ionization of H2. However, in spite of several experimental and theoretical studies, similar effects have not been found for electron-impact ionization of N2. Here we report the first evidence for two-center interference for electron-impact ionization of N2.

Electron Impact K-shell Ionization of Atomic Targets

NASA Astrophysics Data System (ADS)

Saha, Bidhan; Basak, Arun K.; Alfaz Uddin, M.; Patoary, A. A. R.

2008-05-01

In spite of considerable progress -both theoretically and experimentally- recently in evaluating accurate K-shell ionization cross sections that play a decisive role for quantitative analyses using (i) electron probe microanalysis, (ii) Auger electron spectroscopy and (iii) electron energy loss spectra, attempts are still continuing to search for a model that can easily generate reliable cross sections for a wide range of energies and for various targets needed for plasma modeling code We report few modifications of the widely used binary encounter approximation (BEA) [1,2] and have tested by evaluating the electron impact K-shell ionization of few neutral targets at various projectile energies. Details will be presented at the meeting. [1] M. Gryziniski, Phys. Rev. A 138, 336 (1965); [2] L. Vriens, Proc. Phys. Soc. (London) 89, 13, (1966). [3M. A. Uddin , A. K. F. Haque, M. M. Billah, A. K. Basak, K, R, Karim and B. C. Saha, ,Phys. Rev. A 71,032715 (2005); [4] M. A. Uddin, A. K. Basak, and B. C. Saha, Int. J. Quan. Chem 100, 184 (2004).

Ultra-trace level analysis of morpholine, cyclohexylamine, and diethylaminoethanol in steam condensate by gas chromatography with multi-mode inlet, and flame ionization detection.

PubMed

Luong, J; Shellie, R A; Cortes, H; Gras, R; Hayward, T

2012-03-16

Steam condensate water treatment is a vital and integral part of the overall cooling water treatment process. Steam condensate often contains varying levels of carbon dioxide and oxygen which acts as an oxidizer. Carbon dioxide forms corrosive carbonic acid when dissolved in condensed steam. To neutralize the harmful effect of the carbonic acid, volatile amine compounds such as morpholine, cyclohexylamine, and diethylaminoethanol are often employed as part of a strategy to control corrosion in the water treatment process. Due to the high stability of these compounds in a water matrix, the indirect addition of such chemicals into the process via steam condensate often results in their presence throughout the process and even into the final product. It is therefore important to understand the impact of these chemicals and their fate within a chemical plant. The ability to analyze such compounds by gas chromatography has historically been difficult due to the lack of chromatographic system inertness at the trace level concentrations especially in an aqueous matrix. Here a highly sensitive, practical, and reliable gas chromatographic approach is described for the determination of morpholine, cyclohexylamine, and diethylaminoethanol in steam condensate at the part-per-billion (ppb) levels. The approach does not require any sample enrichment or derivatization. The technique employs a multi-mode inlet operating in pulsed splitless mode with programmed inlet temperature for sample introduction, an inert base-deactivated capillary column for solute separation and flame ionization detection. Chromatographic performance was further enhanced by the incorporation of 2-propanol as a co-solvent. Detection limits for morpholine, cyclohexylamine, diethylaminoethanol were established to be 100 ppb (v/v), with relative standard deviations (RSD) of less than 6% at the 95% confidence level (n=20) and a percent recovery of 96% or higher for the solutes of interest over a range of 0

Low-energy electron-impact ionization of helium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schow, E.; Hazlett, K.; Childers, J. G.

2005-12-15

Normalized doubly differential cross sections for the electron-impact ionization of helium at low energies are presented. The data are taken at the incident electron energies of 26.3, 28.3, 30.3, 32.5, 34.3, 36.5, and 40.7 eV and for scattering angles of 10 deg. -130 deg. The measurements involve the use of the moveable target method developed at California State University Fullerton to accurately determine the continuum background in the energy-loss spectra. Normalization of experimental data is made on a relative scale to well-established experimental differential cross sections for excitation of the n=2 manifold of helium and then on an absolute scalemore » to the well-established total ionization cross sections of Shah et al. [J. Phys. B 21, 2751 (1988)]. Comparisons are made with available experimental data and the results of the convergent close-coupling theory.« less

On ionizing shock waves

NASA Astrophysics Data System (ADS)

Kaniel, A.; Igra, O.; Ben-Dor, G.; Mond, M.

The flow field in the ionizing relaxation zone developed behind a normal shock wave in an electrically neutral, homogeneous, two temperature mixture of thermally ideal gases (molecules, atoms, ions, electrons) was numerically solved. The heat transfer between the electron gas and the other components was taken into account while all the other transport phenomena (molecular, turbulent and radiative) were neglected in the relaxation zone, since it is dominated by inelastic collisions. The threshold cross sections measured by Specht (1981), for excitation of argon by electron collisions, were used. The calculated results show good agreement with the results of the shock tube experiments presented by Glass and Liu (1978), especially in the electron avalanche region. A critical examination was made of the common assumptions regarding the average energy with which electrons are produced by atom-atom collisions and the relative effectiveness of atom-atom collisions (versus electron-atom collisions) in ionizing excited argon.

Composition of fatty acids in virgin olive oils from cross breeding segregating populations by gas chromatography separation with flame ionization detection.

PubMed

Sánchez de Medina, Verónica; El Riachy, Milad; Priego-Capote, Feliciano; Luque de Castro, María Dolores

2015-11-01

Recent technological advances to improve the quality of virgin olive oil (VOO) have been focused on olive breeding programs by selecting outstanding cultivars and target progenies. Fatty acid (FA) composition, with special emphasis on oleic acid (C18:1) and palmitic acid (C16:0), is one of the most critical quality factors to be evaluated in VOO. For this reason, the profile of FAs is frequently used as a decision tool in olive breeding programs. A method based on gas chromatography with flame ionization detection (GC-FID) was used to study the influence of genotype on the concentration of ten of the most important FAs in VOOs from target crosses Arbequina × Arbosana, Picual × Koroneiki and Sikitita × Arbosana and their corresponding genitors Arbequina, Arbosana, Koroneiki, Picual and Sikitita. For this purpose, a targeted approach was selected for determination of esterified FAs (EFAs) and non-esterified FAs (NEFAs) in a dual analysis by the same chromatographic method. A Pearson analysis revealed correlations between pairs of FAs, which allowed detecting metabolic connections through desaturation and elongation enzymes. An ANOVA test (with P < 0.01) led to identification of C16:0 EFA, C16:1 EFA and C18:1 EFA and also C16:1 NEFA and C18:0 NEFA as the FAs more influenced by cross breeding. Statistical analysis was carried out by unsupervised analysis using principal component analysis (PCA) and cluster analysis (CA) to look for variability sources. Crosses with a common genitor (Arbequina × Arbosana and Sikitita × Arbosana) were partially overlapped in the PCAs using the profile of FAs. The CA results revealed clear differences between Sikitita × Arbosana and Picual × Koroneiki crosses in the composition of the most significant FAs, while Arbequina × Arbosana was not properly discriminated from the other crosses. © 2014 Society of Chemical Industry.

Energy dependence of effective electron mass and laser-induced ionization of wide band-gap solids

NASA Astrophysics Data System (ADS)

Gruzdev, V. E.

2008-10-01

Most of the traditional theoretical models of laser-induced ionization were developed under the assumption of constant effective electron mass or weak dependence of the effective mass on electron energy. Those assumptions exclude from consideration all the effects resulting from significant increase of the effective mass with increasing of electron energy in real the conduction band. Promotion of electrons to the states with high effective mass can be done either via laserinduced electron oscillations or via electron-particle collisions. Increase of the effective mass during laser-material interactions can result in specific regimes of ionization. Performing a simple qualitative analysis by comparison of the constant-mass approximation vs realistic dependences of the effective mass on electron energy, we demonstrate that the traditional ionization models provide reliable estimation of the ionization rate in a very limited domain of laser intensity and wavelength. By taking into account increase of the effective mass with electron energy, we demonstrate that special regimes of high-intensity photo-ionization are possible depending on laser and material parameters. Qualitative analysis of the energy dependence of the effective mass also leads to conclusion that the avalanche ionization can be stopped by the effect of electron trapping in the states with large values of the effective mass.

Mechanism of Runaway Electron Generation at Gas Pressures from a Few Atmospheres to Several Tens of Atmospheres

NASA Astrophysics Data System (ADS)

Zubarev, N. M.; Ivanov, S. N.

2018-04-01

The mechanism of runaway electron generation at gas pressures from a few atmospheres to several tens of atmospheres is proposed. According to this mechanism, the electrons pass into the runaway mode in the enhanced field zone that arises between a cathode micropoint—a source of field-emission electrons—and the region of the positive ion space charge accumulated near the cathode in the tails of the developing electron avalanches. As a result, volume gas ionization by runaway electrons begins with a time delay required for the formation of the enhanced field zone. This process determines the delay time of breakdown. The influence of the gas pressure on the formation dynamics of the space charge region is analyzed. At gas pressures of a few atmospheres, the space charge arises due to the avalanche multiplication of the very first field-emission electron, whereas at pressures of several tens of atmospheres, the space charge forms as a result of superposition of many electron avalanches with a relatively small number of charge carriers in each.