WorldWideScience

Sample records for backflush thermal desorption

  1. Magic-angle thermal desorption mass spectroscopy

    Science.gov (United States)

    Pauls, Steven W.; Campbell, Charles T.

    1990-02-01

    Accurate quantitative measurements of desorption rates or adsorbate coverages in thermal desorption mass spectroscopy (TDS) using line-of-sight mass spectrometers are hindered by the fact that the angular distributions of desorption flux can vary widely from desorbate to desorbate, ranging from cos 1ø to cos 9 ø for most species studied to date (ø = polar angle from surface normal). These differences can easily lead to errors exceeding 400% in measuring the relative desorption rates of different species. We show here that, by placing the mass spectrometer's ion source or entrance aperture at a "magic-angle" ø mthese errors can be reduced to less than 26% maximum deviation (or ± 7% standard deviation). Depending upon the sample-to-detector distance, ø m varies from ~ 42° to 34°. It is recommended that TDS experiments be performed at this "magic-angle" for improvement in the quantitative accuracy of coverage or rate measurements.

  2. Spatially resolved thermal desorption/ionization coupled with mass spectrometry

    Science.gov (United States)

    Jesse, Stephen; Van Berkel, Gary J; Ovchinnikova, Olga S

    2013-02-26

    A system and method for sub-micron analysis of a chemical composition of a specimen are described. The method includes providing a specimen for evaluation and a thermal desorption probe, thermally desorbing an analyte from a target site of said specimen using the thermally active tip to form a gaseous analyte, ionizing the gaseous analyte to form an ionized analyte, and analyzing a chemical composition of the ionized analyte. The thermally desorbing step can include heating said thermally active tip to above 200.degree. C., and positioning the target site and the thermally active tip such that the heating step forms the gaseous analyte. The thermal desorption probe can include a thermally active tip extending from a cantilever body and an apex of the thermally active tip can have a radius of 250 nm or less.

  3. Thermal desorption of deuterium implanted into beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Markin, A.V.; Chernikov, V.N.; Zakharov, A.P. [Institute of Physical Chemistry, Moscow (Russian Federation)] [and others

    1995-09-01

    By means of TDS measurements it is shown that the desorption of deuterium from Be implanted with 5 keV D ions to fluences, {Phi}, from 1x10{sup 20} D/m{sup 2} to 1x10{sup 21} D/m{sup 2} proceeds in one high temperature stage B, while at {Phi} {ge} 1.2x10{sup 21}D/m{sup 2} one more stage A is added. The desorption maximum A is narrow and consists of two peaks A{sub 1} and A{sub 2} at about 460 K and 490 K, respectively. Peak A{sub 1} is attributed to the desorption of deuterium from the walls of opened channels formed under D ion implantation. Peak {sub A}2 is a consequence of the opening of a part of closed bubbles/channels to the outer surface. The position of maximum B shifts noticeably and nonsteadily on the fluence in a range from 850 to 1050 K. The origin of this maximum is the liberation of D atoms bound at vacancy complexes discussed previously by Wampler. The dependence of Tm(B) on the fluence is governed by the interaction of freely migrating D atoms with partly opened or fully closed gas cavity arrangements which are created under temperature ramping, but differently in specimens implanted with D ions to different fluences.

  4. Laser-induced thermal desorption of aniline from silica surfaces

    Science.gov (United States)

    Voumard, Pierre; Zenobi, Renato

    1995-10-01

    A complete study on the energy partitioning upon laser-induced thermal desorption of aniline from silica surfaces was undertaken. The measurements include characterization of the aniline-quartz adsorption system using temperature-programmed desorption, the extrapolation of quasiequilibrium desorption temperatures to the regime of laser heating rates on the order of 109-1010 K/s by computational means, measurement of the kinetic energy distributions of desorbing aniline using a pump-probe method, and the determination of internal energies with resonance-enhanced multiphoton ionization spectroscopy. The measurements are compared to calculations of the surface temperature rise and the resulting desorption rates, based on a finite-difference mathematical description of pulsed laser heating. While the surface temperature of laser-heated silica reaches about 600-700 K at the time of desorption, the translational temperature of laser-desorbed aniline was measured to be Tkin=420±60 K, Tvib was 360±60 K, and Trot was 350±100 K. These results are discussed using different models for laser-induced thermal desorption from surfaces.

  5. The study of 'microsurfaces' using thermal desorption spectroscopy

    Science.gov (United States)

    Thomas, M. E.; Poppa, H.; Pound, G. M.

    1979-01-01

    The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

  6. Thermal Desorption of Helium Implanted in Tungsten at RT

    Institute of Scientific and Technical Information of China (English)

    ZHANGFu; XUZengyu; LIUXiang; CHENJiming; XUYing; N.Yoshida; H.Iwakiri

    2002-01-01

    Tungsten is envisaged as one of the main candidate materials for divertor plate of ITER and future fusion reactors. Due to D-T reaction, PFMs would suffer helium irradiation from plasma additional to the high heat loads. Helium retention and thermal desorption behavior are largely concerned.

  7. Thermally assisted desorption processes in electron bombarded alkali halides

    Energy Technology Data Exchange (ETDEWEB)

    Kolodziej, J.; Czuba, P.; Piatkowski, P.; Postawa, Z.; Kempter, V.; Szymonski, M. (Uniwersytet Jagiellonski, Cracow (Poland). Inst. Fizyki)

    The desorption of alkali and halogen atoms induced by the interaction of energetic electrons with surfaces of alkali halide crystals has been studied by means of an angular-resolved and mass-selected time-of-flight spectroscopy. It has been found that a considerable fraction of halogen atoms was ejected with hyperthermal energies of the order of 0.1 eV. However, alkali atoms and the remaining part of halogen emission had thermal (Maxwellian) spectra of kinetic energies. In this paper we will report on systematic investigations of these thermal desorption processes for single crystal (100) NaCl, KCl, KBr, RbBr, and Kl surfaces. The relative yield of the thermal component has been measured as a function of electron beam energy and beam current density at various sample temperatures. It will be shown that thermal halogen emission can be explained by thermally assisted diffusion of interstitial halogen atoms produced in the bulk of the crystal from decaying self-trapped excitons. The origin of the alkali atom component will be described as due to neutralization and subsequent thermal evaporation of excess alkali atoms from the halogen deficient surface. (Author).

  8. Thermal Desorption of Water-Ice in the Interstellar Medium

    CERN Document Server

    Fraser, H J; McCoustra, M R S; Williams, D A; Fraser, Helen J.; Collings, Mark P.; Coustra, Martin R.S. Mc; Williams, David A.

    2001-01-01

    Water (H2O) ice is an important solid constituent of many astrophysical environments. To comprehend the role of such ices in the chemistry and evolution of dense molecular clouds and comets, it is necessary to understand the freeze-out, potential surface reactivity, and desorption mechanisms of such molecular systems. Consequently, there is a real need from within the astronomical modelling community for accurate empirical molecular data pertaining to these processes. Here we give the first results of a laboratory programme to provide such data. Measurements of the thermal desorption of H2O ice, under interstellar conditions, are presented. For ice deposited under conditions that realistically mimic those in a dense molecular cloud, the thermal desorption of thin films (~50 molecular layers) is found to occur with zero order kinetics characterised by a surface binding energy, E_{des}, of 5773 +/- 60 K, and a pre-exponential factor, A, of 10^(30 +/- 2) molecules cm^-2 s^-1. These results imply that, in the den...

  9. Thermal desorption of helium from homogeneously implanted graphite

    Science.gov (United States)

    Jung, P.; Schroeder, H.

    1991-11-01

    Super-fine grain graphite (FGG) and pyrolytic carbon (PYC) of thicknesses around 200 μm were homogeneously implanted at room temperature with α-particles (0.5 MeV ≤ Eα ≤ 22 MeV). Thermal helium desorption spectrometry in the temperature range from 400 to 1900 K can be described by diffusion kinetics with an activation energy of 1.1 eV in FGG and about 0.75 eV in PYC. Desorption during temperature ramping at a constant rate of 0.83 K/s also shows significant differences of the two graphite species. It is found that in FGG and especially in PYC a considerable fraction of the implanted helium is retained even beyond 1000 K. This is in contrast to results reported after low energy implantations to high doses for various graphite species.

  10. Study of Thermal Desorption of Helium from Hydrogenated Zirconium

    Institute of Scientific and Technical Information of China (English)

    SUN Wei-Ming; WEI Yu-Cheng; SHI Li-Qun

    2006-01-01

    @@ A new method prepared for helium and hydrogen co-containing Zr films is presented to simulate aging metal tritides, in which direct current magnetron sputtering with a He/H/Ar mixture is used. The retained amount and depth profiles of helium and hydrogen are determined by elastic recoil detection analysis. Thermal desorption spectrometry is applied to investigate He thermal release and the effect of hydrogen. It is found that the hightemperature peaks with a large mount of helium release obviously shifted toward lower temperature at high hydrogen concentration, especially at the hydride transformation region, and that the shapes of the release peaks also changed due to the additional hydrogen. However, at the low-temperature releasing region the peak intense decreases when phase transformation takes place. The mechanism of helium thermal release and the effect of hydrogen are also discussed.

  11. Thermal desorption of circumstellar and cometary ice analogs

    CERN Document Server

    Martín-Doménech, Rafael; Bueno, Juan; Goesmann, Fred

    2014-01-01

    Thermal annealing of interstellar ices takes place in several stages of star formation. Knowledge of this process comes from a combination of astronomical observations and laboratory simulations under astrophysically relevant conditions. For the first time we present the results of temperature programmed desorption (TPD) experiments with pre-cometary ice analogs composed of up to five molecular components: H2 O, CO, CO2, CH3 OH, and NH3 . The experiments were performed with an ultra-high vacuum chamber. A gas line with a novel design allows the controlled preparation of mixtures with up to five molecular components. Volatiles desorbing to the gas phase were monitored using a quadrupole mass spectrometer, while changes in the ice structure and composition were studied by means of infrared spectroscopy. The TPD curves of water ice containing CO, CO2, CH3 OH, and NH3 present desorption peaks at temperatures near those observed in pure ice experiments, volcano desorption peaks after water ice crystallization, and...

  12. Thermal desorption of PCBs from contaminated soil with copper dichloride.

    Science.gov (United States)

    Liu, Jie; Qi, Zhifu; Li, Xiaodong; Chen, Tong; Buekens, Alfons; Yan, Jianhua; Ni, Mingjiang

    2015-12-01

    Copper dichloride is an important catalyst both in the dechlorination of chlorinated aromatic compounds and the formation of PCDD/Fs. The effect of copper dichloride on polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) was studied in treated soil and off gas after thermal desorption of PCB-contaminated soil at 300, 400, 500, 600 °C. The presence of copper dichloride clearly enhances thermal desorption by promoting PCBs removal, destruction, and dechlorination. After thermal treatment at 600 °C for 1 h, the removal efficiency and destruction efficiency for PCBs reached 98.1 and 93.9%, respectively. Compared with the positive influence on PCBs, copper dichloride catalyzed large amount of PCDFs formation at 300 °C, with the concentration ratio of 2.35. The effect of CuCl2 on PCDFs formation weakened with the rising temperature since PCDFs destruction became dominant under higher temperature. Different from PCDFs, PCDDs concentration in treated soil and off gas decreased continuously with the increasing temperature.

  13. Wheat Growth in Soils Treated by Ex Situ Thermal Desorption.

    Science.gov (United States)

    O'Brien, Peter L; DeSutter, Thomas M; Casey, Francis X M; Wick, Abbey F; Khan, E

    2017-07-01

    Successful remediation of oil-contaminated agricultural land may include the goal of returning the land to prespill levels of agricultural productivity. This productivity may be measured by crop yield, quality, and safety, all of which are influenced by soil characteristics. This research was conducted to determine if these metrics are affected in hard red spring wheat ( L. cultivar Barlow) when grown in soils treated by ex situ thermal desorption (TD) compared with wheat grown in native topsoil (TS). Additionally, TD soils were mixed with TS at various ratios to assess the effectiveness of soil mixing as a procedure for enhancing productivity. In two greenhouse studies, TD soils alone produced similar amounts of grain and biomass as TS, although grain protein in TD soils was 22% (±7%) lower. After mixing TS into TD soils, the mean biomass and grain yield were reduced by up to 60%, but grain protein increased. These trends are likely the result of nutrient availability determined by soil organic matter and nutrient cycling performed by soil microorganisms. Thermal desorption soil had 84% (±2%) lower soil organic carbon than TS, and cumulative respiration was greatly reduced (66 ± 2%). From a food safety perspective, grain from TD soils did not show increased uptake of polycyclic aromatic hydrocarbons. Overall, this research suggests that TD soils are capable of producing safe, high-quality grain yields. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  14. Orbital dynamics of a solar sail accelerated by thermal desorption of coatings

    OpenAIRE

    2016-01-01

    In this study we considered a solar sail coated with materials that undergo thermal desorption at a specific temperature, as a result of heating by solar radiation at a particular heliocentric distance. Three different scenarios, that only differ in the way the sail approaches the Sun, were analyzed and compared. In every case once the perihelion is reached, the sail coat undergoes thermal desorption. When the desorption process ends, the sail then escapes the Solar System having the conventi...

  15. Apparatus for low temperature thermal desorption spectroscopy of portable samples

    Science.gov (United States)

    Stuckenholz, S.; Büchner, C.; Ronneburg, H.; Thielsch, G.; Heyde, M.; Freund, H.-J.

    2016-04-01

    An experimental setup for low temperature thermal desorption spectroscopy (TDS) integrated in an ultrahigh vacuum-chamber housing a high-end scanning probe microscope for comprehensive multi-tool surface science analysis is described. This setup enables the characterization with TDS at low temperatures (T > 22 K) of portable sample designs, as is the case for scanning probe optimized setups or high-throughput experiments. This combination of techniques allows a direct correlation between surface morphology, local spectroscopy, and reactivity of model catalysts. The performance of the multi-tool setup is illustrated by measurements of a model catalyst. TDS of CO from Mo(001) and from Mo(001) supported MgO thin films were carried out and combined with scanning tunneling microscopy measurements.

  16. Orbital dynamics of a solar sail accelerated by thermal desorption of coatings

    CERN Document Server

    Ancona, Elena

    2016-01-01

    In this study we considered a solar sail coated with materials that undergo thermal desorption at a specific temperature, as a result of heating by solar radiation at a particular heliocentric distance. Three different scenarios, that only differ in the way the sail approaches the Sun, were analyzed and compared. In every case once the perihelion is reached, the sail coat undergoes thermal desorption. When the desorption process ends, the sail then escapes the Solar System having the conventional acceleration due to solar radiation pressure. Thermal desorption here comes as an additional source of solar sail acceleration beside traditional propulsion systems for extrasolar space exploration. The compared scenarios are the following: i. Hohmann transfer plus thermal desorption. In this scenario the sail would be carried as a payload to the perihelion with a conventional propulsion system by an Hohmann transfer from Earth's orbit to an orbit very close to the Sun (almost at 0.1 AU) and then be deployed there. i...

  17. Mercury speciation during in situ thermal desorption in soil

    Energy Technology Data Exchange (ETDEWEB)

    Park, Chang Min, E-mail: cmpark80@gmail.com; Katz, Lynn E.; Liljestrand, Howard M.

    2015-12-30

    Highlights: • Impact of soil conditions on distribution and phase transitions of Hg was identified. • Metallic Hg was slowly transformed to Hg{sup 0} gas until the temperature reached 358.15 K. • Phase change of HgCl{sub 2(s)} completely occurred without decomposition at 335.15 K. • HgS remained solid in dry soil sharply decreased in the narrow temperature range. • Hg gas can be easily captured with higher vapor pressures of soil compositions. - Abstract: Metallic mercury (Hg{sup 0}) and its compounds are highly mobile and toxic environmental pollutants at trace level. In situ thermal desorption (ISTD) is one of the soil remediation processes applying heat and vacuum simultaneously. Knowledge of thermodynamic mercury speciation is imperative to understand the fate and transport of mercury during thermal remediation and operate the treatment processes in a cost-effective manner. Hence, speciation model for inorganic mercury was developed over a range of environmental conditions to identify distribution of dissolved mercury species and potential transformations of mercury at near source environment. Simulation of phase transitions for metallic mercury, mercury(II) chloride and mercury sulfide with temperature increase showed that complete vaporization of metallic mercury and mercury(II) chloride were achieved below the boiling point of water. The effect of soil compositions on mercury removal was also evaluated to better understand thermal remediation process. Higher vapor pressures expected both from soil pore water and inorganic carbonate minerals in soil as well as creation of permeability were significant for complete vaporization and removal of mercury.

  18. Thermal desorption of deuterium from modified carbon nanotubes and its correlation to the microstructure

    NARCIS (Netherlands)

    Lisowski, W.; Keim, E.G.; Berg, van den A.H.J.; Smithers, M.A.

    2006-01-01

    The process of deuterium desorption from single-wall carbon nanotubes (SWNTs) modified by atomic (D) and molecular (D2) deuterium treatment was investigated in an ultrahigh vacuum environment using thermal desorption mass spectroscopy (TDMS). Microstructural and chemical analyses of SWNT material, m

  19. Desorption of isopropyl alcohol from adsorbent with non-thermal plasma.

    Science.gov (United States)

    Shiau, Chen Han; Pan, Kuan Lun; Yu, Sheng Jen; Yan, Shaw Yi; Chang, Moo Been

    2016-11-24

    Effective desorption of isopropyl alcohol (IPA) from adsorbents with non-thermal plasma is developed. In this system, IPA is effectively adsorbed with activated carbon while dielectric barrier discharge is applied to replace the conventional thermal desorption process to achieve good desorption efficiency, making the treatment equipment smaller in size. Various adsorbents including molecular sieves and activated carbon are evaluated for IPA adsorption capacity. The results indicate that BAC has the highest IPA adsorption capacity (280.31 mg IPA/g) under the operating conditions of room temperature, IPA of 400 ppm, and residence time of 0.283 s among 5 adsorbents tested. For the plasma desorption process, the IPA selectivity of 89% is achieved with BAC as N2 is used as desorbing gas. In addition, as air or O2 is used as desorbing gas, the IPA desorption concentration is reduced, because air and O2 plasmas generate active species to oxidize IPA to form acetone, CO2, and even CO. Furthermore, the results of the durability test indicate that the amount of IPA desorbed increases with increasing desorption times and plasma desorption process has a higher energy efficiency if compared with thermal desorption. Overall, this study indicates that non-thermal plasma is a viable process for removing VOCs to regenerate adsorbent.

  20. Bonding configurations for nickelocene on Ag(100) and steric effects in thermal desorption

    Energy Technology Data Exchange (ETDEWEB)

    Borca, C.N.; Welipitiya, D.; Dowben, P.A.; Boag, N.M.

    2000-02-10

    The molecular adsorption and desorption of nickelocene, Ni(C{sub 5}H{sub 5}){sub 2}, on Ag(100) has been studied by coverage dependent angle-resolved thermal desorption. The angle-resolved thermal desorption of nickelocene is unusual in that the molecular orientation is seen to affect the angular dependence of molecular desorption. The coexistence of two chemisorption phases for molecular nickelocene adsorption on Ag(100) near the desorption temperature of approximately 230 K is identified. One phase, with the bonding configuration of the nickelocene molecular axis along the surface normal, appears to dominate at higher coverages. The results are discussed in the context of rehybridization and recent angle-resolved photoemission and high-resolution electron energy loss measurements.

  1. Decomposition kinetics study of zirconium hydride by interrupted thermal desorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Mingwang; Liang, Li; Tang, Binghua; Xiang, Wei; Wang, Yuan; Cheng, Yanlin; Tan, Xiaohua, E-mail: caepiee@163.com

    2015-10-05

    Highlights: • Interrupted TDS was applied to investigate the mechanism of ZrH{sub 2} decomposition. • The activation energies for the five desorption peaks were determined. • The origins of the five desorption peaks were identified. • The γZrH phase was observed at ambient conditions. - Abstract: Thermal desorption kinetics of zirconium hydride powder were studied using thermogravimetry and simultaneous thermal desorption spectroscopy. The activation energies for observed desorption peaks were estimated according to Kissinger relation. The intermediate phase composition was studied using X-ray diffraction by rapid cooling on different stages of heating. The origins of the peaks were described as the equilibrium hydrogen pressure of a number of consecutive phase regions that decomposition reaction passed through. The zirconium monohydride γZrH was observed for extended periods of time at ambient conditions, which has been supposed to be metastable for a long time.

  2. Adsorption, Diffusion and Thermal Desorption Features of Cyclopentane and Cyclohexane in Silicalite-1

    Institute of Scientific and Technical Information of China (English)

    DUAN, Lin-Hai; SONG, Li-Juan; ZHANG, Xiao-Tong; TANG, Ke; DAI, Zhen-Hua; SUN, Zhao-Lin

    2006-01-01

    Adsorption, diffusion and thermal desorption features of cyclopentane and cyclohexane in silicalite-1 have been investigated using the intelligent gravimetric technique. Both the saturation adsorption loadings and diffusion coefficient of cyclopentane were greater than those of cyclohexane. The diffusivity of cyclopentane was about one order of magnitude greater than that of cyclohexane at the same temperature and initial loading. For cyclopentane, there was only one kind of desorption process at adsorption loadings lower than 4 muc (molecule per unit cell), but two desorption processes appeared at the adsorption loadings higher than 4 muc. While for cyclohexane, one desorption process was found in the whole range of loadings. Both thermal desorption peaks of cyclopentane and cyclohexane moved to higher temperature region with increasing loading.

  3. Treating high-mercury-containing lamps using full-scale thermal desorption technology.

    Science.gov (United States)

    Chang, T C; You, S J; Yu, B S; Chen, C M; Chiu, Y C

    2009-03-15

    The mercury content in high-mercury-containing lamps are always between 400 mg/kg and 200,000 mg/kg. This concentration is much higher than the 260 mg/kg lower boundary recommended for the thermal desorption process suggested by the US Resource Conservation and Recovery Act. According to a Taiwan EPA survey, about 4,833,000 cold cathode fluorescent lamps (CCFLs), 486,000 ultraviolet lamps and 25,000 super high pressure mercury lamps (SHPs) have been disposed of in the industrial waste treatment system, producing 80, 92 and 9 kg-mercury/year through domestic treatment, offshore treatment and air emissions, respectively. To deal with this problem we set up a full-scale thermal desorption process to treat and recover the mercury from SHPs, fluorescent tube tailpipes, fluorescent tubes containing mercury-fluorescent powder, and CCFLs containing mercury-fluorescent powder and monitor the use of different pre-heating temperatures and desorption times. The experimental results reveal that the average thermal desorption efficiency of SHPs and fluorescent tube tailpipe were both 99.95%, while the average thermal desorption efficiencies of fluorescent tubes containing mercury-fluorescent powder were between 97% and 99%. In addition, a thermal desorption efficiency of only 69.37-93.39% was obtained after treating the CCFLs containing mercury-fluorescent powder. These differences in thermal desorption efficiency might be due to the complexity of the mercury compounds contained in the lamps. In general, the thermal desorption efficiency of lamps containing mercury-complex compounds increased with higher temperatures.

  4. Modelling of hydrogen thermal desorption spectrum in nonlinear dynamical boundary-value problem

    Science.gov (United States)

    Kostikova, E. K.; Zaika, Yu V.

    2016-11-01

    One of the technological challenges for hydrogen materials science (including the ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermal desorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a distributed boundary-value problem of thermal desorption and a numerical method for TDS spectrum simulation, where only integration of a nonlinear system of low order (compared with, e.g., the method of lines) ordinary differential equations (ODE) is required. This work is supported by the Russian Foundation for Basic Research (project 15-01-00744).

  5. Decomposition of thin titanium deuteride films; thermal desorption kinetics studies combined with microstructure analysis

    NARCIS (Netherlands)

    Lisowski, Wojciech; Keim, Enrico G.; Kaszkur, Zbigniew; Smithers, Mark A.

    2008-01-01

    The thermal evolution of deuterium from thin titanium films, prepared under UHV conditions and deuterated in situ at room temperature, has been studied by means of thermal desorption mass spectrometry (TDMS) and a combination of scanning electron microscopy (SEM), transmission electron microscopy (T

  6. Thermal desorption of CH4 retained in CO2 ice

    CERN Document Server

    Luna, R; Domingo, M; Satorre, M A

    2008-01-01

    CO2 ices are known to exist in different astrophysical environments. In spite of this, its physical properties (structure, density, refractive index) have not been as widely studied as those of water ice. It would be of great value to study the adsorption properties of this ice in conditions related to astrophysical environments. In this paper, we explore the possibility that CO2 traps relevant molecules in astrophysical environments at temperatures higher than expected from their characteristic sublimation point. To fulfil this aim we have carried out desorption experiments under High Vacuum conditions based on a Quartz Crystal Microbalance and additionally monitored with a Quadrupole Mass Spectrometer. From our results, the presence of CH4 in the solid phase above the sublimation temperature in some astrophysical scenarios could be explained by the presence of several retaining mechanisms related to the structure of CO2 ice.

  7. ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE THERMAL DESORPTION UNIT - APPLICATIONS ANALYSIS REPORT

    Science.gov (United States)

    ELI ECO Logic International, Inc.'s Thermal Desorption Unit (TDU) is specifically designed for use with Eco Logic's Gas Phase Chemical Reduction Process. The technology uses an externally heated bath of molten tin in a hydrogen atmosphere to desorb hazardous organic compounds fro...

  8. Offline thermal-desorption proton-transfer-reaction mass spectrometry to study composition of organic aerosol

    NARCIS (Netherlands)

    Timkovsky, J.; Dusek, U.; Henzing, J. S.; Kuipers, T. L.; Röckmann, T.; Holzinger, R.

    2015-01-01

    We present a novel approach to study the organic composition of aerosol filter samples using thermal-desorption proton-transfer-reaction mass spectrometry (TD-PTR-MS) in the laboratory. The method is tested and validated based on the comparison with in situ TD-PTR-MS measurements. In general, we obs

  9. Helium concentration measurement in tungsten fuzz-like nanostructures by means of thermal desorption spectroscopy

    NARCIS (Netherlands)

    Gasparyan, Y.; Efimov, V.; Bystrov, K.

    2016-01-01

    The concentration of helium in tungsten fuzz-like nanostructures has been measured by means of thermal desorption spectroscopy. Fuzz was formed on the W surface under intensive plasma irradiation at 1500 K. The helium content was measured first in the as-irradiated sample, and then in a similar samp

  10. Thermal desorption from surfaces with laser-induced defects

    Energy Technology Data Exchange (ETDEWEB)

    Szabelski, Pawel; Panczyk, Tomasz; Rudzinski, Wladyslaw

    2002-12-30

    Monte Carlo simulation method was used to mimic surface damage development caused by short laser pulses. The influence of pulsed laser irradiation on the creation of defect concentration was examined in the case of a model surface. In particular, the dependence of the intact surface area on a number of laser scans was studied and compared with the experimental results obtained for Rh(1 1 1) crystal face. Changes in the adsorptivoperties of the surface produced by laser irradiation are explained with the help of a simple geometric model connecting the laser intensity and the disordered area generated by a single laser shot. It was demonstrated that exponential decay of the Low Energy Electron Diffraction (LEED) signal with the number of laser scans, which is observed experimentally, may result directly from the overlapping of the laser spots created on the surface. This effect becomes enhanced when the laser intensity, hence the spot size, increases. The importance of laser-induced defects in the kinetics of catalytic/separation processes was examined in the case of temperature programmed desorption (TPD) spectra from surfaces subjected to a different number of laser shots. The spectra were simulated by employing the Monte Carlo method as well as by application of the absolute rate theory (ART) coupled with the mean field approximation. The results obtained with both methods were in a good agreement even when weak lateral interactions in the adsorbed phase were allowed.

  11. Impact of Thermal Decomposition on Thermal Desorption Instruments: Advantage of Thermogram Analysis for Quantifying Volatility Distributions of Organic Species.

    Science.gov (United States)

    Stark, Harald; Yatavelli, Reddy L N; Thompson, Samantha L; Kang, Hyungu; Krechmer, Jordan E; Kimmel, Joel R; Palm, Brett B; Hu, Weiwei; Hayes, Patrick L; Day, Douglas A; Campuzano-Jost, Pedro; Canagaratna, Manjula R; Jayne, John T; Worsnop, Douglas R; Jimenez, Jose L

    2017-08-01

    We present results from a high-resolution chemical ionization time-of-flight mass spectrometer (HRToF-CIMS), operated with two different thermal desorption inlets, designed to characterize the gas and aerosol composition. Data from two field campaigns at forested sites are shown. Particle volatility distributions are estimated using three different methods: thermograms, elemental formulas, and measured partitioning. Thermogram-based results are consistent with those from an aerosol mass spectrometer (AMS) with a thermal denuder, implying that thermal desorption is reproducible across very different experimental setups. Estimated volatilities from the detected elemental formulas are much higher than from thermograms since many of the detected species are thermal decomposition products rather than actual SOA molecules. We show that up to 65% of citric acid decomposes substantially in the FIGAERO-CIMS, with ∼20% of its mass detected as gas-phase CO2, CO, and H2O. Once thermal decomposition effects on the detected formulas are taken into account, formula-derived volatilities can be reconciled with the thermogram method. The volatility distribution estimated from partitioning measurements is very narrow, likely due to signal-to-noise limits in the measurements. Our findings indicate that many commonly used thermal desorption methods might lead to inaccurate results when estimating volatilities from observed ion formulas found in SOA. The volatility distributions from the thermogram method are likely the closest to the real distributions.

  12. Activation energy of thermal desorption of silicon oxide layers on silicon substrates

    Science.gov (United States)

    Enta, Yoshiharu; Osanai, Shodai; Ogasawara, Takahito

    2017-02-01

    Thermal desorption rates of silicon oxide layers, from 20 to 120 nm in thickness, on silicon substrates in vacuum have been accurately obtained from intervals between ring structures formed inside voids on the oxide layers. From the temperature dependence of the desorption rate, the activation energy and frequency factor of the desorption reaction have been derived as a function of the oxide thickness. The obtained values are compared with the previous studies, and as a result, the activation energy is found to be almost constant ( 4 eV) in a wide range of the oxide thickness. The frequency factor decreases as the inverse square of the oxide thickness. The decomposition kinetics of the oxide layer is also discussed from the obtained results.

  13. Non-isothermal kinetics of the thermal desorption of mercury from a contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, F. A.; Sierra, M. J.; Rodriguez, O.; Millan, R.; Alguacil, F. J.

    2014-04-01

    The Almaden mining district (Ciudad Real, Spain) was the largest cinnabar (mercury sulphide) mine in the world. Its soils have high levels of mercury a consequence of its natural lithology, but often made much worse by its mining history. The present work examines the thermal desorption of two contaminated soils from the Almaden area under non-isothermal conditions in a N{sub 2} atmosphere, using differential scanning calorimetry (DSC). DSC was performed at different heating rates between room temperature and 600 degree centigrade. Desorption temperatures for different mercury species were determined. The Friedman, Flynn-Wall-Ozawa and Coasts Redfern methods were employed to determine the reaction kinetics from the DSC data. The activation energy and pre-exponential factor for mercury desorption were calculated. (Author)

  14. PCDD/F formation during thermal desorption of p,p'-DDT contaminated soil.

    Science.gov (United States)

    Zhao, Zhonghua; Ni, Mingjiang; Li, Xiaodong; Buekens, Alfons; Yan, Jianhua

    2017-05-01

    Thermal treatment of polychlorinated biphenyls (PCB) contaminated soil was shown in earlier work to generate polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). In this study, the PCDD/F were studied arising during the remediation of p,p'-DDT contaminated soil by thermal desorption. Three kinds of soil (sandy, clayey and lateritic soil) were tested to investigate the effect of soil texture on PCDD/F formation. Those soils were artificially polluted with p,p'-DDT, obtaining a concentration level of 100 mg/kg. Thermal desorption experiments were conducted for 10 min at 300 °C in an air atmosphere. The total concentration of PCDD/F generated for three soils were 331, 803 and 865 ng/kg, respectively, and TeCDD and TeCDF were dominant among all PCDD/F congeners. After thermal desorption, the total amount of PCDD/F generated both in soil and in off-gas correlated positively with the amount of DDT added to soil. In addition, a possible pathway of the formation of PCDD/F was presented.

  15. Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

    Science.gov (United States)

    Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; Martinez, Raul E.; Walker, Michael J.; Kreisberg, Nathan M.; Goldstein, Allen H.; Docherty, Kenneth S.; Jimenez, Jose L.

    2016-04-01

    Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality and, often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analyze thermal decomposition products as measured by a thermal desorption aerosol gas chromatograph (TAG) capable of separating thermal decomposition products from thermally stable molecules. The TAG impacts particles onto a collection and thermal desorption (CTD) cell, and upon completion of sample collection, heats and transfers the sample in a helium flow up to 310 °C. Desorbed molecules are refocused at the head of a gas chromatography column that is held at 45 °C and any volatile decomposition products pass directly through the column and into an electron impact quadrupole mass spectrometer. Analysis of the sample introduction (thermal decomposition) period reveals contributions of NO+ (m/z 30), NO2+ (m/z 46), SO+ (m/z 48), and SO2+ (m/z 64), derived from either inorganic or organic particle-phase nitrate and sulfate. CO2+ (m/z 44) makes up a major component of the decomposition signal, along with smaller contributions from other organic components that vary with the type of aerosol contributing to the signal (e.g., m/z 53, 82 observed here for isoprene-derived secondary OA). All of these ions are important for ambient aerosol analyzed with the aerosol mass spectrometer (AMS), suggesting similarity of the thermal desorption processes in both instruments. Ambient observations of these decomposition products compared to organic, nitrate, and sulfate mass concentrations measured by an AMS reveal good correlation, with improved correlations for OA when compared to the AMS oxygenated OA (OOA

  16. VAC*TRAX - thermal desorption for mixed wastes

    Energy Technology Data Exchange (ETDEWEB)

    McElwee, M.J.; Palmer, C.R. [RUST-Clemson Technical Center, Anderson, SC (United States)

    1995-10-01

    The patented VAC*TRAX process was designed in response to the need to remove organic constituents from mixed waste, waste that contains both a hazardous (RCRA or TSCA regulated) component and a radioactive component. Separation of the mixed waste into its hazardous and radioactive components allows for ultimate disposal of the material at existing, permitted facilities. The VAC*TRAX technology consists of a jacketed vacuum dryer followed by a condensing train. Solids are placed in the dryer and indirectly heated to temperatures as high as 2600{degrees}C, while a strong vacuum (down to 50 mm Hg absolute pressure) is applied to the system and the dryer is purged with a nitrogen carrier gas. The organic contaminants in the solids are thermally desorbed, swept up in the carrier gas and into the condensing train where they are cooled and recovered. The dryer is fitted with a filtration system that keeps the radioactive constituents from migrating to the condensate. As such, the waste is separated into hazardous liquid and radioactive solid components, allowing for disposal of these streams at a permitted incinerator or a radioactive materials landfill, respectively. The VAC*TRAX system is designed to be highly mobile, while minimizing the operational costs with a simple, robust process. These factors allow for treatment of small waste streams at a reasonable cost.

  17. Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

    OpenAIRE

    Williams, Brent J.; Zhang, Yaping; Zuo, Xiaochen; Martinez, Raul E.; Walker, Michael J.; Kreisberg, Nathan M.; Goldstein, Allen H.; Docherty, Kenneth S.; Jimenez, Jose L.

    2016-01-01

    Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality and, often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analy...

  18. Organic and inorganic decomposition products from the thermal desorption of atmospheric particles

    OpenAIRE

    B. J. Williams; Y. Zhang; X. Zuo; R. E. Martinez; Walker, M. J.; N. M. Kreisberg; Goldstein, A. H.; K. S. Docherty; Jimenez, J.L.

    2015-01-01

    Atmospheric aerosol composition is often analyzed using thermal desorption techniques to evaporate samples and deliver organic or inorganic molecules to various designs of detectors for identification and quantification. The organic aerosol (OA) fraction is composed of thousands of individual compounds, some with nitrogen- and sulfur-containing functionality, and often contains oligomeric material, much of which may be susceptible to decomposition upon heating. Here we analy...

  19. Layer resolved spectroscopy of potassium adsorbed on a Ru(001) surface: Photoemission and thermal desorption study

    Energy Technology Data Exchange (ETDEWEB)

    Hrbek, J. (Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973 (US)); Shek, M. (Department of Physics, Hunter College of CUNY, New York, New York 10021); Sham, T.K. (Department of Chemistry, University of Western Ontario, London, Ontario N6A 5B7, Canada); Xu, G. (Chemistry Department, Brookhaven National Laboratory, Upton, New York, 11973)

    1989-11-01

    High-resolution photoemission spectroscopy and thermal desorption were used to study the coverage dependence of the K 3{ital p}{sub 3/2,1/2} core levels of K overlayers on Ru(001). Three doublets were observed to evolve sequentially and to shift to higher binding energy with increasing coverage of potassium. The doublets were assigned to photoemission from the interface (first layer), bulk'' (second layer), and surface (third layer). Spin--orbit splitting was observed for the first time in the condensed potassium phase by photoemission. The results are discussed in terms of the equivalent core approximation using a Born--Haber cycle. In the thermal desorption data three coverage regimes can be distinguished: a first layer desorbing with first-order kinetics and a strongly decreasing heat of adsorption ({ital E}{sub {ital A}} =2.80--0.87 eV); a second layer with zero-order desorption kinetics and {ital E}{sub {ital A}} =0.78 eV; a third layer and multilayers with the same kinetic order but with {ital E}{sub {ital A}} increasing from 0.78 to 0.93 eV, which is close to the heat of sublimation of potassium.

  20. Application of thermal desorption for the identification of mercury species in solids derived from coal utilization.

    Science.gov (United States)

    Rumayor, M; Diaz-Somoano, M; Lopez-Anton, M A; Martinez-Tarazona, M R

    2015-01-01

    The speciation of mercury is currently attracting widespread interest because the emission, transport, deposition and behaviour of toxic mercury species depend on its chemical form. The identification of these species in low concentrations is no easy task and it is even more complex in coal combustion products due to the fact that these products contain organic and mineral matter that give rise to broad peaks and make it difficult to carry out qualitative and quantitative analysis. In this work, a solution to this problem is proposed using a method based on thermal desorption. A sequential extraction procedure was employed for the comparison and validation of the method developed. Samples of fly ashes and soils were analyzed by both of these methods, and thermal desorption was found to be an appropriate technique for mercury speciation. Even in the case of low mercury contents, recovery percentages were close to 100%. The main mercury species identified in the samples studied were HgS and, to a lesser extent, HgO and HgSO4. In addition, although the presence of mercury complexes cannot be demonstrated, the desorption behaviour and sequential extraction results suggest that this element might be associated with the mineral matrix or with carbon particles in some of the solids. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Non-thermal desorption from interstellar dust grains via exothermic surface reactions

    CERN Document Server

    Garrod, R T; Herbst, E

    2007-01-01

    Aims: The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely contrained by theoretical work. Results: Our results ...

  2. Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Masashi Shimada; M. Hara; T. Otsuka; Y. Oya; Y. Hatano

    2014-05-01

    Accurately estimating tritium retention in plasma facing components (PFCs) and minimizing its uncertainty are key safety issues for licensing future fusion power reactors. D-T fusion reactions produce 14.1 MeV neutrons that activate PFCs and create radiation defects throughout the bulk of the material of these components. Recent studies show that tritium migrates and is trapped in bulk (>> 10 µm) tungsten beyond the detection range of nuclear reaction analysis technique [1-2], and thermal desorption spectroscopy (TDS) technique becomes the only established diagnostic that can reveal hydrogen isotope behavior in in bulk (>> 10 µm) tungsten. Radiation damage and its recovery mechanisms in neutron-irradiated tungsten are still poorly understood, and neutron-irradiation data of tungsten is very limited. In this paper, systematic investigations with repeated plasma exposures and thermal desorption are performed to study defect annealing and thermal desorption of deuterium in low dose neutron-irradiated tungsten. Three tungsten samples (99.99 at. % purity from A.L.M.T. Co., Japan) irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to high flux (ion flux of (0.5-1.0)x1022 m-2s-1 and ion fluence of 1x1026 m-2) deuterium plasma at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy (TDS) was performed with a ramp rate of 10 °C/min up to 900 °C, and the samples were annealed at 900 °C for 0.5 hour. These procedures were repeated three (for 100 and 200 °C samples) and four (for 500 °C sample) times to uncover damage recovery mechanisms and its effects on deuterium behavior. The results show that deuterium retention decreases approximately 90, 75, and 66 % for 100, 200, and 500 °C, respectively after each annealing. When subjected to the same TDS recipe, the desorption temperature shifts from 800 °C to 600 °C after 1st annealing

  3. Hydrogen solubility and diffusion in austenitic stainless steels studied with thermal desorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yagodzinskyy, Y.; Todoshchenko, O.; Papula, S.; Haenninen, H. [Laboratory of Engineering Materials, School of Science and Technology, Aalto University, Espoo (Finland)

    2011-01-15

    Hydrogen solubility and diffusion in austenitic stainless steels, namely AISI 310, AISI 301LN and AISI 201, are studied with thermal desorption spectroscopy (TDS) after electrochemical potentiostatic hydrogen pre-charging. Temperature dependencies of hydrogen desorption for all studied steels manifest a complex main peak caused by hydrogen releasing from the steel lattice by diffusion. Depending on the steel and heating rate the peak is situated from 350 to 500 K and its shape reflects a specific of hydrogen diffusion in stainless steels, which are multicomponent alloys. Analysis of the TDS curves is based on the hydrogen diffusion model taking into account trapping of hydrogen atoms in the energetically deep interstitial positions in the steel crystal lattice. Diffusion coefficient of hydrogen and its total content after the same charging procedure are obtained from the TDS curves and compared for the studied steels. (Copyright copyright 2011 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Thermal desorption characterisation of molecularly imprinted polymers. Part I: A novel study using direct-probe GC-MS analysis.

    Science.gov (United States)

    Cummins, Wayne; Duggan, Patrick; McLoughlin, Peter

    2008-06-01

    A novel thermal desorption technique using a direct-probe device (Chromatoprobe) attached to a gas chromatograph-mass spectrometer is presented for the thermal pretreatment, characterisation and analysis of molecularly imprinted polymers. The technique is demonstrated as effective for the removal of volatile materials, including template and unreacted monomers, from methacrylic acid-ethylene glycol dimethacrylate copolymers imprinted with 2-aminopyridine. Mass spectrometry is a powerful technique for polymer bleed characterisation. Thermal desorption studies on reloaded template and related compounds are reported as a means of assessing polymer morphology, specific binding by imprinted polymers compared with reference non-imprinted polymers and selective binding by an imprinted polymer for its template. Calibration studies on the thermal desorption technique using an internal standard are presented with R(2) > 0.999. The technique provides a novel method for assessment of polymer thermal stability, composition and morphology.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-09-01

    Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief

  6. Precursor ion scan profiles of acylcarnitines by atmospheric pressure thermal desorption chemical ionization tandem mass spectrometry.

    Science.gov (United States)

    Paglia, Giuseppe; D'Apolito, Oceania; Corso, Gaetano

    2008-12-01

    The fatty acyl esters of L-carnitine (acylcarnitines) are useful biomarkers for the diagnosis of some inborn errors of metabolism analyzed by liquid chromatography/tandem mass spectrometry. In this study the acylcarnitines were analyzed by atmospheric pressure thermal desorption chemical ionization using a commercial tandem mass spectrometer (APTDCI-MS/MS). The method is based on the precursor ion scan mode determination of underivatized acylcarnitines desorbed from samples by a hot desolvation gas flow and ionized by a corona pin discharge. During desorption/ionization step the temperature induces the degradation of acylcarnitines; nevertheless, the common fragment to all acylcarnitines [MH-59](+) is useful for analyzing their profile. APTDCI parameters, including angle of collection and incidence, gas flows and temperatures, were optimized for acylcarnitines. The experiments were performed drying 2 microL of an equimolar mixture of acylcarnitine standards on a glass slide. The specificity was evaluated by comparing product ion spectra and the precursor ion spectra of 85 m/z of acylcarnitines obtained by the APTDCI method and by electrospray ionization flow injection analysis (ESI-FIA). The method was also employed to analyze acylcarnitines extracted from a pathological dried blood spot and a control. The method enables analysis of biological samples and recognition of some acylcarnitines that are diagnostic markers of inherited metabolic diseases. The intrinsic high-throughput analysis of the ambient desorption ionization methods offers a new opportunity either for its potential application in clinical chemistry and for the expanded screening of some inborn errors of metabolism.

  7. Surface reconstruction and thermal desorption: {O}/{Ag(110) } an experimental study

    Science.gov (United States)

    Canepa, M.; Salvietti, M.; Traverso, M.; Mattera, L.

    1995-07-01

    We have studied the associative desorption of oxygen from well-defined O( n×1)Ag(110) phases ( n ranging from 8 to 2) by thermal desorption mass spectrometry. Desorption peak profiles have been compared with calculations based on a lattice-gas model [V.P. Zhdanov, Surf. Sci. 277 (1992) 155] which takes into account the missing-row reconstruction of the substrate and adsorbate-adsorbate interactions along independent OAgO rows. The model works well at low coverage accurately reproducing the peak profiles. For the O(8 × 1), O(6 × 1) and O(4 × 1) phases, assuming a value of v = 10 15 s -1 for the pre-factor, values of ≈ 39 kcal/mol for the activation energy and ≈ -2.5 kcal/mol for the OO effective oxygen-oxygen interaction along OAgO rows are obtained. At high coverage the assumption of independence of OAgO chains is no longer valid and repulsive interactions perpendicularly to the chains have to be taken into account.

  8. Reliability of a BTEX radial diffusive sampler for thermal desorption: field measurements

    Science.gov (United States)

    Bruno, P.; Caputi, M.; Caselli, M.; de Gennaro, G.; de Rienzo, M.

    Radiello ®, a radial symmetry diffusive sampler, has been evaluated for its potential for ambient air quality monitoring, in particular for benzene, toluene, ethyl benzene, p-xylene, m-xylene, o-xylene (BTEX) measurements. BTEX were first sampled onto adsorbing cartridges before analyses were performed by thermal desorption and GC-MS. Tests were carried out to determine blank values and any storage effects. The results of an investigation into repeatability of the Radiello ® sampler and the influence of sampling time under field conditions are reported. Inter-comparison with automatic instruments is also illustrated.

  9. Thermal proton transfer reactions in ultraviolet matrix-assisted laser desorption/ionization.

    Science.gov (United States)

    Chu, Kuan Yu; Lee, Sheng; Tsai, Ming-Tsang; Lu, I-Chung; Dyakov, Yuri A; Lai, Yin Hung; Lee, Yuan-Tseh; Ni, Chi-Kung

    2014-03-01

    One of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10(-4)) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10(-7) at a high laser fluence and less than 10(-7) at a low laser fluence. Therefore, reexamining the possible contributions of thermally induced reactions in MALDI may be worthwhile. In this study, the concept of polar fluid was employed to explain the generation of primary ions in MALDI. A simple model, namely thermal proton transfer, was used to estimate the ion-to-neutral ratios in MALDI. We demonstrated that the theoretical calculations of ion-to-neutral ratios exhibit the same trend and similar orders of magnitude compared with those of experimental measurements. Although thermal proton transfer may not generate all of the ions observed in MALDI, the calculations demonstrated that thermally induced reactions play a crucial role in UV-MALDI.

  10. Suppression of PCDD/Fs during thermal desorption of PCBs-contaminated soil.

    Science.gov (United States)

    Zhao, Zhonghua; Ni, Mingjiang; Li, Xiaodong; Buekens, Alfons; Yan, Jianhua

    2016-12-01

    Thermal treatment of polychlorinated biphenyls (PCBs) contaminated soil was shown in earlier work to generate new PCBs, as well as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). In this study, this thermal desorption was conducted with addition of three distinct inhibitors, including ammonium sulphate, urea and calcium oxide, to inhibit the formation of PCDDs and PCDFs when remediating PCBs-contaminated soil. Experiments were conducted for 40 min at 400 °C after adding 1 wt.% of inhibitor. Both the total PCDD/Fs and international toxic equivalent quantity (I-TEQ) reduced when inhibitors were introduced. Of the three compounds tested, CaO shows the highest inhibition efficiency, 92.2 % for total PCDD/Fs and 95.6 % for I-TEQ. The amount of CaO added also influences the suppression efficiency of PCDD/Fs. These results suggest that promoting desorption and destruction of precursors is probably the mechanism of suppression.

  11. Evaluation of minimum desorption temperatures of thermal compressors in adsorption refrigeration cycles

    Energy Technology Data Exchange (ETDEWEB)

    Saha, B.B.; El-Sharkawy, I.I.; Chakraborty, A.; Koyama, S.; Srinivasan, K. [Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-koen Kasuga, Fukuoka 816-8580 (Japan); Banker, N.D.; Dutta, P. [Department of Mechanical Engineering, Indian Institute of Science, Bangalore (India); Prasad, M. [Thermal Systems Division, ISRO Satellite Centre, Bangalore (India)

    2006-11-15

    The purpose of this paper is to identify the minimum desorption temperatures required to operate thermally driven adsorption beds of a solid sorption refrigeration system. The method is based on the evaluation of uptake efficiency of the adsorption bed and estimating there from conditions under which the compressor ceases to provide any throughput. The difference in the densities of the refrigerant between the inlet and outlet, the adsorption characteristics of the adsorbate-refrigerant pair and the void volume in the thermal compressor are the contributors to the manifestation of the desorption state. Among them, the void volume is a controllable parameter whose role is analogous to the clearance volume in a positive displacement compressor. The methodology has been tested out with three systems, namely, silica gel+water, activated carbon fiber+ethanol and activated carbon+HFC 134a systems. It is shown that waste heat at as low as 60{sup o}C can operate these systems which make them good energy conservation devices through recovery of low grade process waste heat. (author)

  12. Ion intensity and thermal proton transfer in ultraviolet matrix-assisted laser desorption/ionization.

    Science.gov (United States)

    Lu, I-Chung; Lee, Chuping; Chen, Hui-Yuan; Lin, Hou-Yu; Hung, Sheng-Wei; Dyakov, Yuri A; Hsu, Kuo-Tung; Liao, Chih-Yu; Lee, Yin-Yu; Tseng, Chien-Ming; Lee, Yuan-Tseh; Ni, Chi-Kung

    2014-04-17

    The ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) was investigated by measuring the total cation intensity (not including sodiated and potasiated ions) as a function of analyte concentration (arginine, histidine, and glycine) in a matrix of 2,4,6-trihydroxyacetophenone (THAP). The total ion intensity increased up to 55 times near the laser fluence threshold as the arginine concentration increased from 0% to 1%. The increases were small for histidine, and a minimal increase occurred for glycine. Time-resolved fluorescence intensity was employed to investigate how analytes affected the energy pooling of the matrix. No detectable energy pooling was observed for pure THAP and THAP/analyte mixtures. The results can be described by using a thermal proton transfer model, which suggested that thermally induced proton transfer is crucial in the primary ion generation in UV-MALDI.

  13. Helium implanted Eurofer97 characterized by positron beam Doppler broadening and Thermal Desorption Spectroscopy

    Science.gov (United States)

    Carvalho, I.; Schut, H.; Fedorov, A.; Luzginova, N.; Desgardin, P.; Sietsma, J.

    2013-11-01

    Reduced Activation Ferritic/Martensitic steels are being extensively studied because of their foreseen application in fusion and Generation IV fission reactors. To produce irradiation induced defects, Eurofer97 samples were implanted with helium at energies of 500 keV and 2 MeV and doses of 1 × 1015-1016 He/cm2, creating atomic displacements in the range 0.07-0.08 dpa. The implantation induced defects were characterized by positron beam Doppler Broadening (DB) and Thermal Desorption Spectroscopy (TDS). Results show that up to ˜600 K peaks that can be attributed to He desorption from overpressured HenVm (n > m) clusters and vacancy assisted mechanism in the case of helium in the substitutional position. The temperature range 600-1200 K is related to the formation of larger clusters HenVm (n < m). The dissociation of the HeV and the phase transition attributed to a sharp peak in the TDS spectra at 1200 K. Above this temperature, the release of helium from bubbles is observed.

  14. A Solid Trap and Thermal Desorption System with Application to a Medical Electronic Nose

    Directory of Open Access Journals (Sweden)

    Xuntao Xu

    2008-11-01

    Full Text Available In this paper, a solid trap/thermal desorption-based odorant gas condensation system has been designed and implemented for measuring low concentration odorant gas. The technique was successfully applied to a medical electronic nose system. The developed system consists of a flow control unit, a temperature control unit and a sorbent tube. The theoretical analysis and experimental results indicate that gas condensation, together with the medical electronic nose system can significantly reduce the detection limit of the nose system and increase the system’s ability to distinguish low concentration gas samples. In addition, the integrated system can remove the influence of background components and fluctuation of operational environment. Even with strong disturbances such as water vapour and ethanol gas, the developed system can classify the test samples accurately.

  15. Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Masashi, E-mail: Masashi.Shimada@inl.gov [Fusion Safety Program, Idaho National Laboratory, Idaho Falls, ID (United States); Hara, Masanori [Hydrogen Isotope Research Center, University of Toyama, Toyama (Japan); Otsuka, Teppei [Kyushu University, Interdisciplinary Graduate School of Engineering Science, Higashi-ku, Fukuoka (Japan); Oya, Yasuhisa [Radioscience Research Laboratory, Faculty of Science, Shizuoka University, Shizuoka (Japan); Hatano, Yuji [Hydrogen Isotope Research Center, University of Toyama, Toyama (Japan)

    2015-08-15

    Three tungsten samples irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to deuterium plasma (ion fluence of 1 × 10{sup 26} m{sup −2}) at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy was performed with a ramp rate of 10 °C min{sup −1} up to 900 °C, and the samples were annealed at 900 °C for 0.5 h. These procedures were repeated three times to uncover defect-annealing effects on deuterium retention. The results show that deuterium retention decreases approximately 70% for at 500 °C after each annealing, and radiation damages were not annealed out completely even after the 3rd annealing. TMAP modeling revealed the trap concentration decreases approximately 80% after each annealing at 900 °C for 0.5 h.

  16. Thermal desorption from self-damaged tungsten exposed to deuterium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Gasparyan, Yu.M., E-mail: gasparyan.yury@plasma.mephi.ru [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Kashirskoe sh.31, 115409 Moscow (Russian Federation); Ogorodnikova, O.V. [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Kashirskoe sh.31, 115409 Moscow (Russian Federation); Max-Planck-Institut für Plasmaphysik, EURATOM Association, Boltzmannstr. 2, D-85748 Garching (Germany); Efimov, V.S.; Mednikov, A.; Marenkov, E.D.; Pisarev, A.A. [National Research Nuclear University MEPhI (Moscow Engineering Physics Institute), Kashirskoe sh.31, 115409 Moscow (Russian Federation); Markelj, S.; Čadež, I. [Jožef Stefan Institute and Association EURATOM-MHEST, Jamova Cesta 39, 1000 Ljubljana (Slovenia)

    2015-08-15

    Deuterium retention in tungsten damaged by 2–20 MeV W ions and then exposed to D atoms was investigated by means of thermal desorption spectroscopy. Experimental data demonstrate a significant increase of deuterium retention in the presence of radiation defects. A remarkable amount of deuterium is trapped even at the temperature of 800 K. TDS spectra were simulated using the computer code DIFTRAP based on kinetic rate equations to derive parameters of deuterium interaction with radiation defects. It was shown that irradiation by MeV W ions forms in W a high concentration of strong traps with the detrapping energy of 1.7–2 eV. These traps play major role in the D retention at elevated temperatures. The experimental spectra have peculiarities that are not described by the standard modeling; and the reasons for that are discussed.

  17. Detection of deuterium trapping sites in tungsten by thermal desorption spectroscopy and positron annihilation spectroscopy

    Directory of Open Access Journals (Sweden)

    K. Sato

    2016-12-01

    Full Text Available Thermal desorption spectroscopy (TDS of tungsten implanted with D2+ ions was performed after irradiation with 8 MeV-electrons, 5.0keV-D2+, and 6.0 MeV-Fe3+. The release peak temperatures of the TDS spectra are discussed. Positron annihilation lifetime (PAL measurements of electron-irradiated tungsten were also performed, showing that single vacancies migrate a sufficient distance to arrive at a sink or meet interstitial-type defects during annealing at 673K. A decrease in the PAL was detected for single vacancies that contain deuterium atoms. The peak temperature of deuterium release from dislocations was lower than that from single vacancies. In samples irradiated with 6.0 MeV-Fe3+, the effect of Fe contamination on deuterium trapping and the deuterium release from voids were detected. These tendencies correspond to previous works.

  18. Annealing Behaviour of Helium Bubbles in Titanium Films by Thermal Desorption Spectroscopy and Positron Beam Analysis

    Institute of Scientific and Technical Information of China (English)

    LIU Chao-Zhuo; ZHOU Zhu-Ying; SHI Li-Qun; WANG Bao-Yi; HAO Xiao-Peng; ZHAO Guo-Qing

    2007-01-01

    @@ Helium-containing Ti films are prepared using magnetron sputtering in the helium-argon atmosphere. Isochronal annealing at different temperatures for an hour is employed to reveal the behaviour of helium bubble growth. Ion beam analysis is used to measure the retained helium content. Helium can release largely when annealing above 970 K. A thermal helium desorption spectroscopy system is constructed for assessment of the evolution of helium bubbles in the annealed samples by linear heating (0.4K/s) from room temperature to 1500K. Also, Doppler broadening measurements of positron annihilation radiation spectrum are performed by using changeable energy positron beam. Bubble coarsening evolves gradually below 680K, migration and coalescence of small bubbles dominates in the range of 680-970K, and the Ostwald ripening mechanism enlarges the bubbles with a massive release above 970K.

  19. MGP remediation using thermal desorption: emerging technology yields a permanent solution

    Energy Technology Data Exchange (ETDEWEB)

    Umfleet, D.E.; Bachman, S.A.; Highland, E. [Barr Engineering Company, Ann Arbor, MI (United States)

    1997-12-01

    An investigation of a former manufactured gas plant (MGP) at the site for Northwestern Public Service`s new operations buildings uncovered evidence of MGP residuals in the moist, clay-rich soils. On site-thermal desorption was selected as the remedial method. A low-temperature, counter-flow, direct-fired rotary desorber heats soils up to 1200{degree}F to volatilize organic fractions. Soils containing polyaromatic hydrocarbon (PAH) compounds were excavated, treated effectively, and reused at the site as backfill. For the approximately 47,000 tons of soil processed, remediation costs were 82 dollars per ton. Site-specific factors affecting project costs included the volume of soil treated, soil type and condition, inclement weather, and market conditions. Soils were treated to below state-approved performance criterion, and remediation of the site was completed just 18 months after the project began. 1 fig., 2 tabs.

  20. Analysis of organic contaminants from silicon wafer and disk surfaces by thermal desorption-GC-MS

    Science.gov (United States)

    Camenzind, Mark J.; Ahmed, Latif; Kumar, Anurag

    1999-03-01

    Organic contaminants can affect semiconductor wafer processing including gate oxide integrity, polysilicon growth, deep ultraviolet photoresist line-width, and cleaning & etching steps. Organophosphates are known to counter dope silicon wafers. Organic contaminants in disk drives can cause failures due to stiction or buildup on the heads. Therefore, it is important to identify organic contaminants adsorbed on wafer or disk surfaces and find their sources so they can be either completely eliminated or at least controlled. Dynamic headspace TD-GC-MS (Thermal Desorption-Gas Chromatography-Mass Spectrometry) methods are very sensitive and can be used to identify organic contaminants on disks and wafers, in air, or outgassing from running drives or their individual components.

  1. Quantification of Selected Vapour-Phase Compounds using Thermal Desorption-Gas Chromatography

    Directory of Open Access Journals (Sweden)

    McLaughlin DWJ

    2014-12-01

    Full Text Available A robust method for the analysis of selected vapour phase (VP compounds in mainstream smoke (MSS is described. Cigarettes are smoked on a rotary smoking machine and the VP that passes through the Cambridge filter pad collected in a TedlarA¯ bag. On completion of smoking, the bag contents are sampled onto an adsorption tube containing a mixed carbon bed. The tube is subsequently analysed on an automated thermal desorption (TD system coupled to a gas chromatography-flame ionization detector (GC-FID using a PoraPLOT-Q column. Quantification of 14 volatile compounds including the major carbonyls is achieved. Details of the method validation data are included in this paper. This method has been used to analyse the VP of cigarette MSS over a wide range of ‘tar’ deliveries and configurations with excellent repeatability. Results for the University of Kentucky reference cigarette 1R4F are in good agreement with reported values.

  2. Operable Unit 7-13/14 in situ thermal desorption treatability study work plan

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, P.; Nickelson, D.; Hyde, R.

    1999-05-01

    This Work Plan provides technical details for conducting a treatability study that will evaluate the application of in situ thermal desorption (ISTD) to landfill waste at the Subsurface Disposal Area (SDA) at the Idaho National Engineering and Environmental Laboratory (INEEL). ISTD is a form of thermally enhanced vapor vacuum extraction that heats contaminated soil and waste underground to raise its temperature and thereby vaporize and destroy most organics. An aboveground vapor vacuum collection and treatment system then destroys or absorbs the remaining organics and vents carbon dioxide and water to the atmosphere. The technology is a byproduct of an advanced oil-well thermal extraction program. The purpose of the ISTD treatability study is to fill performance-based data gaps relative to off-gas system performance, administrative feasibility, effects of the treatment on radioactive contaminants, worker safety during mobilization and demobilization, and effects of landfill type waste on the process (time to remediate, subsidence potential, underground fires, etc.). By performing this treatability study, uncertainties associated with ISTD as a selected remedy will be reduced, providing a better foundation of remedial recommendations and ultimate selection of remedial actions for the SDA.

  3. DEMONSTRATION BULLETIN: THE ECO LOGIC THERMAL DESORPTION UNIT - MIDDLEGROUND LANDFILL - BAY CITY, MI - ELI ECO LOGIC INTERNATIONAL, INC.

    Science.gov (United States)

    ECO Logic has developed a thermal desorption unit 0"DU) for the treatment of soils contaminated with hazardous organic contaminants. This TDU has been designed to be used in conjunction with Eco Logic's patented gas-phase chemical reduction reactor. The Eco Logic reactor is the s...

  4. DEMONSTRATION BULLETIN: THE ECO LOGIC THERMAL DESORPTION UNIT - MIDDLEGROUND LANDFILL - BAY CITY, MI - ELI ECO LOGIC INTERNATIONAL, INC.

    Science.gov (United States)

    ECO Logic has developed a thermal desorption unit 0"DU) for the treatment of soils contaminated with hazardous organic contaminants. This TDU has been designed to be used in conjunction with Eco Logic's patented gas-phase chemical reduction reactor. The Eco Logic reactor is the s...

  5. Thermal desorption-gas chromatography for the determination of benzene, aniline, nitrobenzene and chlorobenzene in workplace air.

    Science.gov (United States)

    Patil, S F; Lonkar, S T

    1992-05-29

    Sampling on Tenax TA of different mesh sizes followed by thermal desorption and gas chromatography was evaluated as a simple method for the determination of benzene, aniline, nitrobenzene and chlorobenzene in the workplace air. An alternative sampling technique in place of pump sampling was developed. Quantitative recoveries were obtained in the mass range 0.04-10 micrograms. It was found that air humidity had no effect on recovery. The charged tubes can be stored at room temperature for 5 days with no change in recovery. The particle size of Tenax TA has no significant effect on adsorption and desorption.

  6. Non-isothermal kinetics of the thermal desorption of mercury from a contaminated soil

    Directory of Open Access Journals (Sweden)

    López, Félix A.

    2014-03-01

    Full Text Available The Almadén mining district (Ciudad Real, Spain was the largest cinnabar (mercury sulphide mine in the world. Its soils have high levels of mercury a consequence of its natural lithology, but often made much worse by its mining history. The present work examines the thermal desorption of two contaminated soils from the Almadén area under non-isothermal conditions in a N2 atmosphere, using differential scanning calorimetry (DSC. DSC was performed at different heating rates between room temperature and 600 °C. Desorption temperatures for different mercury species were determined. The Friedman, Flynn-Wall-Ozawa and Coasts–Redfern methods were employed to determine the reaction kinetics from the DSC data. The activation energy and pre-exponential factor for mercury desorption were calculated.El distrito minero de Almadén (Ciudad Real, España tiene la mayor mina de cinabrio (sulfuro de mercurio del mundo. Sus suelos tienen altos niveles de mercurio como consecuencia de su litología natural, pero a menudo su contenido en mercurio es mucho más alto debido a la historia minera de la zona. Este trabajo examina la desorción térmica de dos suelos contaminados procedentes de Almadén bajo condiciones isotérmicas en atmósfera de N2, empleando calorimetría diferencial de barrido (DSC. La calorimetría se llevó a cabo a diferentes velocidades de calentamiento desde temperatura ambiente hasta 600 °C. Se determinaron las diferentes temperaturas de desorción de las especies de mercurio presentes en los suelos. Para determinar la cinética de reacción a partir de los datos de DSC se utilizaron los métodos de Friedman, Flynn-Wall-Ozawa y Coasts–Redfern. Además se calcularon las energías de activación y los factores pre-exponenciales para la desorción del mercurio.

  7. Broad spectrum infrared thermal desorption of wipe-based explosive and narcotic samples for trace mass spectrometric detection.

    Science.gov (United States)

    Forbes, Thomas P; Staymates, Matthew; Sisco, Edward

    2017-08-07

    Wipe collected analytes were thermally desorbed using broad spectrum near infrared heating for mass spectrometric detection. Employing a twin tube filament-based infrared emitter, rapid and efficiently powered thermal desorption and detection of nanogram levels of explosives and narcotics was demonstrated. The infrared thermal desorption (IRTD) platform developed here used multi-mode heating (direct radiation and secondary conduction from substrate and subsequent convection from air) and a temperature ramp to efficiently desorb analytes with vapor pressures across eight orders of magnitude. The wipe substrate experienced heating rates up to (85 ± 2) °C s(-1) with a time constant of (3.9 ± 0.2) s for 100% power emission. The detection of trace analytes was also demonstrated from complex mixtures, including plastic-bonded explosives and exogenous narcotics, explosives, and metabolites from collected artificial latent fingerprints. Manipulation of the emission power and duration directly controlled the heating rate and maximum temperature, enabling differential thermal desorption and a level of upstream separation for enhanced specificity. Transitioning from 100% power and 5 s emission duration to 25% power and 30 s emission enabled an order of magnitude increase in the temporal separation (single seconds to tens of seconds) of the desorption of volatile and semi-volatile species within a collected fingerprint. This mode of operation reduced local gas-phase concentrations, reducing matrix effects experienced with high concentration mixtures. IRTD provides a unique platform for the desorption of trace analytes from wipe collections, an area of importance to the security sector, transportation agencies, and customs and border protection.

  8. Characterisation of Dissolved Organic Carbon by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

    Science.gov (United States)

    Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

    2017-04-01

    Dissolved organic carbon (DOC) is an integral component of the global carbon cycle. DOC represents an important terrestrial carbon loss as it is broken down both biologically and photochemically, resulting in the release of carbon dioxide (CO2) to the atmosphere. The magnitude of this carbon loss can be affected by land management (e.g. drainage). Furthermore, DOC affects autotrophic and heterotrophic processes in aquatic ecosystems, and, when chlorinated during water treatment, can lead to the release of harmful trihalomethanes. Numerous methods have been used to characterise DOC. The most accessible of these use absorbance and fluorescence properties to make inferences about chemical composition, whilst high-performance size exclusion chromatography can be used to determine apparent molecular weight. XAD fractionation has been extensively used to separate out hydrophilic and hydrophobic components. Thermochemolysis or pyrolysis Gas Chromatography - Mass Spectrometry (GC-MS) give information on molecular properties of DOC, and 13C NMR spectroscopy can provide an insight into the degree of aromaticity. Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. So far, PTR-MS has been used in various environmental applications such as real-time monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols etc. However, as the method is not compatible with water, it has not been used for analysis of organic traces present in natural water samples. The aim of this work was to develop a method based on thermal desorption PTR-MS to analyse water samples in order to characterise chemical composition of dissolved organic carbon. We developed a clean low-pressure evaporation/sublimation system to remove water from samples and thermal desorption system to introduce

  9. GoAmazon 2014/15 Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Smith, JN [Univ. of California, Irvine, CA (United States)

    2016-04-01

    The Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) deployment to the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility T3 site in Manacapuru, Brazil, was motivated by two main scientific objectives of the Green Ocean Amazon (GoAmazon) 2014/15 field campaign. 1) Study the interactions between anthropogenic and biogenic emissions by determining important molecular species in ambient nanoparticles. To address this, TDCIMS data will be combined with coincident measurements such as gas-phase sulfuric acid to determine the contribution of sulfuric acid condensation to nucleation and growth. We can then compare that result to TDCIMS-derived nanoparticle composition to determine the fraction of growth that can be attributed to the uptake of organic compounds. The molecular composition of sampled particles will also be used to attribute specific chemical species and mechanisms to growth, such as the condensation of low-volatility species or the oligomerization of α-dicarbonyl compounds. 2) Determine the source of new ambient nanoparticles in the Amazon. The hypothesis prior to measurements was that potassium salts formed from the evaporation of primary particles emitted by fungal spores can provide a unique and important pathway for new particle production in the Amazon basin. To explore this hypothesis, the TDCIMS recorded the mass spectra of sampled ambient particles using a protonated water cluster Chemical Ionization Mass Spectrometer (CIMS). Laboratory tests performed using potassium salts show that the TDCIMS can detect potassium with high sensitivity with this technique.

  10. Inelastic scattering of OH radicals from organic liquids: isolating the thermal desorption channel.

    Science.gov (United States)

    King, Kerry L; Paterson, Grant; Rossi, Giovanni E; Iljina, Marija; Westacott, Robin E; Costen, Matthew L; McKendrick, Kenneth G

    2013-08-21

    Inelastic scattering of OH radicals from liquid surfaces has been investigated experimentally. An initially translationally and rotationally hot distribution of OH was generated by 193 nm photolysis of allyl alcohol. These radicals were scattered from an inert reference liquid, perfluorinated polyether (PFPE), and from the potentially reactive hydrocarbon liquids squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) and squalene (C30H50, trans-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene). The scattered OH v = 0 products were detected by laser-induced fluorescence. Strong correlations were observed between the translational and rotational energies of the products. The high-N levels are translationally hot, consistent with a predominantly direct, impulsive scattering mechanism. Impulsive scattering also populates the lower-N levels, but a component of translationally relaxed OH, with thermal-desorption characteristics, can also be seen clearly for all three liquids. More of this translationally and rotationally relaxed OH survives from squalane than from squalene. Realistic molecular dynamics simulations confirm that double-bond sites are accessible at the squalene surface. This supports the proposition that relaxed OH may be lost on squalene via an addition mechanism.

  11. Implications of Using Thermal Desorption to Remediate Contaminated Agricultural Soil: Physical Characteristics and Hydraulic Processes.

    Science.gov (United States)

    O'Brien, Peter L; DeSutter, Thomas M; Casey, Francis X M; Derby, Nathan E; Wick, Abbey F

    2016-07-01

    Given the recent increase in crude oil production in regions with predominantly agricultural economies, the determination of methods that remediate oil contamination and allow for the land to return to crop production is increasingly relevant. Ex situ thermal desorption (TD) is a technique used to remediate crude oil pollution that allows for reuse of treated soil, but the properties of that treated soil are unknown. The objectives of this research were to characterize TD-treated soil and to describe implications in using TD to remediate agricultural soil. Native, noncontaminated topsoil and subsoil adjacent to an active remediation site were separately subjected to TD treatment at 350°C. Soil physical characteristics and hydraulic processes associated with agricultural productivity were assessed in the TD-treated samples and compared with untreated samples. Soil organic carbon decreased more than 25% in both the TD-treated topsoil and the subsoil, and total aggregation decreased by 20% in the topsoil but was unaffected in the subsoil. The alteration in these physical characteristics explains a 400% increase in saturated hydraulic conductivity in treated samples as well as a decrease in water retention at both field capacity and permanent wilting point. The changes in soil properties identified in this study suggest that TD-treated soils may still be suitable for sustaining vegetation, although likely at a slightly diminished capacity when directly compared with untreated soils.

  12. Rapid determination of nicotine in urine by direct thermal desorption ion trap mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Wise, M.B.; Ilgner, R.H.; Guerin, M.R.

    1990-01-01

    The measurement of nicotine and cotinine in physiological fluids (urine, blood serum, and saliva) is widely used as a means of assessing human exposure to environmental tobacco smoke (ETS). Although numerous analytical methods exist for these measurements, they generally involve extensive sample preparation which increases cost and decreases sample throughput. We report the use of thermal desorption directly into an ion trap mass spectrometer (ITMS) for the rapid determination of nicotine and cotinine in urine. A 1{mu}L aliquot of urine is injected into a specially designed inlet and flash vaporized directly into an ITMS through an open-split capillary restrictor interface. Isobutane chemical ionization is used to generate (M+H){sup +} ions of the analytes and collision induced dissociation is used to generate characteristic fragment ions which are used to confirm their identity. Quantification is achieved by integrating the ion current for the characteristic ions and comparing with an external working curve. Detection limits are approximately 50 pg per analyte and the sample turnaround time is approximately 3 minutes without the need for extensive sample preparation. 12 refs., 5 figs.

  13. Atomic force microscope controlled topographical imaging and proximal probe thermal desorption/ionization mass spectrometry imaging.

    Science.gov (United States)

    Ovchinnikova, Olga S; Kjoller, Kevin; Hurst, Gregory B; Pelletier, Dale A; Van Berkel, Gary J

    2014-01-21

    This paper reports on the development of a hybrid atmospheric pressure atomic force microscopy/mass spectrometry imaging system utilizing nanothermal analysis probes for thermal desorption surface sampling with subsequent atmospheric pressure chemical ionization and mass analysis. The basic instrumental setup and the general operation of the system were discussed, and optimized performance metrics were presented. The ability to correlate topographic images of a surface with atomic force microscopy and a mass spectral chemical image of the same surface, utilizing the same probe without moving the sample from the system, was demonstrated. Co-registered mass spectral chemical images and atomic force microscopy topographical images were obtained from inked patterns on paper as well as from a living bacterial colony on an agar gel. Spatial resolution of the topography images based on pixel size (0.2 μm × 0.8 μm) was better than the resolution of the mass spectral images (2.5 μm × 2.0 μm), which were limited by current mass spectral data acquisition rate and system detection levels.

  14. Age determination of ballpoint pen ink by thermal desorption and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Bügler, Jürgen H; Buchner, Hans; Dallmayer, Anton

    2008-07-01

    Two main approaches can be used for determining the age of an ink: indirect dating and direct dating. Indirect dating is based on the chemical analysis of an ink followed by comparison with known samples in a reference collection. The collection should contain information about the inks including the market introduction dates. This approach may allow for an anachronism to be detected. The second concept is based on measuring ink components that change with age. The analysis of solvents in ballpoint inks may be a useful parameter for determining the age of ink on paper. In a previous study, the authors demonstrated that thermal desorption of ink directly from paper, followed by chemical analysis using gas chromatography-mass spectrometry (GC-MS), is a promising procedure for characterizing ink-binder resins and solvents. Preliminary tests showed that monitoring the evaporation of ink solvent from ink on paper is not a suitable method for ink dating. Thermal analysis of ink on paper in two steps revealed that fresh ink releases a relative amount of solvent at a certain low temperature in a defined period of time, which decreases as the ink ages. As a consequence, this relative amount of solvent released at a certain low temperature, and its decrease with time, can be used to estimate ink age. This age-dependent parameter was studied in 85 different inks ranging in age from 1 week to 1.5 years. It was found that some inks showed a significant decrease of this parameter up to an age of several months, and that the aging process can be monitored within this period. For other inks, however, the age-dependent parameter decreases relatively fast, e.g., within a few days, to a constant level, which can be too fast for casework. Based on these results, a general procedure for assessing the age of ballpoint pen inks on paper was developed.

  15. Effects of He, D interaction on thermal desorption of He and D2 and microstructural evolution in pure Fe

    Science.gov (United States)

    Xu, Q.; Zhang, J.

    2016-10-01

    He and H atoms are produced in (n, α) and (n, p) nuclear reactions. In fusion reactors, energetic T and D, being isotopes of H, and He particles damage the surface materials. To investigate the He-D interaction, Fe, which is a model metal of choice in ferritic stainless steel that is used in fusion reactors, was irradiated separately by He or D2 ions and by combinations of He + D2 or D2 + He ions with the energy of 5 keV. The dose for single-species irradiation and each step of double-species irradiation was 1.0 × 1020 ions/m2. Thermal desorption analysis indicates that, in the case of single ion species irradiation, thermal desorption of D occurs at temperatures below 700 K, while the main thermal desorption of He occurs at 750 K and above 1200 K. The binding energy of He and defects is higher than that of D and defects. In the case of irradiation with combinations of ions species, however, the obtained thermal desorption spectra are the same, although the peak intensities are different, suggesting that the He-D interaction is weak. The sorption of D is more predominant for irradiations with He + D2. On the microstructure level, the irradiated samples exhibited larger voids following combined irradiations compared with those for irradiation with a single ion species after annealing to 1323 K. During the He + D2 irradiation, D atoms are effectively trapped owing to the defects induced by pre-irradiation with He.

  16. Polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran formation and emission in the thermal desorption waste treatment process

    Energy Technology Data Exchange (ETDEWEB)

    Leckey, J.H.

    1995-03-01

    It is extremely unlikely that significant amounts of polychlorinated dibenzo-p-dioxins (PCDDs) or polychlorinated dibenzofurans (PCDFs) will be emitted in the off-gas stream from the thermal desorption process, or the treated waste, particularly if the baseline design and anticipated operating conditions of the enhanced bench-scale (EBS) system are used. However, because of the acute toxicity of these compounds and because most of the data on their formation have been extrapolated from studies more related to incineration and fire conditions than thermal desorption, specific laboratory tests and specific EBS runs should be performed to monitor the rate of emission of PCDDs and PCDFs under thermal desorption conditions. In general, the following four conditions need to exist for significant amounts of PCDD or PCDF to be formed: (1) the presence of fly ash; (2) the presence of an oxidizing source; (3) a suitable temperature, and (4) the presence of a suitable precursor. Although the EBS system provides some of these conditions, it is unlikely that enough fly ash will be produced in the system to allow a significant amount of PCDD or PCDF formation. Additionally, particulate matter controls will be used to remove airborne particulates from the gas phase. If PCDD/Fs are presented in a waste stream being evaluated in the EBS, they will likely volatilize in the kiln and subsequently condense in the venturi scrubber system.

  17. Filtration efficiency validation of glass wool during thermal desorption-gas chromatography-mass spectrometer analysis of fine atmospheric particles.

    Science.gov (United States)

    Hao, Liang; Wu, Dapeng; Ding, Kun; Meng, Hu; Yan, Xiaohui; Guan, Yafeng

    2015-02-06

    Thermal desorption-gas chromatography-mass spectrometer (TD-GC-MS) technique has been widely used for analysis of semi-violate organic compounds on atmospheric aerosol. To prevent GC column from being damaged by fine solid particles during thermal desorption process, glass wool as filter mat is indispensible. However, the filtration efficiency has never been validated. In this paper, the most penetrating particle size and the minimum packing thickness of glass wool were calculated based on classical filtration theory. According to the calculation results, packing parameters of glass wool were optimized experimentally using silica particles. It is demonstrated that glass wool with a packing thickness of 30 mm, solidity of 0.039 can effectively block these fine solid particles from penetrating at normal thermal desorption conditions (T=300°C, u=0.4-4 cm/s). Finally, the filtration efficiency of glass wool was further confirmed with real PM2.5 samples. Under the validated filtration condition, TD-GC-MS was applied for the analysis of non-polar organic compounds on real PM2.5 samples, and very good results were obtained.

  18. Identification of sink spots in two thermal desorption GC/MS systems for the analysis of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Li, Yingjie; Zhu, Jiping

    2017-04-08

    Thermal desorption (TD) GC/MS has been used for the analysis of polycyclic aromatic hydrocarbons (PAHs) and other semi-volatile organic compounds. However, thermal desorption recovery of PAHs have not been well studied and the cause of PAH residues in a TD system has not been clearly understood. Our results showed that low volatility of PAHs can lead to their incomplete recovery in a TD system: for the PAHs with low vapour pressures, up to 10% and 3% could be lost in a two-stage (TS) TD system and a short-path (SP) TD system, respectively. Within the TSTD system, the majority of residues were found in the 4-port valve and in the spot where internal trap and the 4-port valve connects. Within the SPTD system, residues were largely confined to the tube needle connecting the sample tube and GC injection port as well as inside the injection port. Since the volatility of PAHs can represent the range typical of semi-volatile organic compounds (SVOCs), our results have a wide implication for the thermal desorption of SVOCs in general. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  19. Leidenfrost phenomenon-assisted thermal desorption (LPTD) and its application to open ion sources at atmospheric pressure mass spectrometry.

    Science.gov (United States)

    Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2013-03-01

    This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution 'Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10(-9) M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

  20. Trapping state of hydrogen isotopes in carbon and graphite investigated by thermal desorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Atsumi, H. [Department of Electric and Electronic Engineering, Kinki University, Higashiosaka (Japan); Tanabe, T. [Interdisciplinary Graduat School of Engineering Sciences, Kyushu University, Fukuoka (Japan); Shikama, T. [Institute for Materials Research, Tohoku University, Sendai (Japan)

    2015-03-15

    Thermal desorption spectrometry (TDS) has been investigated to obtain fundamental information of tritium behavior in graphite and carbon materials especially at high temperatures. 29 brands of graphite, HOPG, glassy carbon and CFC materials charged with deuterium gas are tested up to the temperature of 1735 K with a heating rate of 0.1 K/s. TDS spectra have five peaks at 600-700 K, around 900 K, 1200 K, 1300-1450 K and 1600-1650 K. The amounts of released deuterium have been compared with crystallographic parameters derived from XRD analysis. The results can be summarized as follows. First, TDS spectra of deuterium were quite varied among the samples tested, such as existence of peaks, peak temperatures and release amounts of deuterium. Secondly, TDS spectra may consist of five peaks, which are peak 1 (600-700 K), peak 2 (around 900 K), peak 3 (around 1200 K), peak 4 (1300-1450 K) and peak 5 (1600-1650 K). Thirdly, the correlations between the estimated surface area of edge surface and the total amount of released deuterium could be observed for peaks 4 and 5. Fourthly, high energy trapping site (peak 5) may exist even at edge surface or a near surface region, not only for intercalary. And fifth, in order to obtain the lower tritium retention for graphite and CFC materials, the material should be composed of a filler grain with a smaller crystallite size or having the smaller net edge surface in its structure. It is shown that heat treatment does not reduce originally existing trapping sites but trapping sites generated by neutron irradiation for instance can be reduced in some degree.

  1. Direct thermal desorption of semivolatile organic compounds from diffusion denuders and gas chromatographic analysis for trace concentration measurement.

    Energy Technology Data Exchange (ETDEWEB)

    Tobias, D. E.; Perlinger, J. A.; Morrow, P. S.; Doskey, P. V.; Perram, D.L.; Environmental Science Division; Michigan Technological Univ.

    2007-01-01

    A novel method for collection and analysis of vapor-phase semivolatile organic compounds (SOCs) in ambient air is presented. The method utilizes thermal desorption of SOCs trapped in diffusion denuders coupled with cryogenic preconcentration on Tenax-TA and analysis by high resolution gas chromatography (GC)-electron-capture detection (ECD). The sampling and analysis methods employ custom-fabricated multicapillary diffusion denuders, a hot gas spike (HGS) apparatus to load known quantities of thermally stable standards into diffusion denuders prior to sample collection, a custom-fabricated oven to thermally desorb SOCs from the diffusion denuder, and a programmable temperature vaporization (PTV) inlet containing a liner packed with Tenax-TA for effective preconcentration of the analytes and water management. High flow rates into the PTV inlet of 750 mL min-1during thermal desorption are ca. a factor of ten greater than typically used. To improve resolution and retention time stability, the thermal desorption and PTV inlet programming procedure includes three steps to prevent water from entering the analytic column while effectively transferring the analytes into the GC system. The instrumentation and procedures provide virtually complete and consistent transfer of analytes collected from ambient air into the GC evidenced by recovery of seven replicates of four internal standards of 90.7 {+-} 4.0-120 {+-} 23% (mean {+-} 95% confidence interval, CI). Retention time based compound identification is facilitated by low retention time variability with an average 95% CI of 0.024 min for sixteen replicates of eight standards. Procedure details and performance metrics as well as ambient sampling results are presented.

  2. Direct thermal desorption of semivolatile organic compounds from diffusion denuders and gas chromatographic analysis for trace concentration measurement.

    Science.gov (United States)

    Tobias, David E; Perlinger, Judith A; Morrow, Patrick S; Doskey, Paul V; Perram, David L

    2007-01-26

    A novel method for collection and analysis of vapor-phase semivolatile organic compounds (SOCs) in ambient air is presented. The method utilizes thermal desorption of SOCs trapped in diffusion denuders coupled with cryogenic preconcentration on Tenax-TA and analysis by high resolution gas chromatography (GC)-electron-capture detection (ECD). The sampling and analysis methods employ custom-fabricated multicapillary diffusion denuders, a hot gas spike (HGS) apparatus to load known quantities of thermally stable standards into diffusion denuders prior to sample collection, a custom-fabricated oven to thermally desorb SOCs from the diffusion denuder, and a programmable temperature vaporization (PTV) inlet containing a liner packed with Tenax-TA for effective preconcentration of the analytes and water management. High flow rates into the PTV inlet of 750mLmin(-1)during thermal desorption are ca. a factor of ten greater than typically used. To improve resolution and retention time stability, the thermal desorption and PTV inlet programming procedure includes three steps to prevent water from entering the analytic column while effectively transferring the analytes into the GC system. The instrumentation and procedures provide virtually complete and consistent transfer of analytes collected from ambient air into the GC evidenced by recovery of seven replicates of four internal standards of 90.7+/-4.0-120+/-23% (mean+/-95% confidence interval, CI). Retention time based compound identification is facilitated by low retention time variability with an average 95% CI of 0.024min for sixteen replicates of eight standards. Procedure details and performance metrics as well as ambient sampling results are presented.

  3. Rapid identification of pesticides in human oral fluid for emergency management by thermal desorption electrospray ionization/mass spectrometry.

    Science.gov (United States)

    Lee, Chi-Wei; Su, Hung; Chen, Peng-Yu; Lin, Shiang-Jiun; Shiea, Jentaie; Shin, Shyi-Jang; Chen, Bai-Hsiun

    2016-02-01

    Self-poisoning with pesticides accounts for approximately one-third of all suicides worldwide. To expedite rescue in the emergency department, it is essential to develop a point-of-care analytical method for rapid identification of ingested pesticides. In this study, five of the most common pesticides ingested by self-poisoning patients in Taiwan were analyzed from oral fluid samples. Pesticide-oral fluid mixtures were applied on a cotton swab and then transferred into methanol. A metallic probe was used to sample the methanol solution for subsequent thermal desorption-electrospray ionization mass spectrometry analysis. Altogether, pesticide sampling, transfer, desorption, ionization, and detection took less than 1 min. The reproducibility of this method (n = 6) was shown in the observed low-relative standard deviation (four human subjects by thermal desorption-electrospray ionization mass spectrometry were between 1-10 ppb with relative standard deviation 10.7%. Moreover, in this study, linear responses of five pesticides in oral fluid with concentrations between 1 ppb-1 ppm (R2 between 0.9938 and 0.9988) were observed. As the whole analytical process is extremely short, this technique allows for early non-invasive point-of-care identification of pesticides in the oral fluid of self-poisoning patients in the emergency room, providing important toxicological information for decision-making during critical resuscitation.

  4. Evaluation of Water Repellency in Petroleum Drilling Cuttings Treated by Thermal Desorption: Implications for Use in Construction and Agriculture

    Science.gov (United States)

    Domínguez-Rodríguez, Verónica I.; Guzmán-Osorio, Francisco J.; Adams Schroeder, Randy H.; Bautista-Margulis, Raúl G.

    2010-05-01

    Thermal desorption is one of many methods used for the remediation of hydrocarbon contaminated soils and similar materials. It has several advantages over competing technologies, especially with respect to treatment times. While the biological treatment of contaminated soils may take several months depending principally on the type of hydrocarbons and starting concentration, thermal desorption typically takes less than one month, depending on the treatment capacities of the equipment involved, and the volume of material requiring treatment. In the petroleum producing region of southeastern Mexico, this has been one of the principal methods used for the treatment of drilling cuttings, due mostly to the short time required. As with most remediation projects, as well as in the treatment of exploration and production (E&P) wastes, the criteria used to consider the remediation finalized is the concentration of hydrocarbons in the treated material. This is based on the supposition that at some (relatively low) hydrocarbon concentration, the toxicological affects are reduced to acceptable levels. However, little attention has been paid to the physical-chemical properties of supposedly treated material, which may suffer from water repellency, especially in thermal treatment methods. This could greatly reduce the options for final use of treated materials, especially to support plant growth. Conversely, there may be some construction uses of treated material in which some water repellence could be beneficial (caps for land fills, for example). Considering the relevance of the physical-chemical impacts of petroleum on soil and similar materials, we felt it was important to evaluate the efficiency of the principal method used to treat E&P wastes in Mexico (thermal desporption) based on these factors. In this study different operating conditions (temperature and residence time) of a sub-pilot scale thermal desorption unit were evaluated with respect not only to reduction in

  5. Quantification of diesel exhaust gas phase organics by a thermal desorption proton transfer reaction mass spectrometer

    Directory of Open Access Journals (Sweden)

    M. H. Erickson

    2012-02-01

    Full Text Available A new approach was developed to measure the total abundance of long chain alkanes (C12 and above in urban air using thermal desorption with a proton transfer reaction mass spectrometer (PTR-MS. These species are emitted in diesel exhaust and may be important precursors to secondary organic aerosol production in urban areas. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The yield of the fragment ions is a function of drift conditions. At a drift field strength of 80 Townsends, the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Higher drift field strengths yield greater normalized sensitivity implying that the proton affinity of the long chain n-alkanes is less than H2O. Analysis of diesel fuel shows the mass spectrum was dominated by alkanes (CnH2n+1, monocyclic aromatics, and an ion group with formula CnH2n−1 (m/z 97, 111, 125, 139. The PTR-MS was deployed in Sacramento, CA during the Carbonaceous Aerosols and Radiative Effects Study field experiment in June 2010. The ratio of the m/z 97 to 85 ion intensities in ambient air matched that found in diesel fuel. Total diesel exhaust alkane concentrations calculated from the measured abundance of m/z 85 ranged from the method detection limit of ~1 μg m−3 to 100 μg m−3 in several air pollution episodes. The total diesel exhaust alkane concentration determined by this method was on average a factor of 10 greater than the sum of alkylbenzenes associated with spark ignition vehicle exhaust.

  6. The use of thermal desorption in monitoring for the chemical weapons demilitarization program.

    Science.gov (United States)

    Harper, Martin

    2002-10-01

    Under international treaty, the United States and Russia are disposing of their aging stockpile of chemical weapons. Incineration and chemical neutralization are options for sites in the United States, although Russia prefers the latter. The storage and disposal of bulk and chemical agents and weapons involve unique hazards of handling extremely toxic materials. There are three major areas of concern--the storage stockpile, the disposal area, and the discovery and destruction of "found" material not considered part of the stockpile. Methods have been developed to detect the presence of chemical agents in the air, and these are used to help assure worker protection and the safety of the local population. Exposure limits for all chemical agents are low, sometimes nanograms per cubic meter for worker control limits and picograms per cubic meter for general population limits. There are three types of monitoring used in the USA: alarm, confirmation, and historical. Alarm monitors are required to give relatively immediate real-time responses to agent leaks. They are simple to operate and rugged, and provide an alarm in near real-time (generally a few minutes). Alarm monitors for the demilitarization program are based on sorbent pre-concentration followed by thermal desorption and simple gas chromatography. Alarms may need to be confirmed by another method, such as sample tubes collocated with the alarm monitor and analyzed in a laboratory by more sophisticated chromatography. Sample tubes are also used for historical perimeter monitoring, with sample periods typically of 12 h. The most common detector is the flame photometric detector, in sulfur or phosphorous mode, although others, such as mass-selective detectors, also have been used. All agents have specific problems with collection, chromatography and detection. Monitoring is not made easier by interferences from pesticide spraying, busy roadways or military firing ranges. Exposure limits drive the requirements for

  7. Thermal decomposition of AlH{sub 3} studied by in situ synchrotron X-ray diffraction and thermal desorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, J.P. [Institute for Energy Technology, P.O. Box 40, Kjeller No-2027 (Norway); Yartys, V.A. [Institute for Energy Technology, P.O. Box 40, Kjeller No-2027 (Norway)], E-mail: volodymyr.yartys@ife.no; Denys, R.V. [Institute for Energy Technology, P.O. Box 40, Kjeller No-2027 (Norway); Physico-Mechanical Institute of the National Academy of Science of Ukraine, 5, Naukova Str., 79601 Lviv (Ukraine); Fichtner, M.; Frommen, Ch. [Institute of Nanotechnology, Forschungszentrum Karlsruhe GmbH, P.O. Box 30640, D-76021 Karlsruhe (Germany); Bulychev, B.M. [Chemistry Department, Moscow State University, Leninskie Gori, Moscow 119992, MSU, Chemistry Department (Russian Federation); Pattison, P.; Emerich, H.; Filinchuk, Y.E.; Chernyshov, D. [Swiss-Norwegian Beam Line, ESRF, BP 220, F-38043 Grenoble (France)

    2007-10-31

    The thermal decomposition of alane was investigated by application of synchrotron X-ray diffraction (SR-XRD) and thermal desorption spectroscopy (TDS). Two polymorphs were studied, {alpha}- and {gamma}-AlH{sub 3}. Activation energies, anisotropic volume expansions, and phase transformation paths were found. In addition, the crystal structure data, including structure of hydrogen sublattice, and small charge transfer from the aluminium towards the hydrogen sites were observed during a high-resolution SR-XRD study of {alpha}-AlH{sub 3}.

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

    Science.gov (United States)

    Ramírez, Noelia; Marcé, Rosa Maria; Borrull, Francesc

    2010-06-25

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

  9. The thermal desorption of CO2 from amine carbamate solutions for the 13C isotope enrichment

    Science.gov (United States)

    Dronca, S.; Varodi, C.; Gligan, M.; Stoia, V.; Baldea, A.; Hodor, I.

    2012-02-01

    The CO2 desorption from amine carbamate in non-aqueous solvents is of major importance for isotopic enrichment of 13C. A series of experiments were carried out in order to set up the conditions for the CO2 desorption. For this purpose, a laboratory- scale plant for 13C isotope separation by chemical exchange between CO2 and amine carbamate was designed and used. The decomposition of the carbamate solution was mostly produced in the desorber and completed in the boiler. Two different-length desorbers were used, at different temperatures and liquid flow rates of the amine-non-aqueous solvent solutions. The residual CO2 was determined by using volumetric and gaschromatographic methods. These results can be used for enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvents.

  10. Biological functioning of PAH-polluted and thermal desorption-treated soils assessed by fauna and microbial bioindicators.

    Science.gov (United States)

    Cébron, Aurélie; Cortet, Jérôme; Criquet, Stéven; Biaz, Asmaa; Calvert, Virgile; Caupert, Cécile; Pernin, Céline; Leyval, Corinne

    2011-11-01

    A large number of soil bioindicators were used to assess biological diversity and activity in soil polluted with polycyclic aromatic hydrocarbons (PAHs) and the same soil after thermal desorption (TD) treatment. Abundance and biodiversity of bacteria, fungi, protozoa, nematodes and microarthropods, as well as functional parameters such as enzymatic activities and soil respiration, were assessed during a two year period of in situ monitoring. We investigated the influence of vegetation (spontaneous vegetation and Medicago sativa) and TD treatment on biological functioning. Multivariate analysis was performed to analyze the whole data set. A principal response curve (PRC) technique was used to evaluate the different treatments (various vegetation and contaminated vs. TD soil) contrasted with control (bare) soil over time. Our results indicated the value of using a number of complementary bioindicators, describing both diversity and functions, to assess the influence of vegetation on soil and discriminate polluted from thermal desorption (TD)-treated soil. Plants had an influence on the abundance and activity of all organisms examined in our study, favoring the whole trophic chain development. However, although TD-treated soil had a high abundance and diversity of microorganisms and fauna, enzymatic activities were weak because of the strong physical and chemical modifications of this soil. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

  11. Application of Thermal Desorption Unit (TDU) to treat low-toxicity mineral oil base cuttings in Barinas District, Venezuela

    Energy Technology Data Exchange (ETDEWEB)

    Rendon, Ruben [Petroleos de Venezuela, Caracas (Venezuela); Luzardo, Janeth; Alcoba, Alcides [M-I SWACO, Houston, TX (United States)

    2008-07-01

    The potential environmental impact of oil-based drill cuttings is generating increased scrutiny in the oil and gas industry. If left untreated, oil-based cuttings not only increase the risk of environmental liabilities, but also affect revenue, as drilling generates wastes that in most cases require special treatment before disposal. Consequently, the oil industry is looking for technologies to help minimize environmental liabilities. Accordingly, the Barinas District of PDVSA has started a pilot trial to treat oil-based drilling cuttings by applying thermal desorption technology. The main objective of this technology is recovering trapped hydrocarbons, while minimizing wastes and preparing solids to be disposed of through a mobile treatment plant. This novel technology has been used worldwide to treat organic pollutants in soil. Thermal desorption is a technology based on the application of heat in soils polluted with organic compounds. With this technology, target temperatures vary according to the type and concentration of detected pollutants along with its characterization, in such a way that compounds are disposed of by volatilization. As part of the integral waste management development along with the pilot trial for hydrocarbon-contaminated solid waste treatment, trials on soils were undertaken by applying process-generated ashes in equally-sized bins, with different mixtures (ashes, ashes organic material, ashes-organic material-sand, ashes-land). The resulting process offers an immediate soil remediation and final disposal solution for toxic and dangerous waste. (author)

  12. Cloud point extraction and gas chromatography with direct microvial insert thermal desorption for the determination of haloanisoles in alcoholic beverages.

    Science.gov (United States)

    Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

    2016-11-01

    A sensitive analytical procedure for the determination of four haloanisoles (2,4,6 trichloroanisole, 2,4,6-tribromoanisole, 2,3,4,6-tetrachloroanisole and pentachloroanisole) related with cork taint defects in wines, in different types of alcoholic beverages has been developed. The analytes were extracted from the matrix samples by cloud point extraction (CPE) using Triton X-114 heated to 75°C, and the surfactant rich phase was separated by centrifugation. By means of direct microvial insert thermal desorption, 20µL of the CPE obtained extract was submitted to gas chromatography-mass spectrometry (GC-MS) analysis. The parameters affecting the CPE and microvial insert thermal desorption were optimized. Quantification was carried by matrix-matched calibration using an internal standard. Detection limits ranged between 12.9 and 20.8ngL(-1), depending on the compound, for beer and wine samples, whereas for whiskies values in the 46.3-48ngL(-1) range were obtained, since these samples were diluted for analysis. Recoveries for alcoholic beverages were in the 89-111% range, depending on the analyte and the sample.

  13. Ion-to-Neutral Ratios and Thermal Proton Transfer in Matrix-Assisted Laser Desorption/Ionization.

    Science.gov (United States)

    Lu, I-Chung; Chu, Kuan Yu; Lin, Chih-Yuan; Wu, Shang-Yun; Dyakov, Yuri A; Chen, Jien-Lian; Gray-Weale, Angus; Lee, Yuan-Tseh; Ni, Chi-Kung

    2015-07-01

    The ion-to-neutral ratios of four commonly used solid matrices, α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), sinapinic acid (SA), and ferulic acid (FA) in matrix-assisted laser desorption/ionization (MALDI) at 355 nm are reported. Ions are measured using a time-of-flight mass spectrometer combined with a time-sliced ion imaging detector. Neutrals are measured using a rotatable quadrupole mass spectrometer. The ion-to-neutral ratios of CHCA are three orders of magnitude larger than those of the other matrices at the same laser fluence. The ion-to-neutral ratios predicted using the thermal proton transfer model are similar to the experimental measurements, indicating that thermal proton transfer reactions play a major role in generating ions in ultraviolet-MALDI.

  14. Thermal desorption of deuterium from Be, and Be with helium bubbles

    Energy Technology Data Exchange (ETDEWEB)

    Fedorov, A.V.; Van Veen, A.; Busker, G.J. [Delft Univ. of Technology (Netherlands). Interfaculty Reactor Inst.

    1998-01-01

    Deuterium desorption measurements carried out on a single-crystalline beryllium sample are presented. Deuterium ions were implanted at room temperature at the energy of 0.7 and 1.2 keV up to doses ranging from 10{sup 19} to 3.6 x 10{sup 21} m{sup -2}. In order to eliminate the influence of the beryllium-oxide surface layer, before the implantation the surface of the sample was cleaned by argon sputtering. After the implantation the sample was annealed up to 1200 K at a constant rate of 10 K/s. Deuterium released from the sample was monitored by a calibrated quadrupole mass-spectrometer. The desorption spectra revealed two different contributions. One is a well defined and very narrow peak centered around 450 K. This peak is observed only at high implantation doses > 7.8 x 10{sup 20} m{sup -2}, which is close to the deuterium saturation limit of 0.3 D/Be and is related to deuterium release from blisters or interconnected bubbles. The activation energy of 1.1 eV and the threshold implantation dose are consistent with the values reported in literature. The second contribution in the release spectra is found in the temperature range from 600 to 900 K and is present throughout the whole range of the implantation doses. The activation energies corresponding to this release lie in the range between 1.8 and 2.5 eV and are ascribed to the release from deuterium-vacancy type of defects. In a number of experiments the deuterium implantation was preceded by helium implantation followed by partial annealing to create helium bubbles. The resulting deuterium desorption spectra indicate that deuterium detrapping from helium bubbles is characterized by an activation energy of 2.7 eV. (author)

  15. Direct Detection of Pharmaceuticals and Personal Care Products from Aqueous Samples with Thermally-Assisted Desorption Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Campbell, Ian S.; Ton, Alain T.; Mulligan, Christopher C.

    2011-07-01

    An ambient mass spectrometric method based on desorption electrospray ionization (DESI) has been developed to allow rapid, direct analysis of contaminated water samples, and the technique was evaluated through analysis of a wide array of pharmaceutical and personal care product (PPCP) contaminants. Incorporating direct infusion of aqueous sample and thermal assistance into the source design has allowed low ppt detection limits for the target analytes in drinking water matrices. With this methodology, mass spectral information can be collected in less than 1 min, consuming ~100 μL of total sample. Quantitative ability was also demonstrated without the use of an internal standard, yielding decent linearity and reproducibility. Initial results suggest that this source configuration is resistant to carryover effects and robust towards multi-component samples. The rapid, continuous analysis afforded by this method offers advantages in terms of sample analysis time and throughput over traditional hyphenated mass spectrometric techniques.

  16. Thermal desorption study of catalytic systems. Communication 20. Adsorption of water vapors on the calcium aluminate components of catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Nissenbaum, V.D.; Danyushevskii, V.Y.; Golosman, E.Z.; Rubinstein, A.M.; Yakerson, V.I.

    1985-05-01

    Ca aluminates are used as a component of catalysts of gas-phase processes, some of which take place with the participation of water. Nickel calcium aluminate catalysts are thus used for hydrogenation of CO and CO/sub 2/ to CH/sub 4/ and water; zinc calcium aluminate catalysts are used for sulfur purification of process gases, where water is liberated during sulfiding of ZnO; and copper zinc calcium aluminate catalysts are used in low-temperature conversion of CO with water vapor. It is also known that Ca aluminates undergo various transformations in aqueous media with the formation of Ca hydroaluminates. This paper discusses the adsorption of water from the gas phase on calcium aluminate systems, which was investigated by the thermal desorption method. Samples of varying phase composition, different CaO/Al/sub 2/O/sub 3/ ratios, and specific surface areas were also studied and are reported on here.

  17. Analysis of roasted and unroasted Pistacia terebinthus volatiles using direct thermal desorption-GCxGC-TOF/MS.

    Science.gov (United States)

    Gogus, F; Ozel, M Z; Kocak, D; Hamilton, J F; Lewis, A C

    2011-12-01

    The objective of this study was to determine the effects of roasting time on volatile components of Pistacia terebinthus L., a fruit growing wild in Turkey. The whole fruit samples were pan roasted for 0, 5, 10, 15, 20 and 25min at 200°C. Volatile compounds were isolated and identified using the direct thermal desorption (DTD) method coupled with comprehensive gas chromatography - time of flight mass spectrometry (GCxGC-TOF/MS). The major components of the fresh hull of P. terebinthus were α-pinene (10.37%), limonene (8.93%), β-pinene (5.53%), 2-carene (4.47%) and γ-muurolene (4.29%). Eighty-three constituents were characterised from the volatiles of fresh whole P. terebinthus fruits obtained by direct thermal desorption with α-pinene (9.62%), limonene (5.54%), γ-cadinane (5.48%), β-pinene (5.46%), β-caryophyllene (5.24%) being the major constituents. The type and the number of constituents characterised were observed to change with differing roasting times. Limonene (5.56%), α-pinene (4.84%), 5-methylfurfural (4.78%), 5-hydroxymethylfurfural (5-HMF, 3.89%), dimethylmetoxyfuranone (3.67%) and 3-methyl-2(5H)furanone (3.12%) were identified as the major components among the 104 compounds characterised in the volatiles of P. terebinthus, roasted for 25min. In addition, volatiles of fully roasted P. terebinthus fruits contained furans and furanones (15.42%), pyridines (4.45%) and benzene derivatives (3.81%) as the major groups.

  18. Solid-phase extraction-thermal desorption-gas chromatography with mass selective detection for the determination of drugs in urine

    NARCIS (Netherlands)

    van Hout, MWJ; de Zeeuw, RA; Franke, JP; de Jong, GJ

    2003-01-01

    Solid-phase extraction (SPE) was combined with thermal desorption (TD) and gas chromatographic (GC) analysis to determine drugs in urine. The extraction was performed inside a fritted GC liner using about 5 mg TENAX that was inserted into the liner on top of the frit. After extraction, the liner was

  19. Characterization of olive oil volatiles by multi-step direct thermal desorption-comprehensive gas chromatography-time-of-flight mass spectrometry using a programmed temperature vaporizing injector

    NARCIS (Netherlands)

    de Koning, S.; Kaal, E.; Janssen, H.-G.; van Platerink, C.; Brinkman, U.A.Th.

    2008-01-01

    The feasibility of a versatile system for multi-step direct thermal desorption (DTD) coupled to comprehensive gas chromatography (GC × GC) with time-of-flight mass spectrometric (TOF-MS) detection is studied. As an application the system is used for the characterization of fresh versus aged olive oi

  20. Determination of off-flavor compounds, 2-methylisoborneol and geosmin, in salmon fillets using stir bar sorptive extraction–thermal desorption coupled with gas chromatography–mass spectrometry

    Science.gov (United States)

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

  1. 24-HOUR DIFFUSIVE SAMPLING OF 1,3-BUTADIENE IN AIR ONTO CARBOPACK X SOLID ADSORBENT FOLLOWED BY THERMAL DESORPTION/GC/MS ANALYSIS - FEASIBILITY STUDY

    Science.gov (United States)

    Diffusive sampling of 1,3-butadiene for 24 hr onto the graphitic adsorbent Carbopack X packed in a stainless steel tube badge (6.3 mm o.d., 5 mm i.d., and 90 mm in length) with analysis by thermal desorption/gas chromatography (GC)/mass spectrometry (MS) has been evaluated in con...

  2. Thermal Desorption/Ultraviolet Photolysis Process Technology Research, Test, and Evaluation Performed at the Naval Construction Battalion Center, Gulfport, Mississippi, for the USAF Installation Restoration Program. Volume 2

    Science.gov (United States)

    1987-12-01

    packed in ice. Sampling of vent gas and off- gases from the two thermal desorption technologies will be performie using procedures and techniques...solvent used in it. wash with hot voat Cenaslunug detergent.. inse with copioua aMunts of tap water and severa2 portioc of distilled voter. Drain d4y

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

    Science.gov (United States)

    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.

  4. Thermal desorption counter-flow introduction atmospheric pressure chemical ionization for direct mass spectrometry of ecstasy tablets.

    Science.gov (United States)

    Inoue, Hiroyuki; Hashimoto, Hiroaki; Watanabe, Susumu; Iwata, Yuko T; Kanamori, Tatsuyuki; Miyaguchi, Hajime; Tsujikawa, Kenji; Kuwayama, Kenji; Tachi, Noriyuki; Uetake, Naohito

    2009-09-01

    A novel approach to the analysis of ecstasy tablets by direct mass spectrometry coupled with thermal desorption (TD) and counter-flow introduction atmospheric pressure chemical ionization (CFI-APCI) is described. Analytes were thermally desorbed with a metal block heater and introduced to a CFI-APCI source with ambient air by a diaphragm pump. Water in the air was sufficient to act as the reactive reagent responsible for the generation of ions in the positive corona discharge. TD-CFI-APCI required neither a nebulizing gas nor solvent flow and the accompanying laborious optimizations. Ions generated were sent in the direction opposite to the air flow by an electric field and introduced into an ion trap mass spectrometer. The major ions corresponding to the protonated molecules ([M + H](+)) were observed with several fragment ions in full scan mass spectrometry (MS) mode. Collision-induced dissociation of protonated molecules gave characteristic product-ion mass spectra and provided identification of the analytes within 5 s. The method required neither sample pretreatment nor a chromatographic separation step. The effectiveness of the combination of TD and CFI-APCI was demonstrated by application to the direct mass spectrometric analysis of ecstasy tablets and legal pharmaceutical products.

  5. Demonstration Testing of a Thermal Desorption Unit to Receive and Treat Waste with Unlimited Concentration of PCBs - 13437

    Energy Technology Data Exchange (ETDEWEB)

    Orton, Timothy L. [EnergySolutions, 423 West 300 South, Salt Lake City, UT 84101 (United States); Palmer, Carl R. [TD.X Associates LP, 148 South Dowlen Road, PMB 700, Beaumont, TX 77707 (United States)

    2013-07-01

    For the last nine years, EnergySolutions and TD*X Associates LP have teamed up to provide the most comprehensive organic removal treatment process in the radioactive waste industry. The high performance thermal desorption unit (HP-TDU) located at the EnergySolutions Clive facility in Utah has successfully processed over 1,850 tons of organically contaminated radioactive mixed waste. Products from the HP-TDU system include a radioactively contaminated dry solid material that can be disposed in the on-site landfill and an organic condensate with high thermal energy content that is generally below background radiation and capable of free-release to a non-radioactive incinerator. Over the years, Permits and approvals have been obtained through the state of Utah, United States Environmental Protection Agency (USEPA) Region 8, and USEPA headquarters that enable the treatment of several waste categories including volatile and semi-volatile organic compounds, combustion-coded (CMBST) compounds, volatile metals, and polychlorinated biphenyls (PCBs). The unit has recently successfully completed Demonstration Testing for PCB concentrations up to 660,000 ppm (parts per million). Solid processed material from this Demonstration Testing was less than two ppm PCBs in three separate treatment runs; reprocessing or additional treatment was not needed to meet this limit. Through post-demonstration permitting, the system is unlimited in scope as approval has been given to receive and solidify up to pure PCBs down to this processing limit concentration to complete treatment of mixed waste. (authors)

  6. Application of hybrid coagulation microfiltration with air backflushing to direct sewage concentration for organic matter recovery.

    Science.gov (United States)

    Jin, Zhengyu; Gong, Hui; Wang, Kaijun

    2015-01-01

    The idea of sewage concentration is gradually being accepted as a promising and sustainable way of wastewater resource recovery. In this study, Hybrid coagulation microfiltration (HCM) with air backflushing (AB) was investigated to effectively concentrate organic matter. Compared to direct sewage microfiltration, the addition of coagulation process improved the filtration performance with less fouling trends and better concentration efficiency. The use of AB exhibited even better performance within the same 7-h preliminary concentration period by reducing to one tenth of the resistance and collecting around four times as much organic matter into the product concentrate as in direct sewage microfiltration. During 93-h lab-scale continuous concentration by HCM with AB, a product concentrate with the COD concentration over 15,000 mg/L was achieved and around 70% of total influent organic matter could be recovered. Compared to Direct Membrane Filtration (DMF) with Chemically Enhanced Backwash (CEB), HCM with AB achieved better concentration efficiency with higher concentration extent and concentration velocity along with less organic matter mineralization and the more concentrated product despite with lower organic matter retention. HCM with AB could be a promising effective sewage organic matter concentration for resource recovery under optimization.

  7. Determination of trace organic impurities in water using thermal desorption from XAD resin

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, J.P.; Fritz, J.S.

    1978-10-01

    A small water sample (20 to 250 ml) is passed through a small tube containing XAD-4 resin; this effectively retains the organic impurities present in the water. This tube is connected to the permanent apparatus and the sorbed organics are thermally transferred to a small Tenex pre-column while the water vapor is vented. The pre-column is closed off, preheated to 275 to 280/sup 0/C, and then a valve is opened to plug-inject the vaporized sample into a gas chromatograph. The procedure works well for a variety of model organic compounds added to water and can be used for the analysis of actual water samples.

  8. Total microcystins analysis in water using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

    Science.gov (United States)

    Roy-Lachapelle, Audrey; Fayad, Paul B; Sinotte, Marc; Deblois, Christian; Sauvé, Sébastien

    2014-04-11

    A new approach for the analysis of the cyanobacterial microcystins (MCs) in environmental water matrices has been developed. It offers a cost efficient alternative method for the fast quantification of total MCs using mass spectrometry. This approach permits the quantification of total MCs concentrations without requiring any derivatization or the use of a suite of MCs standards. The oxidation product 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) was formed through a Lemieux oxidation and represented the total concentration of free and bound MCs in water samples. MMPB was analyzed using laser diode thermal desorption-atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). LDTD is a robust and reliable sample introduction method with ultra-fast analysis time (0.999). Limits of detection and quantification were 0.2 and 0.9 μg L(-1), respectively. These values are comparable with the WHO (World Health Organization) guideline of 1 μg L(-1) for total microcystin-LR congener in drinking water. Accuracy and interday/intraday variation coefficients were below 15%. Matrix effect was determined with a recovery of 91%, showing no significant signal suppression. This work demonstrates the use of the LDTD-APCI-MS/MS interface for the screening, detection and quantification of total MCs in complex environmental matrices.

  9. An Optimized Adsorbent Sampling Combined to Thermal Desorption GC-MS Method for Trimethylsilanol in Industrial Environments

    Directory of Open Access Journals (Sweden)

    Jae Hwan Lee

    2012-01-01

    Full Text Available Trimethylsilanol (TMSOH can cause damage to surfaces of scanner lenses in the semiconductor industry, and there is a critical need to measure and control airborne TMSOH concentrations. This study develops a thermal desorption (TD-gas chromatography (GC-mass spectrometry (MS method for measuring trace-level TMSOH in occupational indoor air. Laboratory method optimization obtained best performance when using dual-bed tube configuration (100 mg of Tenax TA followed by 100 mg of Carboxen 569, n-decane as a solvent, and a TD temperature of 300°C. The optimized method demonstrated high recovery (87%, satisfactory precision (<15% for spiked amounts exceeding 1 ng, good linearity (R2=0.9999, a wide dynamic mass range (up to 500 ng, low method detection limit (2.8 ng m−3 for a 20-L sample, and negligible losses for 3-4-day storage. The field study showed performance comparable to that in laboratory and yielded first measurements of TMSOH, ranging from 1.02 to 27.30 μg/m3, in the semiconductor industry. We suggested future development of real-time monitoring techniques for TMSOH and other siloxanes for better maintenance and control of scanner lens in semiconductor wafer manufacturing.

  10. MERCURY QUANTIFICATION IN SOILS USING THERMAL DESORPTION AND ATOMIC ABSORPTION SPECTROMETRY: PROPOSAL FOR AN ALTERNATIVE METHOD OF ANALYSIS

    Directory of Open Access Journals (Sweden)

    Liliane Catone Soares

    2015-08-01

    Full Text Available Despite the considerable environmental importance of mercury (Hg, given its high toxicity and ability to contaminate large areas via atmospheric deposition, little is known about its activity in soils, especially tropical soils, in comparison with other heavy metals. This lack of information about Hg arises because analytical methods for determination of Hg are more laborious and expensive compared to methods for other heavy metals. The situation is even more precarious regarding speciation of Hg in soils since sequential extraction methods are also inefficient for this metal. The aim of this paper is to present a technique of thermal desorption associated with atomic absorption spectrometry, TDAAS, as an efficient tool for quantitative determination of Hg in soils. The method consists of the release of Hg by heating, followed by its quantification by atomic absorption spectrometry. It was developed by constructing calibration curves in different soil samples based on increasing volumes of standard Hg2+ solutions. Performance, accuracy, precision, and quantification and detection limit parameters were evaluated. No matrix interference was detected. Certified reference samples and comparison with a Direct Mercury Analyzer, DMA (another highly recognized technique, were used in validation of the method, which proved to be accurate and precise.

  11. Coupling Laser Diode Thermal Desorption with Acoustic Sample Deposition to Improve Throughput of Mass Spectrometry-Based Screening.

    Science.gov (United States)

    Haarhoff, Zuzana; Wagner, Andrew; Picard, Pierre; Drexler, Dieter M; Zvyaga, Tatyana; Shou, Wilson

    2016-02-01

    The move toward label-free screening in drug discovery has increased the demand for mass spectrometry (MS)-based analysis. Here we investigated the approach of coupling acoustic sample deposition (ASD) with laser diode thermal desorption (LDTD)-tandem mass spectrometry (MS/MS). We assessed its use in a cytochrome P450 (CYP) inhibition assay, where a decrease in metabolite formation signifies CYP inhibition. Metabolite levels for 3 CYP isoforms were measured as CYP3A4-1'-OH-midazolam, CYP2D6-dextrorphan, and CYP2C9-4'-OH-diclofenac. After incubation, samples (100 nL) were acoustically deposited onto a stainless steel 384-LazWell plate, then desorbed by an infrared laser directly from the plate surface into the gas phase, ionized by atmospheric pressure chemical ionization (APCI), and analyzed by MS/MS. Using this method, we achieved a sample analysis speed of 2.14 s/well, with bioanalytical performance comparable to the current online solid-phase extraction (SPE)-based MS method. An even faster readout speed was achieved when postreaction sample multiplexing was applied, where three reaction samples, one for each CYP, were transferred into the same well of the LazWell plate. In summary, LDTD coupled with acoustic sample deposition and multiplexing significantly decreased analysis time to 0.7 s/sample, making this MS-based approach feasible to support high-throughput screening (HTS) assays.

  12. Thermal desorption solid-phase microextraction inlet for differential mobility spectrometry.

    Science.gov (United States)

    Rainsberg, Matthew R; de Harrington, Peter B

    2005-06-01

    A splitless thermal desorber unit that interfaces a differential mobility spectrometry (DMS) sensor has been devised. This device was characterized by the detection of benzene, toluene, and xylene (BTX) in water. The detection of BTX in water is important for environmental monitoring, and ion mobility measurements are traditionally difficult for hydrocarbons in water because water competes for charge and quenches the hydrocarbon signals. This paper reports the use of a DMS with a photoionization source that is directly coupled to a solid-phase microextraction (SPME) desorber. The separation and detection capabilities of the DMS were demonstrated using BTX components. Detection limits for benzene, toluene, and m-xylene were 75, 50, and 5 microg mL(-1), respectively.

  13. Thermal desorption gas chromatography and positron annihilation spectroscopy, contribution to alpha decay studies in actinide-doped matrices

    Energy Technology Data Exchange (ETDEWEB)

    Roudil, D.; Jegou, C.; Vella, F.; Folch, B.; Broudic, V. [Commissariat a l' energie Atomique, Rhone Valley Research Center, 30200 Bagnols-sur-Ceze (France); Pik, R. [CNRS-CRPG, 54506 Vandoeuvre-les-Nancy (France); Barthe, M. F. [CNRS-CEMHTI, 45071 Orleans (France); Cuney, M. [Universite de Nancy, CNRS, CREGU, 54506 Vandoeuvre-les-Nancy (France); Pipon, Y. [IPNL CNRS, IN2P3 UMR 5822, 69622 Villeurbanne (France)

    2009-07-01

    A thermal desorption system coupled with a gas analyzer has been adapted and nuclearized to investigate He behavior in actinide-doped samples used to simulate alpha decay aging. This technique widely used in standard laboratories allows measurements of the helium balance and reduced diffusion coefficients, and a preliminary evaluation of helium locations (related to defects and thermal annealing). In our system implemented in a hot cell, small samples are annealed at up to 1100 C degrees in controlled atmosphere. They are inserted in a 10 to 20 cm{sup 3} vessel connected to a micro gas chromatography detector. Initial system calibration allowed concentration measurements within about 10%. Comparisons with the CNRS/CRPG rare gas analysis laboratory at Nancy (France) were applied on natural uranium oxides originating from Oklo (Gabon) and Mistamisk (Canada). The latest results obtained on Mistamisk samples are in good agreement, with a maximum relative deviation of 14%. The data were used to determine the activation energy of about 1 eV.at{sup -1}. On (U,Pu)O{sub 2} and PuO{sub 2} samples the experiments highlight the impact of defects (up to 100 dpa) on He mobility. The defect population must now be characterized to improve our knowledge of He/defect interactions and mechanisms. In addition and synergy to the macroscopic release measurements by gas chromatography, positron annihilation spectroscopy, an effective nondestructive technique for vacancy defect investigation, was also developed and nuclearized in our hot cell laboratory as part of a project supported by the NOMADE and MATINEX research groups. Specific protocols for doped sample analysis were also developed and validated with UO{sub 2} and (U,Pu)O{sub 2} samples. (authors)

  14. Determination of metformin in mouse, rat, dog and human plasma samples by laser diode thermal desorption/atmospheric pressure chemical ionization tandem mass spectrometry.

    Science.gov (United States)

    Swales, John G; Gallagher, Richard; Peter, Raimund M

    2010-11-02

    A simple, rapid and robust high-throughput assay for the quantitative analysis of metformin in plasma from different species using laser diode thermal desorption interfaced with atmospheric chemical pressure ionization tandem mass spectrometry (LDTD-APCI-MSMS) was developed for use in a pharmaceutical discovery environment. In order to minimize sample preparation a generic protein precipitation method was used to extract metformin from the plasma. Laser diode thermal desorption is a relatively new sample introduction method, the optimization of the instrumental parameters are presented. The method was successfully applied to spiked mouse, rat, dog and human plasma samples and was subsequently used to determine the oral pharmacokinetics of metformin after dosing to male rats in order to support drug discovery projects. The deviations for intra-assay accuracy and precision across the four species were less than 30% at all calibration and quality control levels.

  15. Comparison of two common adsorption materials for thermal desorption gas chromatography - mass spectrometry of biogenic volatile organic compounds.

    Science.gov (United States)

    Marcillo, Andrea; Jakimovska, Viktorija; Widdig, Anja; Birkemeyer, Claudia

    2017-09-08

    Volatile organic compounds (VOCs) are commonly collected from gaseous samples by adsorption to materials such as the porous polymer Tenax TA. Adsorbed compounds are subsequently released from these materials by thermal desorption (TD) and separated then by gas chromatography (GC) with flame ionization (FID) or mass spectrometry (MS) detection. Tenax TA is known to be particularly suitable for non-polar to semipolar volatiles, however, many volatiles from environmental and biological samples possess a rather polar character. Therefore, we tested if the polymer XAD-2, which so far is widely used to adsorb organic compounds from aqueous and organic solvents, could provide a broader coverage for (semi)polar VOCs during gas-phase sampling. Mixtures of volatile compounds covering a wide range of volatility (bp. 20-256°C) and different chemical classes were introduced by liquid spiking into sorbent tubes with one of the two porous polymers, Tenax TA or XAD-2, and analyzed by TD/GC-MS. At first, an internal standard mixture composed of 17 authentic standards was used to optimize desorption temperature with respect to sorbent degradation and loading time for calibration. Secondly, we tested the detectability of a complex standard mixture composed of 57 volatiles, most of them common constituents of the body odor of mammals. Moreover, the performance of XAD-2 compared with Tenax TA was assessed as limit of quantitation and linearity for the internal standard mixture and 33 compounds from the complex standard mixture. Volatiles were analyzed in a range between 0.01-∼250ng/tube depending on the compound and material. Lower limits of quantitation were between 0.01 and 3 ng±0.9). Interestingly, we found different kinetics for compound adsorption with XAD-2, and a partially better sensitivity in comparison with Tenax TA. For these analytes, XAD-2 might be recommended as an alternative of Tenax TA for TD/GC-MS analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Effect of an automated dipping and backflushing system on somatic cell counts.

    Science.gov (United States)

    Olde Riekerink, R G M; Ohnstad, I; van Santen, B; Barkema, H W

    2012-09-01

    Postmilking teat disinfection is an effective management practice to prevent transmission of contagious mastitis pathogens from cow to cow. With farms increasing in size and an increase in the number of rotary milking parlors, the need for automation of postmilking teat disinfection is mounting. Automated teat dipping and backflushing (ADB) systems have existed for some years, but their effect on udder health was never examined in a field study on commercial dairy farms. The objectives of this study were, therefore, to evaluate the effect of introducing an ADB system in a herd on (1) bulk milk somatic cell count (SCC), (2) individual cow SCC, and (3) the proportion of newly elevated SCC. Dairy herd improvement data were collected over a 30-mo period on 25 sets of 3 farms. Each set of 3 farms contained a farm that installed an ADB system, one that disinfected teats using dipping after milking, and one that sprayed teats after milking. Data were analyzed using linear mixed models. Bulk milk SCC on farms that sprayed or dipped before installing an ADB system were 16,000 and 30,000 cells/mL lower in the period 6 to 18 mo after installation, respectively, than on farms that continued spraying or dipping the teats after milking. In the same period after installing an ADB system, proportions of cows with elevated SCC were 4.3 and 1.2% lower, respectively, compared with spraying and with dipping. Similarly, proportions of cows that had newly elevated SCC were 1.5% lower and 0.3% higher, respectively, compared with farms that sprayed or dipped. Installing an ADB system had a beneficial effect on bulk milk SCC, individual cow SCC, and the proportion of newly elevated SCC. The effect was most prominent in the period 6 to 18 mo after installation of an ADB system.

  17. Thermal desorption characterisation of molecularly imprinted polymers. Part II: Use of direct probe GC-MS analysis to study crosslinking effects.

    Science.gov (United States)

    Holland, Niamh; Duggan, Patrick; Owens, Eleanor; Cummins, Wayne; Frisby, June; Hughes, Helen; McLoughlin, Peter

    2008-06-01

    A powerful method utilising direct probe thermal desorption GC-MS is presented for the study of molecularly imprinted polymers (MIPs). A series of 2-aminopyridine (2-apy)-imprinted methacrylic acid-ethyleneglycol dimethacrylate (MAA-EGDMA) copolymers were prepared under identical conditions but with varying amounts of EGDMA (crosslinking monomer). The use of appropriate temperature programmes permitted template removal, and the subsequent assessment of polymer affinity and specificity, all of which were found to be dependent on polymer composition and morphology. The system was sufficiently sensitive to identify a specific response of imprinted polymers over nonimprinted counterparts. Correlations were found to exist between thermal desorption analysis and solution phase binding, which was assessed by UV spectroscopy, where specificity was found to diminish with decreasing EGDMA concentration. This was attributed to the increased number of free carboxyl groups in those polymers containing a lower percentage of EGDMA. Thermal desorption profiles obtained for the analyte were found to be unaffected by the physical and chemical properties of the solvent used for analyte reloading.

  18. Ultra high vacuum high precision low background setup with temperature control for thermal desorption mass spectroscopy (TDA-MS) of hydrogen in metals.

    Science.gov (United States)

    Merzlikin, Sergiy V; Borodin, S; Vogel, D; Rohwerder, M

    2015-05-01

    In this work, a newly developed UHV-based high precision low background setup for hydrogen thermal desorption analysis (TDA) of metallic samples is presented. Using an infrared heating with a low thermal capacity enables a precise control of the temperature and rapid cool down of the measurement chamber. This novel TDA-set up is superior in sensitivity to almost every standard hydrogen analyzer available commercially due to the special design of the measurement chamber, resulting in a very low hydrogen background. No effects of background drift characteristic as for carrier gas based TDA instruments were observed, ensuring linearity and reproducibility of the analysis. This setup will prove to be valuable for detailed investigations of hydrogen trapping sites in steels and other alloys. With a determined limit of detection of 5.9×10(-3)µg g(-1) hydrogen the developed instrument is able to determine extremely low hydrogen amounts even at very low hydrogen desorption rates. This work clearly demonstrates the great potential of ultra-high vacuum thermal desorption mass spectroscopy instrumentation.

  19. Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ovchinnikova, Olga S [ORNL; Nikiforov, Maxim [ORNL; Bradshaw, James A [ORNL; Jesse, Stephen [ORNL; Van Berkel, Gary J [ORNL

    2011-01-01

    Nanometer scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nano-thermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 x 2 array of spots, with 2 m spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (~2x106 nm3), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in automated fashion sub-micrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.

  20. Diffusive uptake in passive and active adsorbent sampling using thermal desorption tubes.

    Science.gov (United States)

    Batterman, Stuart; Metts, Tricia; Kalliokoski, Pentti

    2002-12-01

    Low flow active sampling techniques collecting vapors and gases using thermally desorbable adsorbents are now feasible and desirable in many applications as they permit long integration times, the potential for miniaturized sampling configurations, and other advantages. At very low air flow rates (estimates of the tortuosity and porosity of the glass wool packing used to retain the adsorbent, parameters needed to estimate diffusive fluxes in passive and active sampling; (4) a demonstration that orifice-equipped low flow active samplers can reduce diffusive uptake and improve precision, and (5) a model predicting the saturated adsorbent layer that helps to account for the gradual decline in uptake rates seen in passive sampling. Diffusive uptake will depend on the tube configuration and diffusion coefficient of the substance of interest, but for conventional sampling tubes (0.4-0.5 cm id, 1.5 cm air gap), sample flow rates should be maintained above 1 to 4 ml min(-1) to keep errors below 5%. Laboratory experiments showed close agreement with theoretical calculations, and the field study using 1 to 4 d sampling periods and 0.3 ml min(-1) flows demonstrated that the orifice-equipped samplers essentially eliminated diffusive uptake. No significant practical difficulties are encountered using orifices, e.g., pressure drop is minimal. Experimental estimates of tortuosity (0.79 +/- 0.02) and porosity (0.92 +/- 0.10) of the glass wool packing (0.3 cm length) represent relatively little resistance to diffusion; however, variation in the packing and adsorbent placement can degrade the precision achievable by passive samplers. Diffusion barriers, consisting most simply of an orifice, may be used to lower the diffusive uptake. A needle-type orifice permits flows below 0.1 ml min(-1) and is suitable for sampling periods as long as several weeks, and it provided greater precision than conventional open-ended sampling tubes (8% compared to 13%). Finally, the gradual decrease in

  1. Adsorption, desorption, and film formation of quinacridone and its thermal cracking product indigo on clean and carbon-covered silicon dioxide surfaces

    Science.gov (United States)

    Scherwitzl, Boris; Lassnig, Roman; Truger, Magdalena; Resel, Roland; Leising, Günther; Winkler, Adolf

    2016-09-01

    The evaporation of quinacridone from a stainless steel Knudsen cell leads to the partial decomposition of this molecule in the cell, due to its comparably high sublimation temperature. At least one additional type of molecules, namely indigo, could be detected in the effusion flux. Thermal desorption spectroscopy and atomic force microscopy have been used to study the co-deposition of these molecules on sputter-cleaned and carbon-covered silicon dioxide surfaces. Desorption of indigo appears at temperatures of about 400 K, while quinacridone desorbs at around 510 K. For quinacridone, a desorption energy of 2.1 eV and a frequency factor for desorption of 1 × 1019 s-1 were calculated, which in this magnitude is typical for large organic molecules. A fraction of the adsorbed quinacridone molecules (˜5%) decomposes during heating, nearly independent of the adsorbed amount, resulting in a surface composed of small carbon islands. The sticking coefficients of indigo and quinacridone were found to be close to unity on a carbon covered SiO2 surface but significantly smaller on a sputter-cleaned substrate. The reason for the latter can be attributed to insufficient energy dissipation for unfavorably oriented impinging molecules. However, due to adsorption via a hot-precursor state, the sticking probability is increased on the surface covered with carbon islands, which act as accommodation centers.

  2. Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis.

    Science.gov (United States)

    Hoffmann, William D; Kertesz, Vilmos; Srijanto, Bernadeta R; Van Berkel, Gary J

    2017-02-20

    The use of atomic force microscopy controlled nanothermal analysis probes for reproducible spatially resolved thermally assisted sampling of micrometer-sized areas (ca. 11 × 17 μm wide × 2.4 μm deep) from relatively low number-average molecular weight (Mn mass spectrometric analysis. The procedure and mechanism for material pickup, the sampling reproducibility and sampling size are discussed, and the oligomer distribution information available from slow temperature ramps versus ballistic temperature jumps is presented. For the Mn = 970 P2VP, the Mn and polydispersity index determined from the mass spectrometric data were in line with both the label values from the sample supplier and the value calculated from the simple infusion of a solution of polymer into the commercial atmospheric pressure chemical ionization source on this mass spectrometer. With a P2VP sample of higher Mn (Mn = 2070 and 2970), intact oligomers were still observed (as high as m/z 2793 corresponding to the 26-mer), but a significant abundance of thermolysis products were also observed. In addition, the capability for confident identification of the individual oligomers by slowly ramping the probe temperature and collecting data-dependent tandem mass spectra was also demonstrated. The material type limits to the current sampling and analysis approach as well as possible improvements in nanothermal analysis probe design to enable smaller area sampling and to enable controlled temperature ramps beyond the present upper limit of about 415 °C are also discussed.

  3. Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air.

    Science.gov (United States)

    Sunesson, A L; Sundgren, M; Levin, J O; Eriksson, K; Carlson, R

    1999-02-01

    Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.

  4. Characterization of thermal desorption with the Deans-switch technique in gas chromatographic analysis of volatile organic compounds.

    Science.gov (United States)

    Ou-Yang, Chang-Feng; Huang, Ying-Xue; Huang, Ting-Jyun; Chen, Yong-Shen; Wang, Chieh-Heng; Wang, Jia-Lin

    2016-09-02

    This study presents a novel application based on the Deans-switch cutting technique to characterize the thermal-desorption (TD) properties for gas chromatographic (GC) analysis of ambient volatile organic compounds (VOCs). Flash-heating of the sorbent bed at high temperatures to desorb trapped VOCs to GC may easily produce severe asymmetric or tailing GC peaks affecting resolution and sensitivity if care is not taken to optimize the TD conditions. The TD peak without GC separation was first examined for the quality of the TD peak by analyzing a standard gas mixture from C2 to C12 at ppb level. The Deans switch was later applied in two different stages. First, it was used to cut the trailing tail of the TD peak, which, although significantly improved the GC peak symmetry, led to more loss of the higher boiling compounds than the low boiling ones, thus suggesting compound discrimination. Subsequently, the Deans switch was used to dissect the TD peak into six 30s slices in series, and an uneven distribution in composition between the slices were found. A progressive decrease in low boiling compounds and increase in higher boiling ones across the slices indicated severe inhomogeneity in the TD profile. This finding provided a clear evidence to answer the discrimination problem found with the tail cutting approach to improve peak symmetry. Through the use of the innovated slicing method based on the Deans-switch cutting technique, optimization of TD injection for highly resolved, symmetric and non-discriminated GC peaks can now be more quantitatively assessed and guided.

  5. Hydrogen sulphide in human nasal air quantified using thermal desorption and selected ion flow tube mass spectrometry.

    Science.gov (United States)

    Wondimu, Taddese; Wang, Rui; Ross, Brian

    2014-09-01

    The discovery that hydrogen sulphide (H2S) acts as a gasotransmitter when present at very low concentrations (sub-parts per billion (ppbv)) has resulted in the need to quickly quantify trace amounts of the gas in complex biological samples. Selected ion flow tube mass spectrometry (SIFT-MS) is capable of real-time quantification of H2S but many SIFT-MS instruments lack sufficient sensitivity for this application. In this study we investigate the utility of combining thermal desorption with SIFT-MS for quantifying H2S in the 0.1-1 ppbv concentration range. Human orally or nasally derived breath, and background ambient air, were collected in sampling bags and dried by passing through CaCl2 and H2S pre-concentrated using a sorbent trap optimised for the capture of this gas. The absorbed H2S was then thermally desorbed and quantified by SIFT-MS. H2S concentrations in ambient air, nasal breath and oral breath collected from 10 healthy volunteers were 0.12  ±  0.02 (mean ± SD), 0.40  ±  0.11 and 3.1  ±  2.5 ppbv respectively, and in the oral cavity H2S, quantified by SIFT-MS without pre-concentration, was present at 13.5  ±  8.6 ppbv. The oral cavity H2S correlates well with oral breath H2S but not with nasal breath H2S, suggesting that oral breath H2S derives mainly from the oral cavity but nasal breath is likely pulmonary in origin. The successful quantification of such low concentrations of H2S in nasal air using a rapid analytical procedure paves the way for the straightforward analysis of H2S in breath and may assist in elucidating the role that H2S plays in biological systems.

  6. Measurement of toxic volatile organic compounds in indoor air of semiconductor foundries using multisorbent adsorption/thermal desorption coupled with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Wu, Chien-Hou; Lin, Ming-Nan; Feng, Chien-Tai; Yang, Kuang-Ling; Lo, Yu-Shiu; Lo, Jiunn-Guang

    2003-05-09

    A method for the qualitative and quantitative analysis of volatile organic compounds (VOCs) in the air of class-100 clean rooms at semiconductor fabrication facilities was developed. Air samples from two semiconductor factories were collected each hour on multisorbent tubes (including Carbopack B, Carbopack C, and Carbosieve SIII) with a 24-h automatic active sampling system and analyzed using adsorption/thermal desorption coupled with gas chromatography-mass spectrometry. Experimental parameters, including thermal desorption temperature, desorption time, and cryofocusing temperature, were optimized. The average recoveries and the method detection limits for the target compounds were in the range 94-101% and 0.31-0.89 ppb, respectively, under the conditions of a 1 L sampling volume and 80% relative humidity. VOCs such as acetone, isopropyl alcohol, 2-heptanone, and toluene, which are commonly used in the semiconductor and electronics industries, were detected and accurately quantified with the established method. Temporal variations of the analyte concentrations observed were attributed to the improper use of organic solvents during operation.

  7. Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

    Science.gov (United States)

    Kulik, Tetiana V; Lipkovska, Natalia O; Barvinchenko, Valentyna M; Palyanytsya, Borys B; Kazakova, Olga A; Dudik, Olesia O; Menyhárd, Alfréd; László, Krisztina

    2016-05-15

    Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability.

  8. Threshold character of temperatures on deuterium thermal desorption in Mg-V composite grown atom-by-atom

    Science.gov (United States)

    Neklyudov, I. M.; Morozov, O. M.; Kulish, V. G.; Zhurba, V. I.; Galitskiy, A. G.; Lomino, N. S.; Kuprin, A. S.; Ovcharenko, V. D.; Reshetnyak, E. N.

    2012-08-01

    The plasma evaporation-sputtering method was applied to make composite materials of the Mg-V system. The ion-implanted deuterium desorption temperature variations as a function of the component concentration were studied. It has been established that, by introducing vanadium into magnesium, the deuterium desorption temperature can be appreciably decreased (to 300-330 K) in comparison with the case of deuterium desorption from magnesium (~800 K). A step-like form of the curve of deuterium desorption temperature evidences on the presence of two different structure states of the Mg-V system depending on the ratio of components. The deuterium temperature decrease can be caused by filamentary inclusions formed, in the process of composite making and annealing, by the insoluble component (vanadium) atoms providing the deuterium diffusion from the sample at a lower temperature (channels for deuterium diffusion through the surface barrier). A necessary high diffusion mobility of deuterium is provided by the amorphous state of Mg83+xVx samples. The deuterium desorption data obtained on the example of Mg-V and Mg-Zr composites provide support for further research into hydrogen storage materials containing low-soluble chemical elements in the alloy components.

  9. Thermal desorption GC-MS as a tool to provide PAH certified standard reference material on particulate matter quartz filters.

    Science.gov (United States)

    Grandesso, Emanuela; Pérez Ballesta, Pascual; Kowalewski, Konrad

    2013-02-15

    Reference materials for particulate matter (PM) on filter media are not available for the quantification of polycyclic aromatic hydrocarbons (PAHs) in ambient air. This is due to the difficulty of obtaining reference material that has a homogeneous distribution on a filter surface that is large enough for characterization and distribution. High volume sample filters from different locations and seasons were considered to validate the feasibility of the use of quartz filters as reference material for PAH concentrations. A rapid thermal desorption (TD) technique coupled with gas chromatography/mass spectroscopy was applied to characterise the material for the content of fifteen different PAHs. TD technique allowed for rapid and accurate analysis of small sections of filter (5mm diameter), leaving enough material for the production of twenty sub-filter cuts (42 mm diameter) that could be used for distribution and control. Stability and homogeneity tests required for material certification were performed as indicated by the ISO guide 34:2009 and ISO 35:2006. The contribution of the heterogeneous distribution of PAHs on the filter surface resulted generally lower than 10% and higher for more volatile PAHs. One year of storage at -18°C indicated no significant variation in PAH concentrations. Nevertheless, a methodology for shipping and storing of the filter material at ambient temperature in especially designed plastic envelopes, was also shown to allow for stabile concentrations within twenty days. The method accuracy was confirmed by the analysis of NIST SRM 1649a (urban dust) and PAH concentrations were validated against the reference values obtained from an inter-laboratory exercise. In the case of benzo[a]pyrene for masses quantified between 100 pg and 10 ng the TD method provided expanded uncertainties of circa 10%, while the inter-laboratory reference value uncertainties ranged between 15 and 20%. The evaluation of these results supports the use of the presented

  10. Low-flow active and passive sampling of VOCs using thermal desorption tubes: theory and application at an offset printing facility.

    Science.gov (United States)

    Batterman, Stuart; Metts, Tricia; Kalliokoski, Pentti; Barnett, Emily

    2002-06-01

    While air sampling techniques using adsorbent-based collection, thermal desorption and chromatographic analysis have found a niche in ambient air sampling, occupational applications have been more limited. This paper evaluates the use of thermal desorption techniques for low flow active and passive sampling configurations which allow conveniently long duration sampling in occupational settings and other high concentration environments. The use of an orifice enables flows as low as 0.5 ml min(-1) and sampling periods up to several days without significant biases. A model is used to predict sampling rates of a passive sampler encompassing an orifice, a void space, glass wool, and the adsorbent. Laboratory and field tests conducted at a commercial offset printing facility, which contained a variety of volatile organic compounds (primarily aromatic but also a few chlorinated and terpene compounds at levels from 1 to 67,000 microg m(-3)), are used to evaluate the approach. Tenax GR and Carbosieve SIII, both singly and together, were employed as adsorbents. Side-by-side tests comparing high flow, low flow and passive samplers show excellent agreement and high linearity (r = 0.95) for concentrations spanning nearly five orders of magnitude. Active samplers were tested at flows as low as 0.5 ml min(-1), compared to typical flows up to 40 ml min(-1). Passive samplers demonstrated a linear range and agreement with predictions for adsorbate loadings from approximately 1 ng to nearly 10 microg. Using a chemical mass balance receptor model, concentrations in the facility were apportioned to solvents, inks and other indoor and outdoor sources. Overall, the use of low flow active and passive sampling approaches employing thermal desorption techniques provides good performance and tremendous flexibility that facilitates use in many applications, including workplace settings.

  11. On-line derivatization for hourly measurements of gas- and particle-phase Semi-Volatile oxygenated organic compounds by Thermal desorption Aerosol Gas chromatography (SV-TAG

    Directory of Open Access Journals (Sweden)

    G. Isaacman

    2014-07-01

    Full Text Available Laboratory oxidation studies have identified a large number of oxygenated organic compounds that can be used as tracers to understand sources and oxidation chemistry of atmospheric particulate matter. Quantification of these compounds in ambient environments has traditionally relied on low time-resolution collection of filter samples followed by offline sample treatment with a derivatizing agent to allow analysis by gas chromatography of otherwise non-elutable organic chemicals with hydroxyl groups. We present here an automated in situ instrument for the measurement of highly polar organic semi-volatile and low-volatility compounds in both the gas- and particle-phase with hourly time-resolution. The dual-cell Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SV-TAG with derivatization collects particle-only and combined particle-plus-vapor samples on two parallel sampling cells that are analyzed in series by thermal desorption into helium saturated with derivatizing agent. Introduction of MSTFA, a silylating agent, yields complete derivatization of all tested compounds, including alkanoic acids, polyols, diacids, sugars, and multifunctional compounds. In laboratory tests, derivatization is found to be highly reproducible (< 3% variability. During field deployment, a regularly injected internal standard is used to correct for variability in detector response, derivatization efficiency, desorption efficiency, and transfer efficiency. Error in quantification from instrument fluctuations is found to be less than 10% for hydrocarbons and less than 15% for all oxygenates for which a functionally similar internal standard is available. After internal standard corrections, calibration curves are found to be linear for all compounds over the span of one month with comparable response on both of the parallel sampling cells.

  12. Online derivatization for hourly measurements of gas- and particle-phase semi-volatile oxygenated organic compounds by thermal desorption aerosol gas chromatography (SV-TAG)

    Science.gov (United States)

    Isaacman, G.; Kreisberg, N. M.; Yee, L. D.; Worton, D. R.; Chan, A. W. H.; Moss, J. A.; Hering, S. V.; Goldstein, A. H.

    2014-12-01

    Laboratory oxidation studies have identified a large number of oxygenated organic compounds that can be used as tracers to understand sources and oxidation chemistry of atmospheric particulate matter. Quantification of these compounds in ambient environments has traditionally relied on low-time-resolution collection of filter samples followed by offline sample treatment with a derivatizing agent to allow analysis by gas chromatography of otherwise non-elutable organic chemicals with hydroxyl groups. We present here an automated in situ instrument for the measurement of highly polar organic semi-volatile and low-volatility compounds in both the gas- and particle-phase with hourly quantification of mass concentrations and gas-particle partitioning. The dual-cell semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) with derivatization collects particle-only and combined particle-plus-vapor samples on two parallel sampling cells that are analyzed in series by thermal desorption into helium saturated with derivatizing agent. Introduction of MSTFA (N-methyl-N-(trimethylsilyl)trifluoroacetamide), a silylating agent, yields complete derivatization of all tested compounds, including alkanoic acids, polyols, diacids, sugars, and multifunctional compounds. In laboratory tests, derivatization is found to be highly reproducible (regularly injected internal standard is used to correct for variability in detector response, consumption of the derivatization agent, desorption efficiency, and transfer losses. Error in quantification from instrument fluctuations is found to be less than 10% for hydrocarbons and less than 15% for all oxygenates for which a functionally similar internal standard is available, with an uncertainty of 20-25% in measurements of particle fraction. After internal standard corrections, calibration curves are found to be linear for all compounds over the span of 1 month, with comparable response on both of the parallel sampling cells.

  13. On-line derivatization for hourly measurements of gas- and particle-phase Semi-Volatile oxygenated organic compounds by Thermal desorption Aerosol Gas chromatography (SV-TAG)

    Science.gov (United States)

    Isaacman, G.; Kreisberg, N. M.; Yee, L. D.; Worton, D. R.; Chan, A. W. H.; Moss, J. A.; Hering, S. V.; Goldstein, A. H.

    2014-07-01

    Laboratory oxidation studies have identified a large number of oxygenated organic compounds that can be used as tracers to understand sources and oxidation chemistry of atmospheric particulate matter. Quantification of these compounds in ambient environments has traditionally relied on low time-resolution collection of filter samples followed by offline sample treatment with a derivatizing agent to allow analysis by gas chromatography of otherwise non-elutable organic chemicals with hydroxyl groups. We present here an automated in situ instrument for the measurement of highly polar organic semi-volatile and low-volatility compounds in both the gas- and particle-phase with hourly time-resolution. The dual-cell Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SV-TAG) with derivatization collects particle-only and combined particle-plus-vapor samples on two parallel sampling cells that are analyzed in series by thermal desorption into helium saturated with derivatizing agent. Introduction of MSTFA, a silylating agent, yields complete derivatization of all tested compounds, including alkanoic acids, polyols, diacids, sugars, and multifunctional compounds. In laboratory tests, derivatization is found to be highly reproducible (regularly injected internal standard is used to correct for variability in detector response, derivatization efficiency, desorption efficiency, and transfer efficiency. Error in quantification from instrument fluctuations is found to be less than 10% for hydrocarbons and less than 15% for all oxygenates for which a functionally similar internal standard is available. After internal standard corrections, calibration curves are found to be linear for all compounds over the span of one month with comparable response on both of the parallel sampling cells.

  14. Effect of Ultrasound on Desorption Equilibrium

    Institute of Scientific and Technical Information of China (English)

    秦炜; 原永辉; 戴猷元

    2001-01-01

    Effects of ultrasound on intensification of separation process were investigated through the experiment of desorption equilibrium behavior. Tri-butyl phosphate (TBP) on NKA-X resin and phenol on a solvent impregnated resin, CL-TBP resin, were used for desorption processes. The desorption rate was measured with and without ultrasound. Desorption equilibrium was studied under various ultrasonic power densities or thermal infusion. Results showed that the desorption rate with ultrasound was much higher than that with normal thermal infusion. Both ultrasound and thermal infusion broke the desorption equilibrium existed at room temperature. However, after the systems were cooled down, the amount of solute desorbed in the liquid phase in the presence of ultrasound was much higher than that at the temperature corresponding to the same ultrasound power. It is proved that the initial desorption equilibrium was broken as a result of the spot energy effect of ultrasound.

  15. Detection of gaseous compounds by needle trap sampling and direct thermal-desorption photoionization mass spectrometry: concept and demonstrative application to breath gas analysis.

    Science.gov (United States)

    Kleeblatt, Juliane; Schubert, Jochen K; Zimmermann, Ralf

    2015-02-01

    A fast detection method to analyze gaseous organic compounds in complex gas mixtures was developed, using a needle trap device (NTD) in conjunction with thermal-desorption photoionization time-of-flight mass spectrometry (TD-PI-TOFMS). The mass spectrometer was coupled via a deactivated fused silica capillary to an injector of a gas chromatograph. In the hot injector, the analytes collected on the NTD were thermally desorbed and directly transferred to the PI-TOFMS ion source. The molecules are softly ionized either by single photon ionization (SPI, 118 nm) or by resonance enhanced multiphoton ionization (REMPI, 266 nm), and the molecular ion signals are detected in the TOF mass analyzer. Analyte desorption and the subsequent PI-TOFMS detection step only lasts ten seconds. The specific selectivity of REMPI (i.e., aromatic compounds) and universal ionization characteristics render PI-MS as a promising detection system. As a first demonstrative application, the alveolar phase breath gas of healthy, nonsmoking subjects was sampled on NTDs. While smaller organic compounds such as acetone, acetaldehyde, isoprene, or cysteamine can be detected in the breath gas with SPI, REMPI depicts the aromatic substances phenol and indole at 266 nm. In the breath gas of a healthy, smoking male subject, several xenobiotic substances such as benzene, toluene, styrene, and ethylbenzene can be found as well. Furthermore, the NTD-REMPI-TOFMS setup was tested for breath gas taken from a mechanically ventilated pig under continuous intravenous propofol (2,6-diisopropylphenol, narcotic drug) infusion.

  16. Application of GC-MS with a SPME and thermal desorption technique for determination of dimethylamine and trimethylamine in gaseous samples for medical diagnostic purposes.

    Science.gov (United States)

    Wzorek, Beata; Mochalski, Paweł; Sliwka, Ireneusz; Amann, Anton

    2010-06-01

    Biogenic amines are interesting compounds which may be of use for medical diagnosis or therapeutic monitoring. The present paper deals with the problems that occur with concentration determination of dimethylamine (DMA) and trimethylamine (TMA). These occur in the breath of people suffering from renal disease. The measurement of amines present in trace concentrations requires the application of suitable analytical methods during sampling, storage and preconcentration. This is particularly so due to their polar and basic properties. In this paper, the application of solid phase microextraction (SPME) and thermal desorption (TD) with subsequent measurement by GC-MS for the determination of amines is discussed. For DMA, preconcentration by SPME did not give satisfactory results. TMA may be analysed using SPME preconcentration with an LOD of 1.5 ppb. Thermal desorption with Tenax as the adsorbing material allows reliable concentration determination for TMA (LOD = 0.5 ppb) and DMA (LOD = 4.6 ppb). DMA cannot be stored reliably in Tedlar bags and longer storage on Tenax (with subsequent TD) does not give good repeatability of results. For TMA, storage can be done on Tenax or in bags, the best results for the latter being achieved with Flex Foil bags.

  17. In situ ionic liquid dispersive liquid-liquid microextraction and direct microvial insert thermal desorption for gas chromatographic determination of bisphenol compounds.

    Science.gov (United States)

    Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel

    2016-01-01

    A new procedure based on direct insert microvial thermal desorption injection allows the direct analysis of ionic liquid extracts by gas chromatography and mass spectrometry (GC-MS). For this purpose, an in situ ionic liquid dispersive liquid-liquid microextraction (in situ IL DLLME) has been developed for the quantification of bisphenol A (BPA), bisphenol Z (BPZ) and bisphenol F (BPF). Different parameters affecting the extraction efficiency of the microextraction technique and the thermal desorption step were studied. The optimized procedure, determining the analytes as acetyl derivatives, provided detection limits of 26, 18 and 19 ng L(-1) for BPA, BPZ and BPF, respectively. The release of the three analytes from plastic containers was monitored using this newly developed analytical method. Analysis of the migration test solutions for 15 different plastic containers in daily use identified the presence of the analytes at concentrations ranging between 0.07 and 37 μg L(-1) in six of the samples studied, BPA being the most commonly found and at higher concentrations than the other analytes.

  18. Critical role of a pre-purge setup in the thermal desorption analysis of volatile organic compounds by gas chromatography with mass spectrometry.

    Science.gov (United States)

    Kim, Yong-Hyun; Kim, Ki-Hyun

    2015-07-01

    In general, volatile organic compounds in ambient air are quantified by following a well-defined standard calibration procedure using a gas-/liquid-phase standard. If the liquid standard is analyzed by a thermal desorption, the solvent effect is unavoidable through the alteration of breakthrough properties or retention times. To learn more about the variables of the thermal desorption-based analysis, the effect of pre-purge conditions was evaluated for 18 volatile organic compounds with different types of sorbent tube materials by fixing standard volume (1 μL) and flow rate (100 mL/min). The gas phase calibration was also carried out as reference for the non-solvent effect. A single tube filled with Tenax TA exhibited the least solvent effect with the short pre-purge (1 min), while being subject to the breakthrough at or above 10 min pre-purge. For a three-bed sorbent tube with Carboxen 1000, at least 10 min of pre-purge was needed for the compounds with a retention time close to methanol (e.g., propanal). Another three-bed tube with Carbopack X reduced the solvent effect efficiently for a short pre-purge (2 min) without the breakthrough. As such, the solvent effect can be adjusted by the proper control of the sorbent tube application.

  19. Determination of five booster biocides in seawater by stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Giráldez, I; Chaguaceda, E; Bujalance, M; Morales, E

    2013-01-04

    Stir bar sorptive extraction (SBSE) and thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS) have been optimized for the determination of five organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051 and TCMTB) in seawater samples. The parameters affecting the desorption and absorption steps were investigated using 10 mL seawater samples. The optimised conditions consisted of an addition of 0.2 g mL(-1) KCl to the sample, which was extracted with 10mm length, 0.5mm film thickness stir bars coated with polydimethylsiloxane (PDMS), and stirred at 900 rpm for 90 min at room temperature (25 °C) in a vial. Desorption was carried out at 280 °C for 5 min under 50 mL min(-1) of helium flow in the splitless mode while maintaining a cryotrapping temperature of 20 °C in the programmed-temperature vaporization (PTV) injector of the GC-MS system. Finally, the PTV injector was ramped to a temperature of 280 °C and the analytes were separated in the GC and detected by MS using the selected-ion monitoring (SIM) mode. The detection limits of booster biocides were found to be in the range of 0.005-0.9 μg L(-1). The regression coefficients were higher than 0.999 for all analytes. The average recovery was higher than 72% (R.S.D.: 7-15%). All these figures of merit were established running samples in triplicate. This simple, accurate, sensitive and selective analytical method may be used for the determination of trace amounts of booster biocides in water samples from marinas.

  20. Dispersive micro solid-phase extraction for the rapid analysis of synthetic polycyclic musks using thermal desorption gas chromatography-mass spectrometry.

    Science.gov (United States)

    Chung, Wu-Hsun; Tzing, Shin-Hwa; Ding, Wang-Hsien

    2013-09-13

    A simple and solvent-free method for the rapid analysis of five synthetic polycyclic musks in water samples is described. The method involves the use of dispersive micro solid-phase extraction (D-μ-SPE) coupled with direct thermal desorption (TD) gas chromatography-mass spectrometry (GC-MS) operating in the selected-ion-storage (SIS) mode. The parameters affecting the extraction efficiency of the target analytes from water sample and the thermal desorption conditions in the GC injection-port were optimized using a central composite design method. The optimal extraction conditions involved immersing 3.2mg of a typical octadecyl (C18) bonded silica adsorbent (i.e., ENVI-18) in a 10mL water sample. After extraction by vigorously shaking for 1.0min, the adsorbents were collected and dried on a filter. The adsorbents were transferred to a micro-vial, which was directly inserted into GC temperature-programmed injector, and the extracted target analytes were then thermally desorbed in the GC injection-port at 337°C for 3.8min. The limits of quantitation (LOQs) were determined to be 1.2-3.0ng/L. Precision, as indicated by relative standard deviations (RSDs), was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 74 and 90%. A preliminary analysis of the river water samples revealed that galaxolide (HHCB) and tonalide (AHTN) were the two most common synthetic polycyclic musks present. Using a standard addition method, their concentrations were determined to in the range from 11 to 140ng/L.

  1. Novel characterization of the adsorption sites in large pore metal-organic frameworks: combination of X-ray powder diffraction and thermal desorption spectroscopy.

    Science.gov (United States)

    Soleimani-Dorcheh, Ali; Dinnebier, Robert E; Kuc, Agnieszka; Magdysyuk, Oxana; Adams, Frank; Denysenko, Dmytro; Heine, Thomas; Volkmer, Dirk; Donner, Wolfgang; Hirscher, Michael

    2012-10-05

    The preferred adsorption sites of xenon in the recently synthesized metal-organic framework MFU-4l(arge) possessing a bimodal pore structure (with pore sizes of 12 Å and 18.6 Å) were studied via the combination of low temperature thermal desorption spectroscopy and in situ X-ray powder diffraction. The diffraction patterns were collected at 110 K and 150 K according to the temperature of the desorption maxima. The maximum entropy method was used to reconstruct the electron density distribution of the structure and to localize the adsorbed xenon using refined data of the Xe-filled and empty sample. First principles calculations revealed that Xe atoms exclusively occupy the Wyckoff 32f position at approximately 2/3 2/3 2/3 along the body diagonal of the cubic crystal structure. At 110 K, Xe atoms occupy all 32 f positions (8 atoms per pore) while at 150 K the occupancy descends to 25% (2 atoms per pore). No Xe occupation of the small pores is observed by neither experimental measurements nor theoretical studies.

  2. Thermal desorption studies of isotopically-labeled oxygen-induced superconductivity in La sub 2 CuO sub 4+. delta

    Energy Technology Data Exchange (ETDEWEB)

    Shinn, N.D.; Bartram, M.E.; Schirber, J.E.; Overmyer, D.L.; Rogers, J.W. Jr. (Sandia National Labs., Albuquerque, NM (USA)); Fisk, Z.; Cheong, S.W. (Los Alamos National Lab., NM (USA))

    1990-01-01

    Isotopically-labeled oxygen enrichment and thermal desorption mass spectroscopy (TDMS) have been combined to study interstitial oxygen desorption from superconducting La{sub 2}CuO{sub 4+{delta}} ({delta} {le} 0.032). Single crystal samples of magnetic insulating La{sub 2}CuO{sub 4.00} were annealed at 860K under 1--3 kbar oxygen pressure for 12--100 hours to yield hole-doped, superconducting La{sub 2}CuO{sub 4+{delta}} samples with 35K < {Tc} < 40K. Whereas no TDMS signals were observed for the insulator, rapid bursts (FWHM < 0.5 sec) of molecular oxygen were observed above 350K while heating the superconductor at less than 1 K sec{sup {minus}1} in high vacuum. A kinetic model is proposed in which the interstitial oxygen diffuses to internal grain boundaries and defects during heating, thereby inducing stress in the lattice as it attempts to revert to the LaCuO{sub 4.00} crystal structure. This stress is relieved by lattice fracture at grain boundaries during the TDMS experiment, releasing the trapped oxygen from the sample as micro-cracks are formed. In addition, the facile oxygen exchange between interstitial and lattice oxygen sites has been discovered by TDMS and weight gain measurements from isotopically-enriched crystals, supporting the structural model of Chaillout, et al. in which the interstitial oxygen atom dimerizes with a lattice oxygen ion.

  3. Multi-residue off-flavour profiling in wine using stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Franc, Céline; David, Frank; de Revel, Gilles

    2009-04-10

    A multi-residue method (MRM) for the detection and quantification of eight compounds responsible for off-flavours in wine using stir bar sorptive extraction (SBSE) followed by thermal desorption (TD) and gas chromatography-mass spectrometry (GC-MS) analysis is presented. The extraction and desorption conditions were optimised in order to get the best compromise for the simultaneous analysis of the eight target solutes, belonging to different chemical classes. The analytical conditions enable the quantification of the solutes below their respective organoleptic perception thresholds in wine. The method displayed good linearity over the concentration ranges explored in wine as well as excellent repeatability (RSD below 6%) and good reproducibility (RSD below 24%). The developed methodology was applied to the analysis of several wines and showed good agreement with the results collected with headspace solid-phase microextraction (HS-SPME) or liquid-liquid extraction (LLE) followed by GC-MS or electron capture detection (ECD). Good correlation was also found between the analytical and sensory results.

  4. Optimization of a Dynamic Headspace-Thermal Desorption-Gas Chromatography/Mass Spectrometry procedure for the determination of furfurals in vinegars.

    Science.gov (United States)

    Manzini, Simona; Durante, Caterina; Baschieri, Carlo; Cocchi, Marina; Sighinolfi, Simona; Totaro, Sara; Marchetti, Andrea

    2011-08-15

    The use of a Dynamic Headspace System (DHS) device combined with a Thermal Desorption Unit (TDU) interfaced to a Gas Chromatography/Mass Spectrometry (GC/MS) system is proposed for the determination of furfurals in oenological products. An experimental design protocol has been employed for the optimization of the instrumental settings concerning DHS and TDU extraction and desorption steps. It has been possible to individuate the following optimized conditions: incubation temperature 40°C, purge volume 800 mL, dry volume 1500 mL, TDU hold time 5 min and incubation time 10 min. The performance of two different SPE sorbents, namely Tenax TA and Tenax GR used for the furfurals trapping, was investigated too. The developed DHS sampling procedure showed good reproducibility values with a RSD% lower than 10% for all the monitored species. The optimized experimental settings have been used to determine furfurals in several vinegar samples obtained by traditional procedure starting from cooked grape musts, i.e. in Aceto Balsamico Tradizionale di Modena (ABTM). In fact, the control of these species is extremely important for quality and safety issues.

  5. Use of thermal desorption gas chromatography-olfactometry/mass spectrometry for the comparison of identified and unidentified odor active compounds emitted from building products containing linseed oil

    DEFF Research Database (Denmark)

    Clausen, P. A.; Knudsen, Henrik Nellemose; Larsen, K.

    2008-01-01

    The emission of odor active volatile organic compounds (VOCs) from a floor oil based on linseed oil, the linseed oil itself and a low-odor linseed oil was investigated by thermal desorption gas chromatography combined with olfactometry and mass spectrometry (TD-GC-O/MS). The oils were applied...... identified by GC-MS. While 92 VOCs were detected from the oil used in the floor oil, only 13 were detected in the low-odor linseed oil. The major odor active VOCs were aldehydes and carboxylic acids. Spearmen rank correlation of the GC-O profiles showed that the odor profile of the linseed oil likely...... influenced the odor profile of the floor oil based on this linseed oil....

  6. Comparative study of thermal desorption and solvent extraction-gas chromatography-mass spectrometric analysis for the quantification of phthalates in polymers.

    Science.gov (United States)

    Kim, Jae Woo; Kim, Young-Min; Moon, Hye Mi; Hosaka, Akihiko; Watanabe, Chuichi; Teramae, Norio; Choe, Eun Kyung; Myung, Seung-Woon

    2016-06-17

    For the quantitative analysis of phthalates in polymers, a thermal desorption (TD)-GC-MS method was compared with solvent extraction (SE)-GC-MS methods which require the long pretreatment procedures using large amount of harmful organic solvents. Calibration curves of TD-GC-MS showed good linearity (r(2)>0.9997) and low method detection limit (phthalate polymer samples (test PTPSs) showed an RSD below 7.4% and acceptable recoveries (78.3-117.4%) as in the standard method of International Electrotechnical Commission. Even in a sample with a high concentration of phthalates (PTPS #3), the method also showed good recovery with low RSD values. The TD-GC-MS results were comparable with those results by SE-GC-MS methods, indicating that TD-GC-MS method also can be used for the quantification of phthalates in polymers. The average recovery (92-103%) and RSD (phthalates in polymers.

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

    Science.gov (United States)

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

    2001-06-01

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

  8. Use of thermal desorption gas chromatography-olfactometry/mass spectrometry for the comparison of identified and unidentified odor active compounds emitted from building products containing linseed oil

    DEFF Research Database (Denmark)

    Clausen, P. A.; Knudsen, Henrik Nellemose; Larsen, K.

    2008-01-01

    The emission of odor active volatile organic compounds (VOCs) from a floor oil based on linseed oil, the linseed oil itself and a low-odor linseed oil was investigated by thermal desorption gas chromatography combined with olfactometry and mass spectrometry (TD-GC-O/MS). The oils were applied...... identified by GC-MS. While 92 VOCs were detected from the oil used in the floor oil, only 13 were detected in the low-odor linseed oil. The major odor active VOCs were aldehydes and carboxylic acids. Spearmen rank correlation of the GC-O profiles showed that the odor profile of the linseed oil likely...... influenced the odor profile of the floor oil based on this linseed oil....

  9. Measurement of Passive Uptake Rates for Volatile Organic Compounds on Commercial Thermal Desorption Tubes and the Effect of Ozone on Sampling

    Energy Technology Data Exchange (ETDEWEB)

    Maddalena, Randy [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Parra, Amanda [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Russell, Marion [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lee, Wen-Yee [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2013-05-01

    Diffusive or passive sampling methods using commercially filled axial-sampling thermal desorption tubes are widely used for measuring volatile organic compounds (VOCs) in air. The passive sampling method provides a robust, cost effective way to measure air quality with time-averaged concentrations spanning up to a week or more. Sampling rates for VOCs can be calculated using tube geometry and Fick’s Law for ideal diffusion behavior or measured experimentally. There is evidence that uptake rates deviate from ideal and may not be constant over time. Therefore, experimentally measured sampling rates are preferred. In this project, a calibration chamber with a continuous stirred tank reactor design and constant VOC source was combined with active sampling to generate a controlled dynamic calibration environment for passive samplers. The chamber air was augmented with a continuous source of 45 VOCs ranging from pentane to diethyl phthalate representing a variety of chemical classes and physiochemical properties. Both passive and active samples were collected on commercially filled Tenax TA thermal desorption tubes over an 11-day period and used to calculate passive sampling rates. A second experiment was designed to determine the impact of ozone on passive sampling by using the calibration chamber to passively load five terpenes on a set of Tenax tubes and then exposing the tubes to different ozone environments with and without ozone scrubbers attached to the tube inlet. During the sampling rate experiment, the measured diffusive uptake was constant for up to seven days for most of the VOCs tested but deviated from linearity for some of the more volatile compounds between seven and eleven days. In the ozone experiment, both exposed and unexposed tubes showed a similar decline in terpene mass over time indicating back diffusion when uncapped tubes were transferred to a clean environment but there was no indication of significant loss by ozone reaction.

  10. Analysis of the chemical composition of organic aerosol at the Mt. Sonnblick observatory using a novel high mass resolution thermal-desorption proton-transfer-reaction mass-spectrometer (hr-TD-PTR-MS)

    NARCIS (Netherlands)

    Holzinger, R.|info:eu-repo/dai/nl/337989338; Kasper-Giebl, A.; Staudinger, M.; Schauer, G.; Roeckmann, T.|info:eu-repo/dai/nl/304838233

    2010-01-01

    For the first time a high mass resolution thermal desorption proton transfer reaction mass spectrometer (hr-TD-PTR-MS) was deployed in the field to analyze the composition of the organic fraction of aerosols. We report on measurements from the remote Mt. Sonnblick observatory in the Austrian alps

  11. Hydrogen desorption from nanostructured magnesium hydride composites

    Directory of Open Access Journals (Sweden)

    Brdarić Tanja P.

    2007-01-01

    Full Text Available The influence of 3d transition metal addition (Fe, Co and Ni on the desorption properties of magnesium hydride were studied. The ball milling of MgH2-3d metal blends was performed under Ar. Microstructural and morphological characterization were performed by XRD and SEM analysis, while the hydrogen desorption properties were investigated by DSC. The results show a strong correlation between the morphology and thermal stability of the composites. The complex desorption behavior (the existence of more than one desorption peak was correlated with the dispersion of the metal additive particles that appear to play the main role in the desorption. The desorption temperature can be reduced by more than 100 degrees if Fe is added as additive. The activation energy for H2 desorption from the MgH2-Fe composite is 120 kJ/mol, implying that diffusion controls the dehydration process.

  12. Analysis of trace contamination of phthalate esters in ultrapure water using a modified solid-phase extraction procedure and automated thermal desorption-gas chromatography/mass spectrometry.

    Science.gov (United States)

    Liu, Hsu-Chuan; Den, Walter; Chan, Shu-Fei; Kin, Kuan Tzu

    2008-04-25

    The present study was aimed to develop a procedure modified from the conventional solid-phase extraction (SPE) method for the analysis of trace concentration of phthalate esters in industrial ultrapure water (UPW). The proposed procedure allows UPW sample to be drawn through a sampling tube containing hydrophobic sorbent (Tenax TA) to concentrate the aqueous phthalate esters. The solid trap was then demoisturized by two-stage gas drying before subjecting to thermal desorption and analysis by gas chromatography-mass spectrometry. This process removes the solvent extraction procedure necessary for the conventional SPE method, and permits automation of the analytical procedure for high-volume analyses. Several important parameters, including desorption temperature and duration, packing quantity and demoisturizing procedure, were optimized in this study based on the analytical sensitivity for a standard mixture containing five different phthalate esters. The method detection limits for the five phthalate esters were between 36 ng l(-1) and 95 ng l(-1) and recovery rates between 15% and 101%. Dioctyl phthalate (DOP) was not recovered adequately because the compound was both poorly adsorbed and desorbed on and off Tenax TA sorbents. Furthermore, analyses of material leaching from poly(vinyl chloride) (PVC) tubes as well as the actual water samples showed that di-n-butyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) were the common contaminants detected from PVC contaminated UPW and the actual UPW, as well as in tap water. The reduction of DEHP in the production processes of actual UPW was clearly observed, however a DEHP concentration of 0.20 microg l(-1) at the point of use was still being quantified, suggesting that the contamination of phthalate esters could present a barrier to the future cleanliness requirement of UPW. The work demonstrated that the proposed modified SPE procedure provided an effective method for rapid analysis and contamination

  13. H{sub 2} thermal desorption and hydride conversion reactions in Li cells of TiH{sub 2}/C amorphous nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Vitucci, F.M., E-mail: francesco.vitucci@roma1.infn.it [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Paolone, A. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Brutti, S. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Dipartimento di Scienze, Univ. Basilicata, V.le Ateneo Lucano, 10, 85100 Potenza (Italy); Munaò, D.; Silvestri, L.; Panero, S. [Dipartimento di Chimica, Sapienza Univ. Roma, P.le A. Moro 5, 00185 Roma (Italy); Reale, P. [ENEA – Centro Ricerche Casaccia,via Anguillarese 301, 00100 Roma (Italy)

    2015-10-05

    Highlights: • Galvanostatic measurements on amorphous TiH{sub 2} is reported. • Variation of ball milling pre-treatment vary the first discharge capacity. • Relation between thermal H{sub 2} desorption and electrochemical properties is proposed. - Abstract: Here we investigate the properties of amorphous TiH{sub 2}/carbon nanocomposites as possible active material in lithium cells. Several TiH{sub 2}/C mixtures are prepared by a mechanochemical route, by varying the carbon/hydride ratio. Materials are tested in electrochemical cells versus lithium metal in EC:DMC LiPF{sub 6} electrolyte by galvanostatic cycling (GC) and are characterized by X-ray diffraction, transmission electron microscopy, thermogravimetry and mass spectrometry. Thermal dehydrogenation processes are altered by the mechanochemical treatment of the sample: milling decreases the hydrogen content of the hydride. On the other hand, the mechanochemical grinding increases the specific capacity delivered during the first GC discharge. We suggest that the electrochemical process is the result of a delicate balance between the absolute quantity of hydrogen and its availability for the hydride conversion reaction.

  14. Analysis of volatile organic compounds in water by dynamic stripping, thermal desorption, cryofocusing, and capillary gas chromatography (journal version)

    Energy Technology Data Exchange (ETDEWEB)

    Vandegrift, S.A.

    1988-01-01

    A dynamic headspace procedure developed for the determination of volatile organic compounds (VOCs) in water is described. The VOCs are purged from a water sample with an inert gas, transferring them to a tube packed with Tenax adsorbent. The adsorbent tube, or trap, is thermally desorbed, the analytes cryofocused, and subsequently transferred to a capillary column gas chromatograph.

  15. Thermal desorption characteristics of CO, O2 and CO2 on non-porous water, crystalline water and silicate surfaces at sub-monolayer and multilayer coverages

    CERN Document Server

    Noble, J A; Dulieu, F; Fraser, H J

    2011-01-01

    The desorption characteristics of molecules on interstellar dust grains are important for modelling the behaviour of molecules in icy mantles and, critically, in describing the solid-gas interface. In this study, a series of laboratory experiments exploring the desorption of three small molecules from three astrophysically relevant surfaces are presented. The desorption of CO, O2 and CO2 at both sub-monolayer and multilayer coverages was investigated from non-porous water, crystalline water and silicate surfaces. Experimental data was modelled using the Polanyi-Wigner equation to produce a mathematical description of the desorption of each molecular species from each type of surface, uniquely describing both the monolayer and multilayer desorption in a single combined model. The implications of desorption behaviour over astrophysically relevant timescales are discussed.

  16. Precautions for in-injection port thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) as applied to aerosol filter samples

    Science.gov (United States)

    Ho, Steven Sai Hang; Chow, Judith C.; Watson, John G.; Ting Ng, Louisa Pan; Kwok, Yuk; Ho, K. F.; Cao, Junji

    2011-03-01

    In-injection port thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) allows for analysis for >130 non-polar organic compounds on small quartz-fiber filter samples without extraction chemicals. TD-GC/MS has been applied to samples from long-term U.S. networks since it is cost effective and less labor intensive. However, analysis of large numbers of samples results in sensitivity reductions over time. Instrument sensitivity and reproducibility were examined after 100, 200, and 500 sample analyses. Analyses of standards between batches of heavily loaded samples from China and Japan showed signal decreases of 28-78% for major organic classes. In the GC injection port, residues can accumulate on the gold-plated seal resulting in analyte adsorption as well as elevating signal background. Decreases in signal response were 28-43% for n-alkanes, 33-45% for hopanes and steranes, 28-56% for PAHs, and 38-78% for phthalates when the gold-plated seal was not replaced after 500 TD-GC/MS sample analyses. Limits of detection (LODs) also increased by 14-76% for the targeted non-polar organic compounds. Residues trapped in the capillary column head can cause peak broadening and overlap. The GC/MS system, including the injection port and gold seal, the column head (where the eluted sample is pre-concentrated), and the ion source should be cleaned after every batch of 50-100 samples.

  17. Simultaneous determination of preservatives in beverages, vinegar, aqueous sauces, and quasi-drug drinks by stir-bar sorptive extraction (SBSE) and thermal desorption GC-MS.

    Science.gov (United States)

    Ochiai, Nobuo; Sasamoto, Kikuo; Takino, Masahiko; Yamashita, Satoru; Daishima, Shigeki; Heiden, Arnd C; Hoffmann, Andreas

    2002-05-01

    A method for the simultaneous determination of seven preservatives - sorbic acid, benzoic acid, and p-hydroxybenzoic acid ethyl, isopropyl, propyl, isobutyl, and butyl esters - in beverages, vinegar, aqueous sauces, and quasi-drug drinks has been developed using the stir-bar sorptive extraction technique then thermal desorption GC-MS analysis. The extraction conditions - pH, sample volume, extraction temperature, salt addition, and extraction time - were examined. d5-Benzoic acid and p-hydroxybenzoic acid sec-butyl ester were added as surrogate internal standards to compensate for the effect of sample matrix and coexisting analytes on the sorptive extraction. The linearity of the method was good over the concentration range from 1 to 1000 microg mL(-1) for sorbic acid, 10-1000 microg mL(-1) for benzoic acid, and 0.1-100 microg mL(-1) for p-hydroxybenzoic acid ethyl, isopropyl, propyl, isobutyl, and butyl esters, and the correlation coefficients were higher than 0.9984. The limit of detection ranged from 0.015 to 3.3 microg mL(-1). The recoveries (95-105%) and precision (RSD: 0.86-6.0%) of the method were examined by analyzing a sparkling soft drink, white wine, red wine, balsamic vinegar, soy sauce, and quasi-drug drink samples fortified at the 5 to 50 microg mL(-1) level.

  18. The gas chromatographic determination of volatile fatty acids in wastewater samples: evaluation of experimental biases in direct injection method against thermal desorption method.

    Science.gov (United States)

    Ullah, Md Ahsan; Kim, Ki-Hyun; Szulejko, Jan E; Cho, Jinwoo

    2014-04-11

    The production of short-chained volatile fatty acids (VFAs) by the anaerobic bacterial digestion of sewage (wastewater) affords an excellent opportunity to alternative greener viable bio-energy fuels (i.e., microbial fuel cell). VFAs in wastewater (sewage) samples are commonly quantified through direct injection (DI) into a gas chromatograph with a flame ionization detector (GC-FID). In this study, the reliability of VFA analysis by the DI-GC method has been examined against a thermal desorption (TD-GC) method. The results indicate that the VFA concentrations determined from an aliquot from each wastewater sample by the DI-GC method were generally underestimated, e.g., reductions of 7% (acetic acid) to 93.4% (hexanoic acid) relative to the TD-GC method. The observed differences between the two methods suggest the possibly important role of the matrix effect to give rise to the negative biases in DI-GC analysis. To further explore this possibility, an ancillary experiment was performed to examine bias patterns of three DI-GC approaches. For instance, the results of the standard addition (SA) method confirm the definite role of matrix effect when analyzing wastewater samples by DI-GC. More importantly, their biases tend to increase systematically with increasing molecular weight and decreasing VFA concentrations. As such, the use of DI-GC method, if applied for the analysis of samples with a complicated matrix, needs a thorough validation to improve the reliability in data acquisition.

  19. Trace analysis of chlorophenols in river water samples by stir bar sorptive extraction with in situ derivatization and thermal desorption-gas chromatography-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kawaguchi, M.; Ishii, Y.; Okanouchi, N.; Sakui, N.; Ito, R.; Inoue, K.; Nakazawa, H. [Hoshi Univ., Tokyo (Japan). Dept. of Analytical Chemistry, Faculty of Pharmaceutical Sciences; Saito, K. [Saitama Institute of Public Health, Saitama (Japan). Dioxin Research Group

    2004-09-15

    Many analytical methods for the determination of chlorophenols in water samples have been reported including gas chromatography-mass spectrometry (GC-MS). However, GC-MS was initially used for the determination of phenol compounds even though derivatization was required. The derivatization leads to sharper peaks and hence to better separation and higher sensitivity for the phenols. However, the derivatization faces the risk of contamination and hence an overestimation of chlorophenols concentration. In order to overcome these problems, in situ derivatization has been developed, which involves the simple addition of a reagent to a liquid sample. Recently, a new sorptive extraction technique that uses a stir bar coated with polydimethylsiloxane (PDMS) was developed. The technique is known as stir bar sorptive extraction (SBSE). We already reported that determination of 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in river water4 and body fluid samples by using SBSE. In addition, SBSE with in situ derivatization has been successfully used in the determination of bisphenol A (BPA) in human body fluid samples6 and phenolic xenoestrogens in river water samples. The aim of this study is to determine trace amounts of chlorophenols in water samples by SBSE with in situ derivatization, followed by thermal desorption (TD)-GC-MS. The developed method was applied to determination of chlorophenols in river water samples.

  20. Separation and analysis of trace volatile formaldehyde in aquatic products by a MoO₃/polypyrrole intercalative sampling adsorbent with thermal desorption gas chromatography and mass spectrometry.

    Science.gov (United States)

    Ma, Yunjian; Zhao, Cheng; Zhan, Yisen; Li, Jianbin; Zhang, Zhuomin; Li, Gongke

    2015-05-01

    An in situ embedded synthesis strategy was developed for the preparation of a MoO3 /polypyrrole intercalative sampling adsorbent for the separation and analysis of trace volatile formaldehyde in aquatic products. Structural and morphological characteristics of the MoO3 /polypyrrole intercalative adsorbent were investigated by a series of characterization methods. The MoO3 /polypyrrole sampling adsorbent possessed a higher sampling capacity and selectivity for polar formaldehyde than commonly used commercial adsorbent Tenax TA. Finally, the MoO3 /polypyrrole adsorbent was packed in the thermal desorption tube that was directly coupled to gas chromatography with mass spectrometry for the analysis of trace volatile formaldehyde in aquatic products. Trace volatile formaldehyde from real aquatic products could be selectively sampled and quantified to be 0.43-6.6 mg/kg. The detection limit was achieved as 0.004 μg/L by this method. Good recoveries for spiked aquatic products were achieved in range of 75.0-108% with relative standard deviations of 1.2-9.0%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Determination of off-flavor compounds, 2-methylisoborneol and geosmin, in salmon fillets using stir bar sorptive extraction-thermal desorption coupled with gas chromatography-mass spectrometry.

    Science.gov (United States)

    Ruan, E D; Aalhus, J L; Summerfelt, S T; Davidson, J; Swift, B; Juárez, M

    2013-12-20

    A sensitive and solvent-less method for the determination of musty and earthy off-flavor compounds, 2-methylisoborneol (MIB) and geosmin (GSM), in salmon tissue was developed using stir bar sorptive extraction-thermal desorption coupled with gas chromatography-mass spectrometry (SBSE-TD-GCMS). MIB and GSM were solid phase extracted using polydimethylsiloxane (PDMS) coated stir bars, analyzed by gas chromatography, and detected in full scan mode of mass selective detector (MSD). Using this method, the calibration curves of MIB and GSM were linear in the range of 0.3-100ng/L, with a correlation coefficient above 0.999 and RSDs less than 4% (n=4). The limit of detection (LOD, S/N=3, n=6) and limit of quantification (LOQ, S/N=10, n=6) of MIB and GSM were both ∼0.3 and 1ng/L, respectively. The recoveries of MIB and GSM were 22% and 29% by spike in 30ng/L standard compounds, 23% and 30% by spike-in 100ng/L standard compounds in salmon tissue samples with good precision (<8% of RSDs, n=6), respectively. The recoveries of MIB and GSM were better than reported methodologies using SPME fibres (<10%) in fish tissue samples. This method was successfully applied to monitor and characterize depurated salmon fillet samples (0, 3, 6 and 10 days).

  2. Ion mobility spectrometry-mass spectrometry studies of ion processes in air at atmospheric pressure and their application to thermal desorption of 2,4,6-trinitrotoluene

    Science.gov (United States)

    Sabo, Martin; Malásková, Michaela; Matejčík, Štefan

    2014-02-01

    In this study we have investigated the negative reactant ion formation in a negative corona discharge (CD) using the corona discharge ion mobility spectrometry orthogonal acceleration time-of-flight (CD-IMS-oaTOF) technique. The reactant ions were formed in the CD operating in the reverse gas flow mode at an elevated temperature of 363.5 K in synthetic and ambient air. Under these conditions mainly O_{2}^{-} and their clusters were formed. We have also studied the influence of CCl4 admixture to air (dopant gas) on the composition of the reactant ions, which resulted in the formation of Cl- and its clusters with a reduced ion mobility of 3.05 cm2 V-1 s-1 as a major reactant ion peak. Additional IMS peaks with reduced ion mobilities of 2.49, 2.25 and 2.03 cm2 V-1 s-1 were detected, and Cl- · (NO2) and Cl- · (NO)n(n = 2, 3) anions were identified. The negative reactant ions were used to detect 2,4,6 trinitrotoluene (TNT) using the thermal desorption (TD) technique using a CD-IMS instrument. Using TD sampling and a negative CD ion source doped by CCl4 we have achieved a limit of detection of 350 pg for direct surface analysis of TNT.

  3. Volatile organic compounds in air at urban and industrial areas in the Tarragona region by thermal desorption and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Ras, Maria Rosa; Marcé, Rosa Maria; Borrull, Francesc

    2010-02-01

    Annual trends of a group of 66 volatile organic compounds (VOCs), containing 20 ozone precursors, were the aim of a sampling campaign carried out for a year in air at urban and industrial areas from Tarragona region. VOCs were determined by active collection on multisorbent tubes, followed by thermal desorption and gas chromatography-mass spectrometry. The analytical method was developed and validated, showing good levels of detection and quantification, recoveries, precision, and linearity for all the compounds in the range being studied. All the industrial and urban samples taken during the sampling campaign were similar in their qualitative composition. The most abundant compound in all urban and industrial sites was i-pentane, with concentrations between 15.2 and 202.1 microg m(-3) in urban sites and between 1.3 and 98.6 microg m(-3) in industrial sites. In urban sites, the following compounds in order of abundance were toluene, n-pentane, m,p-xylene, and o-xylene, with maximum levels of 150.6, 45.8, 42.3, and 31.7 microg m(-3), respectively. In industrial sites, the most abundant compounds depended on the sampled site.

  4. Determination of parabens in house dust by pressurised hot water extraction followed by stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Ramírez, Noelia; Marcé, Rosa Maria; Borrull, Francesc

    2011-09-16

    This study describes the development of a new method for determining p-hydroxybenzoic esters (parabens) in house dust. This optimised method was based on the pressurised hot water extraction (PHWE) of house dust, followed by the acetylation of the extracted parabens, stir bar sorptive extraction (SBSE) with a polydimethylsiloxane stir bar, and finally analysis using thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The combination of SBSE and PHWE allows the analytes to be preconcentrated and extracted from the aqueous extract in a single step with minimal manipulation of the sample. Furthermore the in situ acetylation of parabens prior to SBSE improved their extraction efficiency and their GC-MS signal. The method showed recoveries of between 40 and 80%, good linearity, repeatability and reproducibility (paraben to 2.1 ng g(-1) for methyl paraben) and quantification (from 3.3 ng g(-1) for propyl paraben to 8.5 ng g(-1) for methyl paraben). The proposed method was applied to the analysis of house dust samples. All the target parabens were found in the samples. Methyl and propyl parabens were the most abundant, with concentrations up to 2440 ng g(-1) and 910 ng g(-1), respectively. The high levels of parabens found in the samples confirm the importance of determining organic contaminants in indoor environments.

  5. Carbamazepine in municipal wastewater and wastewater sludge: ultrafast quantification by laser diode thermal desorption-atmospheric pressure chemical ionization coupled with tandem mass spectrometry.

    Science.gov (United States)

    Mohapatra, D P; Brar, S K; Tyagi, R D; Picard, P; Surampalli, R Y

    2012-09-15

    In this study, the distribution of the anti-epileptic drug carbamazepine (CBZ) in wastewater (WW) and aqueous and solid phases of wastewater sludge (WWS) was carried out. A rapid and reliable method enabling high-throughput sample analysis for quicker data generation, detection, and monitoring of CBZ in WW and WWS was developed and validated. The ultrafast method (15s per sample) is based on the laser diode thermal desorption-atmospheric pressure chemical ionization (LDTD-APCI) coupled to tandem mass spectrometry (MS/MS). The optimization of instrumental parameters and method application for environmental analysis are presented. The performance of the novel method was evaluated by estimation of extraction recovery, linearity, precision and detection limit. The method detection limits was 12 ng L(-1) in WW and 3.4 ng g(-1) in WWS. The intra- and inter-day precisions were 8% and 11% in WW and 6% and 9% in WWS, respectively. Furthermore, three extraction methods, ultrasonic extraction (USE), microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) with three different solvent condition such as methanol, acetone and acetonitrile:ethyle acetate (5:1, v/v) were compared on the basis of procedural blank and method recovery. Overall, ASE showed the best extraction efficiency with methanol as compared to USE and MAE. Furthermore, the quantification of CBZ in WW and WWS samples showed the presence of contaminant in all stages of the treatment plant.

  6. Direct quantitative analysis of phthalate esters as micro-contaminants in cleanroom air and wafer surfaces by auto-thermal desorption--gas chromatography--mass spectrometry.

    Science.gov (United States)

    Kang, Yuhao; Den, Walter; Bai, Hsunling; Ko, Fu-Hsiang

    2005-04-01

    This study established an analytical method for the trace analyses of two phthalate esters, including diethyl phthalate (DEP) and di-n-butyl phthalate (DBP), known as the major constituents of cleanroom micro-contamination detrimental to the reliability of semiconductor devices. Using thermal desorption coupled with a GC-MS system, standard tubes were prepared by delivering liquid standards pre-vaporized by a quasi-vaporizer into Tenax GR tubes for calibration. This method was capable of achieving detection limits of 0.05 microg m(-3) for 0.1 m3 air samples and 0.03 ng cm(-2) for 150-mm wafer surface density. Actual samples collected from a semiconductor cleanroom showed that the concentration of DBP in a polypropylene wafer box (0.45 microg m(-3)) was nearly four times higher than that in the cleanroom environment (0.12 microg m(-3)). The surface contamination of DBP was 0.67 ng cm(-2) for a wafer stored in the wafer box for 24 h. Furthermore, among the three types of heat-resistant O-ring materials tested, Kalrez was found to be particularly suitable for high-temperature processes in semiconductor cleanrooms due to their low emissions of organic vapors. This analytical procedure should serve as an effective monitoring method for the organic micro-contamination in cleanroom environments.

  7. Thermal desorption/tunable vacuum-ultraviolet time-of-flight photoionization aerosol mass spectrometry for investigating secondary organic aerosols in chamber experiments.

    Science.gov (United States)

    Fang, Wenzheng; Gong, Lei; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi

    2011-12-01

    This paper describes thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) for the real-time analysis of secondary organic aerosols (SOAs) in smog chamber experiments. SOAs are sampled directly from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. Once the particles have entered the source region, they impact on a heater and are vaporized. The nascent vapor is then softly ionized by tunable VUV synchrotron radiation. TD-VUV-TOF-PIAMS was used in conjunction with the smog chamber to study SOA formation from the photooxidation of toluene with hydroxyl radicals. The ionization energies (IEs) of these SOA products are sometimes very different with each other. As the ideal photon source is tunable, its energy can be adjusted for each molecular to be ionized. The mass spectra obtained at different photon energies are then to be useful for molecular identification. Real-time analysis of the mass spectra of SOAs is compared with previous off-line measurements. These results illustrate the potential of TD-VUV-TOF-PIAMS for direct molecular characterization of SOAs in smog chamber experiments.

  8. Development of a thermal desorption gas chromatography-mass spectrometry method for quantitative determination of haloanisoles and halophenols in wineries' ambient air.

    Science.gov (United States)

    Camino-Sánchez, F J; Ruiz-García, J; Zafra-Gómez, A

    2013-08-30

    An analytical method for the detection and quantification of haloanisoles and their corresponding halophenols in wineries' ambient air was developed. The target analytes were haloanisoles and halophenols, reported by previous scientific literature as responsible for wine taint. A calibrated pump and active tubes filled with Tenax GR™ were used for sampling. These tubes were thermally desorbed and analyzed using gas chromatography-triple quadrupole mass spectrometry in the selected reaction monitoring mode. The adsorption efficiencies of five commercial sampling tubes filled with different materials were evaluated. The efficiencies of the selected adsorbent were close to 100% for all sampled compounds. Desorption, chromatographic and mass spectrometric conditions were accurately optimized allowing very low limits of quantification and wide linear ranges. The limits of quantification in ambient air ranged from 0.8pgtube(-1) for 2,4,6-trichlorophenol, to 28pgtube(-1) for pentachlorophenol. These results are of great importance because human sensory threshold for haloanisoles is very low. The chromatographic method was also validated and the instrumental precision and trueness were established, a maximum RSD of 9% and a mean recovery of 91-106% were obtained. The proposed method involves an easy and sensitive technique for the early detection of haloanisoles and their precursor halophenols in ambient air avoiding contamination of wine or winery facilities.

  9. Determination of dithiocarbamate pesticides in occupational hygiene sampling devices using the isooctane method and comparison with an automatic thermal desorption (ATD) method.

    Science.gov (United States)

    Coldwell, Matthew R; Pengelly, Ian; Rimmer, Duncan A

    2003-01-10

    Two new methods for the determination of dithiocarbamate pesticides in occupational hygiene sampling devices are described. Dithiocarbamate spiked occupational hygiene sampling devices, consisting of glass fibre (GF/A) filters, cotton pads, cotton gloves and disposable overalls, were reduced under acidic conditions and the CS2 evolved as a decomposition product was extracted into isooctane. The isooctane was then analysed using gas chromatography with mass spectrometry, for CS2, which provided a quantitative result for dithiocarbamates. Recoveries obtained were generally within a 70-110% range and reproducibilities better than 15% RSD were typically achieved. The method has been successfully applied to samples collected during occupational exposure surveys. A second method employing automatic thermal desorption-gas chromatography-mass spectrometry (ATD-GC-MS) has also been developed and applied to the direct analysis of GF/A (airborne) samples. The method relies on the thermal degradation of dithiocarbamates to release CS2, which is used to quantify the analytes. Thiram spiked GF/A filters gave an average recovery of 107% with an RSD of 4%. The performance of the two analytical methods were directly compared by analysing sub-portions of GF/A filters collected during a survey to evaluate occupational exposures to thiram during seed treatment operations. Both methods performed well for the analysis of airborne (GF/A) samples and produced results in good agreement. ATD-GC-MS is the preferred method for studies involving GF/A (airborne) samples only. Because of the wider applicability of the isooctane method for other sampling devices, it is the preferred choice when carrying out surveys which require a dermal as well as respirable exposure assessment.

  10. Electronic structure and Schottky-barrier formation on GaAs (100) surfaces prepared by thermal desorption of a protective arsenic coating

    Energy Technology Data Exchange (ETDEWEB)

    Spindt, C.J.; Yamada, M.; Meissner, P.L.; Miyano, K.E.; Kendelewicz, T.; Herrera-Gomez, A.; Spicer, W.E. (Stanford Electronics Laboratories, Stanford University, Stanford, California 94305-4055 (United States)); Arko, A.J. (Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States))

    1992-05-15

    Soft-x-ray photoemission spectroscopy has been used to characterize GaAs(100) surfaces and interfaces grown by molecular-beam epitaxy and prepared by the thermal desorption of a protective As coating. The samples studied were grown and arsenic capped identically to those used in a previous study (Brillson {ital et} {ital al}., J. Vac. Sci. Technol. B 6, 1263 (1988)). In this previous work, unpinned'' Schottky-barrier formation was reported, with barrier heights over a wide (0.75-eV) range. This is a striking result, as it was previously believed that all metals will pin GaAs surfaces in a narrow energy range near the middle of the band gap. This large range of barrier heights later led to the suggestion that the (100) surface could become an insulating layer that could screen out the effects of metal-induced gap states. Motivated by this work, we have studied Al and Au Schottky barriers since the deposition of these two metals gave the extreme low and high barriers in the 0.75-eV range. We have also characterized the clean surfaces prepared by desorbing the As caps at different temperatures. The As 3{ital d} and Ga 3{ital d} core levels showed that the surface stoichiometry could be varied significantly with the desorption temperature. The As 3{ital d} line shape was found to be the best indication of the surface stoichiometry after the anneal. The valence-band spectra did not show any strong features which could be used to determine when the sample was completely decapped. The electronic structure of the surface layer was investigated experimentally, and no evidence of an insulating reconstruction was found. In our study of band bending, we found that the low-doped samples used here and in the earlier study showed significant photovoltages resulting in incorrect band-bending measurements. We also found that the Au measurements are made difficult by the presence of core-level shifts due to Au-Ga alloying.

  11. Thermal desorption and recycling of volatile selective binders used in solid wastes deashing; Desorption thermique et recyclage d'agglomerants selectifs volatils utilises en decendrage de residus solides

    Energy Technology Data Exchange (ETDEWEB)

    Bensakhria, A.; Sajet, P.; Antonini, G. [Universite de Technologie de Compiegne, Centre de Recherches de Royallieu UMR 6067, Genie des Procedes Industriels, 60 - Compiegne (France)

    2001-07-01

    A pilot unit for the deashing of coal tailings by selective agglomeration and recovery of the binder/water mixture by azeotropic desorption of binders has been tested. The effect of different experiment parameters on the deashing efficiency, on the recovery and recycling of the binding agent have been tested. A 90% deashing level with a 94% recovery of the carbonaceous matter has been obtained with a recycling level of about 82% for the agglomerating agent. (J.S.)

  12. Analysis of trimethoprim, lincomycin, sulfadoxin and tylosin in swine manure using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

    Science.gov (United States)

    Solliec, Morgan; Massé, Daniel; Sauvé, Sébastien

    2014-10-01

    A new extraction method coupled to a high throughput sample analysis technique was developed for the determination of four veterinary antibiotics. The analytes belong to different groups of antibiotics such as chemotherapeutics, sulfonamides, lincosamides and macrolides. Trimethoprim (TMP), sulfadoxin (SFX), lincomycin (LCM) and tylosin (TYL) were extracted from lyophilized manure using a sonication extraction. McIlvaine buffer and methanol (MeOH) were used as extraction buffers, followed by cation-exchange solid phase extraction (SPE) for clean-up. Analysis was performed by laser diode thermal desorption-atmospheric pressure chemical-ionization (LDTD-APCI) tandem mass spectrometry (MS/MS) with selected reaction monitoring (SRM) detection. The LDTD is a high throughput sample introduction method that reduces total analysis time to less than 15s per sample, compared to minutes when using traditional liquid chromatography (LC). Various SPE parameters were optimized after sample extraction: the stationary phase, the extraction solvent composition, the quantity of sample extracted and sample pH. LDTD parameters were also optimized: solvent deposition, carrier gas, laser power and corona discharge. The method limit of detection (MLD) ranged from 2.5 to 8.3 µg kg(-1) while the method limit of quantification (MLQ) ranged from 8.3 to 28µgkg(-1). Calibration curves in the manure matrix showed good linearity (R(2)≥ 0.996) for all analytes and the interday and intraday coefficients of variation were below 14%. Recoveries of analytes from manure ranged from 53% to 69%. The method was successfully applied to real manure samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Determination of Glycol Ethers in Ambient Air by Adsorption Sampling and Thermal Desorption with GC/MS Analysis: Performance Evaluation and Field Application

    Directory of Open Access Journals (Sweden)

    Young-Kyo Seo

    2012-01-01

    Full Text Available Some of glycol ethers, such as 2-methoxyethanol (2-ME and 2-ethoxyethanol (2-EE are known to be toxic and classified as hazardous air pollutants in USA, Japan and Germany. In Korea, however, there has been no study conducted so far for these compounds in ambient air. In addition, no clear methodologies for the measurement of glycol ethers have been yet established. We carried out this study to evaluate a sampling and analytical method for the determination of glycol ethers, in ambient air samples collected in specific industrial areas of South Korea. To measure glycol ethers, adsorption sampling and thermal desorption with GC/MS analysis were used in this study. The analytical method showed good repeatability, linearity and sensitivity. The lower detection limits were estimated to be approximately 0.3∼0.5 ppb. Based on storage tests, it was suggested that samples should be analyzed within two weeks. It was also demonstrated that this method can be used for the simultaneous measurement of glycol ethers and other aromatic VOCs such as benzene, toluene, and xylenes. Field sampling campaign was carried out at 2 sites, located in a large industrial area, from October 2006 to June 2007, and a total of 480 samples were collected seasonally. Among them, 2-ME was not detected from any samples, while 2-EE and 2-Ethyloxyethylacetate (2-EEA were found in 7 and 70 samples, respectively. The measured concentrations of 2-EE and 2-EEA for samples were ranged from 0.7-2.5 ppb and from 0.5-10.5 ppb, respectively. To our knowledge, this is the first measurement report for glycol ethers in the ambient atmosphere not only in Korea but also the rest of the world.

  14. Au and Al Schottky barrier formation on GaAs (100) surfaces prepared by thermal desorption of a protective arsenic coating

    Energy Technology Data Exchange (ETDEWEB)

    Spindt, C.J.; Yamada, M.; Meissner, P.L.; Miyano, K.E.; Herrera, A.; Spicer, W.E. (Stanford Electronics Laboratories, Stanford University, Stanford, California 94305-4055 (US)); Arko, A.J. (Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (US))

    1991-07-01

    Soft x-ray photoemission spectroscopy has been used to investigate the initial stages of Schottky barrier formation on GaAs (100) surfaces prepared by the thermal desorption of an As cap. This work was motivated by a previous study (Brillson {ital et} {ital al}., J. Vac. Sci. Technol. B {bold 6}, 1263 (1988)) of identically grown and capped samples which reported unpinned'' Schottky barrier formation, with barrier heights falling over a wide range (0.75 eV) of energies. This large energy range is a striking result, as a considerable number of prior studies on both (110) and (100) surfaces have found that all metals will pin in a narrow (0.25 eV) range near midgap. Since Au and Al are the extremes of the larger 0.75 eV span of Schottky barriers, we have studied the deposition of these two metals. We found that the barrier height measurements on the low doped {ital n}-type samples used in this work and in the paper referenced above are affected by photovoltaic effects, even at room temperature. These photovoltaic effects cause shifts in the band bending, which are an artifact of the measurement. We also performed measurements on more heavily doped samples, and the photovoltaic effects were removed. In addition, we point out that Au--Ga alloying makes the case of Au potentially misleading. With the photovoltaic effects removed, and the Au--Ga alloying carefully accounted for, we found that the barriers heights for Au and Al differ by only 0.25 eV.

  15. MOF-5 metal-organic framework as sorbent for in-field sampling and preconcentration in combination with thermal desorption GC/MS for determination of atmospheric formaldehyde.

    Science.gov (United States)

    Gu, Zhi-Yuan; Wang, Gen; Yan, Xiu-Ping

    2010-02-15

    Metal-organic frameworks (MOFs) are one kind of highly porous crystalline materials, which are constructed by metal-containing inorganic nodes and organic linkers. With large surface area and high thermal stability, MOFs have great potential as sorbents for the preconcentration of trace analytes. However, such application of MOFs to the analysis of real samples has not been reported before. Here we report the utilization of MOF-5 as sorbent for in-field sampling and preconcentration of atmospheric formaldehyde before thermal desorption (TD) GC/MS (TD-GC/MS) determination without the need for any chemical derivatization. MOF-5 gave a 53 and 73 times better concentration effect than Tenax TA (organic polymers) and Carbograph 1TD (graphitized carbon black), respectively, for TD-GC/MS determination of formaldehyde. MOF-5 showed good performance for in-field sampling and preconcentration of formaldehyde from air samples with a relative humidity less than 45%. The collected formaldehyde on MOF-5 sorbent was stable for at least 72 h at room temperature before TD-GC/MS analysis. One tube packed with 300 mg of MOF-5 lasted 200 cycles of adsorption/TD without significant loss of collection efficiency. The breakthrough volume of such a tube was 1.2 L of 28.35 mg m(-3) formaldehyde at a sampling flow rate of 100 mL min(-1). The use of MOF-5 for in-field sampling and preconcentration in combination with TD-GC/MS for the determination of formaldehyde offered a linear range covering 3 orders of magnitude, and a detection limit of 0.6 microg m(-3). The precision for six replicate cycles of in-field sampling and preconcentration for TD-GC/MS determination using one 300 mg MOF-5 packed tube ranged from 2.8% to 5.3%. The tube-to-tube reproducibility of three MOF-5 tubes prepared in parallel was 7.7%. The developed method was applied to analysis of local indoor and outdoor air samples for formaldehyde and validated by the standard method TO-11A of the United States Environmental

  16. Influence of Vegetation on the In Situ Bacterial Community and Polycyclic Aromatic Hydrocarbon (PAH) Degraders in Aged PAH-Contaminated or Thermal-Desorption-Treated Soil▿ †

    Science.gov (United States)

    Cébron, Aurélie; Beguiristain, Thierry; Faure, Pierre; Norini, Marie-Paule; Masfaraud, Jean-François; Leyval, Corinne

    2009-01-01

    The polycyclic aromatic hydrocarbon (PAH) contamination, bacterial community, and PAH-degrading bacteria were monitored in aged PAH-contaminated soil (Neuves-Maisons [NM] soil; with a mean of 1,915 mg of 16 PAHs·kg−1 of soil dry weight) and in the same soil previously treated by thermal desorption (TD soil; with a mean of 106 mg of 16 PAHs·kg−1 of soil dry weight). This study was conducted in situ for 2 years using experimental plots of the two soils. NM soil was colonized by spontaneous vegetation (NM-SV), planted with Medicago sativa (NM-Ms), or left as bare soil (NM-BS), and the TD soil was planted with Medicago sativa (TD-Ms). The bacterial community density, structure, and diversity were estimated by real-time PCR quantification of the 16S rRNA gene copy number, temporal thermal gradient gel electrophoresis fingerprinting, and band sequencing, respectively. The density of the bacterial community increased the first year during stabilization of the system and stayed constant in the NM soil, while it continued to increase in the TD soil during the second year. The bacterial community structure diverged among all the plot types after 2 years on site. In the NM-BS plots, the bacterial community was represented mainly by Betaproteobacteria and Gammaproteobacteria. The presence of vegetation (NM-SV and NM-Ms) in the NM soil favored the development of a wider range of bacterial phyla (Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, Verrucomicrobia, Actinobacteria, Firmicutes, and Chloroflexi) that, for the most part, were not closely related to known bacterial representatives. Moreover, under the influence of the same plant, the bacterial community that developed in the TD-Ms was represented by different bacterial species (Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria) than that in the NM-Ms. During the 2 years of monitoring, the PAH concentration did not evolve significantly. The abundance of gram-negative (GN

  17. Green Ocean Amazon (GoAmazon) 2014/15. Semi-Volatile Thermal Desorption Aerosol Gas Chromatograph (SVTAG) Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Goldstein, A. H. [Univ. of California, Berkeley, CA (United States); Yee, L. D. [Univ. of California, Berkeley, CA (United States); Issacman-VanWertz, G. [Univ. of California, Berkeley, CA (United States); Wernis, R. A. [Univ. of California, Berkeley, CA (United States)

    2016-03-01

    In areas where biogenic emissions are oxidized in the presence of anthropogenic pollutants such as SO2, NOx, and black carbon, it has become increasingly apparent that secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (VOCs) is substantially enhanced. Research is urgently needed to elucidate fundamental processes of natural and anthropogenically influenced VOC oxidation and the contribution of these processes to SOA formation. GoAmazon 2014/15 afforded study of the chemical transformations in the region downwind of Manaus, Brazil, where local biogenic VOC emissions are high, and their chemical oxidation can be studied both inside and outside of the urban plume to differentiate the role of anthropogenic influence on secondary aerosol formation during oxidation of these natural VOC emissions. To understand the connection between primary biogenic VOC emissions and their secondary products that form aerosols, we made time-resolved molecular level measurements by deploying a Semi-Volatile Thermal Desorption Aerosol Gas Chromatograph (SV-TAG) and a sequential filter sampler during two intensive operational periods (IOPs) of the GoAmazon 2014/15 field campaign. The SV-TAG measured semi-volatile organic compounds in both the gas and particle phases and the sequential filter sampler collected aerosols on quartz fiber filters in four-hour increments used for offline analysis. SV-TAG employed novel online derivatization that provided chemical speciation of highly oxygenated or functionalized compounds that comprise a substantial fraction of secondary organic aerosols, yet are poorly characterized. It also provided partitioning of these compounds between the vapor and particle phases at sufficient time resolution to define the importance of competing atmospheric processes. These measurements were supported by offline analysis of the filters using two-dimensional gas chromatography (GC x GC) with high-resolution time-of-flight mass spectrometry

  18. Determination of a wide range of volatile organic compounds in ambient air using multisorbent adsorption/thermal desorption and gas chromatography/mass spectrometry

    Science.gov (United States)

    Pankow, J.F.; Luo, W.; Isabelle, L.M.; Bender, D.A.; Baker, R.J.

    1998-01-01

    Adsorption/thermal desorption with multisorbent air-sampling cartridges was developed for the determination of 87 method analytes including halogenated alkanes, halogenated alkenes, ethers, alcohols, nitriles, esters, ketones, aromatics, a disulfide, and a furan. The volatilities of the compounds ranged from that of dichlorofluoromethane (CFC12) to that of 1,2,3- trichlorobenzene. The eight most volatile compounds were determined using a 1.5-L air sample and a sample cartridge containing 50 mg of Carbotrap B and 280 mg of Carboxen 1000; the remaining 79 compounds were determined using a 5-L air sample and a cartridge containing 180 mg of Carbotrap B and 70 mg of Carboxen 1000. Analysis and detection were by gas chromatography/mass spectrometry. The minimum detectable level (MDL) concentration values ranged from 0.01 parts per billion by volume (ppbv) for chlorobenzene to 0.4 ppbv for bromomethane; most of the MDL values were in the range 0.02-0.06 ppbv. No breakthrough was detected with the prescribed sample volumes. Analyte stability on the cartridges was very good. Excellent recoveries were obtained with independent check standards. Travel spike recoveries ranged from 90 to 110% for 72 of the 87 compounds. The recoveries were less than 70% for bromomethane and chloroethene and for a few compounds such as methyl acetate that are subject to losses by hydrolysis; the lowest travel spike recovery was obtained for bromomethane (62%). Blank values for all compounds were either below detection or very low. Ambient atmospheric sampling was conducted in New Jersey from April to December, 1997. Three sites characterized by low, moderate, and high densities of urbanization/traffic were sampled. The median detected concentrations of the compounds were either similar at all three sites (as with the chlorofluorocarbon compounds) or increased with the density of urbanization/traffic (as with dichloromethane, MTBE, benzene, and toluene). For toluene, the median detected

  19. Survival and growth of Alfalfa (Medicago sativa l.) inoculated with an am fungus (Glomus intraradices) in contaminated soils treated with two different remediation technologies (bio-pile and thermal desorption)

    Energy Technology Data Exchange (ETDEWEB)

    Norini, M.P.; Beguiristain, Th.; Leyval, C. [LIMOS UMR 7137 CNRS-UHP Nancy - Faculty of Sciences, 54 - Vandoeuvre-les-Nancy (France)

    2005-07-01

    Polycyclic aromatic hydrocarbons (PAHs) represent a group of persistent and toxic soil pollutants that are of major public concern due to their mutagenic and carcinogenic property. Phyto-remediation is the use of plants and their associated microorganisms for remediation of polluted soils. Phyto-remediation could be used in conjunction with other remediation technologies to reduce the contamination to safe levels and maintain or restore soil physico-chemical and biological properties. Most plant species form mycorrhizas with symbiotic fungi. It was shown that AM fungi enhance survival and plant growth in PAH contaminated soils. Mycorrhizal fungi also enhance the biotransformation or biodegradation of PAH, although the effect differed between soils. A rhizosphere and myco-rhizosphere gradient of PAH concentrations was observed, with decreased PAH concentration with decreased distance to roots. Different microbial communities were found in the rhizosphere of AM and non-mycorrhizal plants in comparison to bulk soil, suggesting that AM could affect PAH degradation by changing microbial communities. We investigated the effect of mycorrhizal fungi and nutrients on the ability of alfalfa to grow on soil contaminated with PAHs before and after two remediation treatments. We used soil from an industrial site (Homecourt, North East part of France) highly contaminated with PAH (2000 mg kg{sup -1}), which has been partially treated by two different remediation technologies (bio-pile and thermal desorption). The bio-pile treatment consisted of piling the contaminated soil with stimulation of aerobic microbial activity by aeration and addition of nutrient solution, and reduced PAH concentration to around 300 mg kg-1. With the thermal desorption treatment the soil was heated to around 500 deg. C so that PAH vaporized and were separated from the soil. The residual PAH concentration in soil was 40 mg kg{sup -1}. Treated and non-treated contaminated soil was planted with alfalfa

  20. Monitoring of PAHs in air by collection on XAD-2 adsorbent then microwave-assisted thermal desorption coupled with headspace solid-phase microextraction and gas chromatography with mass spectrometric detection.

    Science.gov (United States)

    Wei, Ming-Chi; Chang, Wan-Ting; Jen, Jen-Fon

    2007-02-01

    Microwave-assisted thermal desorption (MAD) coupled to headspace solid-phase microextraction (HS-SPME) has been studied for in-situ, one-step, sample preparation for PAHs collected on XAD-2 adsorbent, before gas chromatography with mass spectrometric detection. The PAHs on XAD-2 were desorbed into the extraction solution, evaporated into the headspace by use of microwave irradiation, and absorbed directly on a solid-phase microextraction fiber in the headspace. After desorption from the SPME fiber in the hot GC injection port, PAHs were analyzed by GC-MS. Conditions affecting extraction efficiency, for example extraction solution, addition of salt, stirring speed, SPME fiber coating, sampling temperature, microwave power and irradiation time, and desorption conditions were investigated. Experimental results indicated that extraction of 275 mg XAD-2, containing 10-200 ng PAHs, with 10-mL ethylene glycol-1 mol L(-1) NaCl solution, 7:3, by irradiation with 120 W for 40 min (the same as the extraction time), and collection with a PDMS-DVB fiber at 35 degrees C, resulted in the best extraction efficiency. Recovery was more than 80% and RSD was less than 14%. Optimum desorption was achieved by heating at 290 degrees C for 5 min. Detection limits varied from 0.02 to 1.0 ng for different PAHs. A real sample was obtained by using XAD-2 to collect smoke from indoor burning of joss sticks. The amounts of PAHs measured varied from 0.795 to 2.53 ng. The method is a simple and rapid procedure for determination of PAHs on XAD-2 absorbent, and is free from toxic organic solvents.

  1. Continuous soil VOCl measurements with automated flux chambers and micro-ECD gas chromatography coupled with the thermal desorption and cooled injection systems

    Science.gov (United States)

    Molodovskaya, M. S.; Svensson, T.; Pitts, A.; Delmonte, J.; Nesic, Z.; Oberg, G.

    2010-12-01

    automated chamber was continuously pumped through the glass tubes filled with carbon-based absorbent (Carbotrap 300) to capture and retain VOCl. At the end of each measurement period, the tubes are brought back to the lab, and the content is analyzed by Agilent 7890 GC/micro-ECD coupled with the Gerstel Thermal Desorption System (TDS) and Cooled Injection System (CIS). The ultra sensitive micro-ECD detection and high-efficiency capillary column (Rtx®-VMS, 20m x 0.18mm ID x 1.0µm) allows rapid separation and quantification of the mid-weight VOCl such as chloroform, carbon tetrachloride, 1,1,1-trichloroethane and bromochloromethane. The GC-method dynamic range is linear within 0.1-200.0ng, and the analytical precision is determined to be 4%. The described system can be used for the analysis of soil/atmosphere exchange of VOCl at the detection limit of 1.9ng m-2 h-1, which is far below previously reported average soil emission levels from forest soils. The high precision GC analysis combined with the automatic chambers makes it possible to study the high spatial and temporal variability of soil VOCl fluxes.

  2. Ultra-fast cyclosporin A quantitation in whole blood by Laser Diode Thermal Desorption-tandem mass spectrometry; comparison with High Performance Liquid Chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Jourdil, Jean-François; Picard, Pierre; Meunier, Cécile; Auger, Serge; Stanke-Labesque, Françoise

    2013-12-17

    In the last decade the quantitation of immunosuppressive drugs has seen vast improvements in analytical methods, optimizing time, accuracy of analysis and cost. Laser Diode Thermal Desorption (LDTD) coupled to Atmospheric Pressure Chemical ionization-tandem mass spectrometry (APCI-MS/MS) represents a technological breakthrough that removes the chromatographic separation step and thereby significantly increases the analytical throughput for the quantitation of cyclosporin A (CsA) in whole blood for therapeutic drug monitoring (TDM). A simple protein precipitation step was used prior to depositing 5 μL of the extract on a 96-well LazWell™ plate and CsA was quantified by LDTD-APCI-MS/MS. The laser pattern was set to ramp from 0 to 45% laser power within 2 s. The APCI parameters were set to negative needle voltage (-2 μA), carrier gas temperature (30°C) and air flow rate (3 L min(-1)). The negative ion single reaction monitoring transitions for CsA and its internal standard cyclosporin D (CsD) were respectively m/z 1201.1/1088.9 and m/z 1214.8/1102.8; obtained with a collision energy of -40 V. The analysis was achieved within 9 s from sample to sample. The extraction procedure yielded high recovery (92%; RSD=9.4%, n=6). The lower limit of quantitation was fixed at the first level of calibration: 23.5 ng mL(-1) (accuracy=112.3%; RSD=9.6%; n=6) and a blank+6 point linear regression up to 965 ng mL(-1) was used. Using 4 levels of quality control (QC), intra-day assays (n=6) ranged from 93.5 to 95.7% (bias) and from 3.4 to 13.1% (RSD) while inter-day assays (n=6) ranged from 92.9 to 105.3% (bias) and from 4.9 to 7.5% (RSD). An inter-sample contamination of CsA of 2.3% was calculated that was considered negligible with respect to the range of CsA concentrations. Whole blood samples (120) from patients under CsA treatment were analyzed by LDTD-APCI-MS/MS and HPLC-ESI-MS/MS, the gold standard reference method for CsA quantification. Both methods agreed (P≥0.99), with a

  3. First field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer for the on-line detection of particle-bound polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Oster, Markus; Elsasser, Michael; Schnelle-Kreis, Jürgen; Zimmermann, Ralf

    2011-12-01

    The on-line analysis of single aerosol particles with mass spectrometrical methods is an important tool for the investigation of aerosols. Often, a single laser pulse is used for one-step laser desorption/ionisation of aerosol particles. Resulting ions are detected with time-of-flight mass spectrometry. With this method, the detection of inorganic compounds is possible. The detection of more fragile organic compounds and carbon clusters can be accomplished by separating the desorption and the ionisation in two steps, e.g. by using two laser pulses. A further method is, using a heated metal surface for thermal desorption of aerosol particles. If an ultraviolet laser is used for ionisation, a selective ionisation of polycyclic aromatic hydrocarbons (PAH) and alkylated PAH is possible via a resonance-enhanced multiphoton-ionisation process. Laser velocimetry allows individual laser triggering for single particles and additionally delivers information on aerodynamic particle diameters. It was shown that particles deriving from different combustion sources can be differentiated according to their PAH patterns. For example, retene, a C(4)-alkylated phenanthrene derivative, is a marker for the combustion of coniferous wood. In this paper, the first field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer during a measurement campaign in Augsburg, Germany in winter 2010 is presented. Larger PAH-containing particles (i.e. with aerodynamic diameters larger than 1 μm), which are suspected to be originated by re-suspension processes of agglomerated material, were in the focus of the investigation. Due to the low concentration of these particles, an on-line virtual impactor enrichment system was used. The detection of particle-bound PAH in ambient particles in this larger size region was possible and in addition, retene could be detected on several particles, which allows to identify wood combustion as

  4. Protective coatings preventing hydrogen desorption from titanium during ion irradiation

    Science.gov (United States)

    Evsin, A. E.; Begrambekov, L. B.; Dovganyuk, S. S.; Kaplevsky, A. S.; Shutikova, M. I.

    2017-05-01

    Effect of yttria and titanium nitride coatings on features of deuterium desorption from titanium layer is investigated. It is shown that both coatings significantly raise the temperature of maximum of deuterium thermal desorption from titanium under linear heating and prevent desorption under prolonged keeping at the operating temperature of a neutron tube target. However, under irradiation with ions of H2 + O2 plasma the barrier properties of titanium nitride appear to degrade.

  5. Application of backflush and micro-flow techniques to the analysis of C5-C13 hydrocarbons in crude oils and its geochemical significance

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C5-C13 hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C5-C13 compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograrns (MID and full scan) could be obtained at the same time. The retension time differences of nC6-nC13 alkanes between GC and TIC were in the range of 0.02-0. 58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C6-C13 hydrocarbon group composition could be used in oil-oil correlation studies.

  6. Analysis of Nitrosamines in Cooked Bacon by QuEChERS Sample Preparation and Gas Chromatography-Tandem Mass Spectrometry with Backflushing.

    Science.gov (United States)

    Lehotay, Steven J; Sapozhnikova, Yelena; Han, Lijun; Johnston, John J

    2015-12-02

    Nitrites are added as a preservative to a variety of cured meats, including bacon, to kill bacteria, extend shelf life, and improve quality. During cooking, nitrites in the meat can be converted to carcinogenic nitrosamines (NAs), the formation of which is mitigated by the addition of antioxidants. In the past, the U.S. Department of Agriculture (USDA) Food Safety and Inspection Service (FSIS) monitored NAs in pan-fried bacon, but FSIS terminated monitoring of NAs in the 1990s due to the very low levels found. FSIS recently chose to conduct a risk assessment of NAs in cooked bacon to determine if current levels warrant routine monitoring of NAs again. To meet FSIS needs, we developed, validated, and implemented a new method of sample preparation and analysis to test cooked bacon for five NAs of most concern, which consist of N-nitroso-dimethylamine, -diethylamine, -dibutylamine, -piperidine, and -pyrrolidine. Sample preparation was based on the QuEChERS (quick, easy, cheap, effective, rugged, and safe) approach and analysis by gas chromatography-tandem mass spectrometry. Ruggedness was improved markedly in the analysis of the complex fatty extracts by backflushing the guard column, injection liner, and half of the analytical column after every injection. Validation results were acceptable with recoveries of 70-120% and bacon gave slightly lower concentrations overall compared to pan-frying.

  7. High sensitivity measurements of active oxysterols with automated filtration/filter backflush-solid phase extraction-liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Roberg-Larsen, Hanne; Strand, Martin Frank; Grimsmo, Anders; Olsen, Petter Angell; Dembinski, Jennifer L; Rise, Frode; Lundanes, Elsa; Greibrokk, Tyge; Krauss, Stefan; Wilson, Steven Ray

    2012-09-14

    Oxysterols are important in numerous biological processes, including cell signaling. Here we present an automated filtration/filter backflush-solid phase extraction-liquid chromatography-tandem mass spectrometry (AFFL-SPE-LC-MS/MS) method for determining 24-hydroxysterol and the isomers 25-hydroxycholesterol and 22S-hydroxycholesterol that enables simplified sample preparation, high sensitivity (~25 pg/mL cell lysis sample) and low sample variability. Only one sample transfer step was required for the entire process of cell lysis, derivatization and determination of selected oxysterols. During the procedure, autoxidation of cholesterol, a potential/common problem using standard analytical methods, was found to be negligible. The reversed phase AFFL-SPE-LC-MS/MS method utilizing a 1mm inner diameter column was validated, and used to determine levels of the oxysterol analytes in mouse fibroblast cell lines SSh-LII and NIH-3T3, and human cancer cell lines, BxPC3, HCT-15 and HCT-116. In BxPC3 cells, the AFFL-SPE-LC-MS/MS method was used to detect significant differences in 24S-OHC levels between vimentin+ and vimentin- heterogenous sub-populations. The methodology also allowed monitoring of significant alterations in 24S-OHC levels upon delivery of the Hedgehog (Hh) antagonist MS-0022 in HCT-116 colorectal carcinoma cell lines.

  8. Determination of phosphine and other fumigants in air samples by thermal desorption and 2D heart-cutting gas chromatography with synchronous SIM/Scan mass spectrometry and flame photometric detection.

    Science.gov (United States)

    Fahrenholtz, Svea; Hühnerfuss, Heinrich; Baur, Xaver; Budnik, Lygia Therese

    2010-12-24

    Fumigants and volatile industrial chemicals are particularly hazardous to health when a freight container is fumigated or the contaminated material is introduced into its enclosed environment. Phosphine is now increasingly used as a fumigant, after bromomethane--the former fumigant of choice--has been banned by the Montreal Protocol. We have enhanced our previously established thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method by integrating a second gas chromatographic dimension and a flame photometric detector to allow the simultaneous detection of phosphine and volatile organic compounds (VOCs), providing a novel application. A thermal desorption system is coupled to a two dimensional gas chromatograph using both mass spectrometric and flame photometric detection (TD-2D-GC-MS/FPD). Additionally, the collection of mass spectrometric SIM and Scan data has been synchronised, so only a single analysis is now sufficient for qualitative scanning of the whole sample and for sensitive quantification. Though detection limits for the herewith described method are slightly higher than in the previous method, they are in the low μL m(-3) range, which is not only below the respective occupational exposure and intervention limits but also allows the detection of residual contamination after ventilation. The method was developed for the separation and identification of 44 volatile substances. For 12 of these compounds (bromomethane, iodomethane, dichloromethane, 1,2-dichlorethane, benzene, tetrachloromethane, 1,2-dichloropropane, toluene, trichloronitromethane, ethyl benzene, phosphine, carbon disulfide) the method was validated as we chose the target compounds due to their relevance in freight container handling.

  9. Highly hydrogen-sensitive thermal desorption spectroscopy system for quantitative analysis of low hydrogen concentration (∼1 × 10(16) atoms/cm(3)) in thin-film samples.

    Science.gov (United States)

    Hanna, Taku; Hiramatsu, Hidenori; Sakaguchi, Isao; Hosono, Hideo

    2017-05-01

    We developed a highly hydrogen-sensitive thermal desorption spectroscopy (HHS-TDS) system to detect and quantitatively analyze low hydrogen concentrations in thin films. The system was connected to an in situ sample-transfer chamber system, manipulators, and an rf magnetron sputtering thin-film deposition chamber under an ultra-high-vacuum (UHV) atmosphere of ∼10(-8) Pa. The following key requirements were proposed in developing the HHS-TDS: (i) a low hydrogen residual partial pressure, (ii) a low hydrogen exhaust velocity, and (iii) minimization of hydrogen thermal desorption except from the bulk region of the thin films. To satisfy these requirements, appropriate materials and components were selected, and the system was constructed to extract the maximum performance from each component. Consequently, ∼2000 times higher sensitivity to hydrogen than that of a commercially available UHV-TDS system was achieved using H(+)-implanted Si samples. Quantitative analysis of an amorphous oxide semiconductor InGaZnO4 thin film (1 cm × 1 cm × 1 μm thickness, hydrogen concentration of 4.5 × 10(17) atoms/cm(3)) was demonstrated using the HHS-TDS system. This concentration level cannot be detected using UHV-TDS or secondary ion mass spectroscopy (SIMS) systems. The hydrogen detection limit of the HHS-TDS system was estimated to be ∼1 × 10(16) atoms/cm(3), which implies ∼2 orders of magnitude higher sensitivity than that of SIMS and resonance nuclear reaction systems (∼10(18) atoms/cm(3)).

  10. Thermal desorption-multiphoton ionization time-of-flight mass spectrometry of individual aerosol particles: a simplified approach for online single-particle analysis of polycyclic aromatic hydrocarbons and their derivatives.

    Science.gov (United States)

    Bente, Matthias; Sklorz, Martin; Streibel, Thorsten; Zimmermann, Ralf

    2009-04-01

    Online single-particle (SP) laser mass spectrometry (MS) is an important tool for fundamental and applied aerosol research. Usually laser desorption/ionization (LDI) is applied for ablation and ionization of atoms and molecular fragments from the nanometer- or micrometer-sized air-borne particles and time-of-flight analysers (TOFMS) are used for mass-selective detection of mainly inorganic analytes. The detection of molecular organic compounds is solely possible under very special experimental conditions and extremely dependent on the particle matrix and thus limited to special applications. Very recently it was shown that by implementation of a two-step laser desorption (LD) resonance-enhanced multiphoton ionization (REMPI) postionization approach the single-particulate molecular signature of polycyclic aromatic hydrocarbons (PAH) and their derivatives can be recorded (LD-REMPI-SP-TOFMS). By this, particles from different sources could be differentiated via the patterns of specific molecular source tracers such as retene for soft wood combustion or larger PAH as indicator for gasoline car emissions. One drawback of the LD-REMPI-SP-TOFMS method in particular for field applications is, however, the necessity of operation and adjustment of two lasers. In this paper the successful implementation of a thermal desorption step in single-particle mass spectrometry is described (TD-REMPI-SP-TOFMS). After size determination by particle velocimetry, individual particles are thermally desorbed on a heated surface in the ion source of the TOFMS. Desorbed molecules are ionized subsequently by REMPI, which addresses selectively PAH and molecular trace indicators. The TD-REMPI-SP-TOFMS concept was tested with reference particles and applied for automotive exhaust and ambient monitoring. The comparison of the results with the ones obtained by the two-laser approach (LD-REMPI-SP-TOFMS) indicates that the patented TD-REMPI-SP-TOFMS technology presented here is nearly equally well

  11. Determination of trichloromethane in workplace air by thermal desorption-gas chromatography%工作场所空气中三氯甲烷的热脱附气相色谱联用测定法

    Institute of Scientific and Technical Information of China (English)

    刘浏; 胡晓宇; 庞平; 傅佳; 钟磊

    2013-01-01

    To establish a method for determination of trichloromethane in workplace air by thermal desorption-gas chromatography.[Methods] The trichloromethane samples were collected from workplace air by Air Toxics adsorption tube,injection was conducted after desorption with Pekin Elmer Tubo Matrix AFD 650 thermal desorption instrument,and detection was performed by flame ionization detector.The retention time was adopted in qualitative analysis,and peak area was applied in quantitative evaluation.The laboratory examination and simulate experiments were conducted according to the Determination methods of air chemicals in workplace.[Results] The standard curve was linear in the content ranges of 0-300 μl,and the regression equation was Y =16.6 X + 2.8,r =1.000.The detection limit was 0.88 μg.The minimum detectable concentration was 0.20 mg/m3 while the sampling volume was 4.5 L.The repeatability was good,the relative standard deviation (RSD) was 3.14%-6.15%,the desorption efficiency was 103.0%-83.7%,and the sampling efficiency was 100%.The samples could be stably stored for 3 days in Air Toxics adsorption tube.[Conclusion] The method is simple and rapid,with high sensitivity,which is suitable for determination of trichloromethane in workplace air.%目的 建立测定工作场所空气中三氯甲烷的热脱附-气相色谱联用检测方法.方法 工作场所空气中的三氯甲烷用Air Toxics吸附管采样,用Pekin Elmer Tubo Matrix ATD-650热脱附仪脱附后进样,经毛细管色谱柱分离,氢火焰离子化检测器检测,以保留时间定性,峰面积定量.方法研究按照《工作场所空气中化学物质测定方法》的要求进行实验室实验及模拟现场实验.结果 该方法在0 ~ 300μl范围内呈线性关系,峰面积与含量的回归方程为Y=16.6X +2.8;r=1.000;检出限为0.88μg,当采样体积为4.5L时最低检出浓度为0.20 mg/m3;方法的重现性较好,不同浓度的相对标准偏差为3.14% ~6,15

  12. Determination of 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene and related compounds in marine pore water by automated thermal desorption-gas chromatography/mass spectrometry using disposable optical fiber

    Science.gov (United States)

    Eganhouse, Robert P.; DiFilippo, Erica L

    2015-01-01

    A method is described for determination of ten DDT-related compounds in marine pore water based on equilibrium solid-phase microextraction (SPME) using commercial polydimethylsiloxane-coated optical fiber with analysis by automated thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Thermally cleaned fiber was directly exposed to sediments and allowed to reach equilibrium under static conditions at the in situ field temperature. Following removal, fibers were rinsed, dried and cut into appropriate lengths for storage in leak-tight containers at -20°C. Analysis by TD-GC/MS under full scan (FS) and selected ion monitoring (SIM) modes was then performed. Pore-water method detection limits in FS and SIM modes were estimated at 0.05-2.4ng/L and 0.7-16pg/L, respectively. Precision of the method, including contributions from fiber handling, was less than 10%. Analysis of independently prepared solutions containing eight DDT compounds yielded concentrations that were within 6.9±5.5% and 0.1±14% of the actual concentrations in FS and SIM modes, respectively. The use of optical fiber with automated analysis allows for studies at high temporal and/or spatial resolution as well as for monitoring programs over large spatial and/or long temporal scales with adequate sample replication. This greatly enhances the flexibility of the technique and improves the ability to meet quality control objectives at significantly lower cost.

  13. Fatty acid profiling of raw human plasma and whole blood using direct thermal desorption combined with gas chromatography-mass spectrometry

    NARCIS (Netherlands)

    Akoto, Lawrence; Vreuls, Rene J. J.; Irth, Hubertus; Pel, Roel; Stellaard, Frans

    2008-01-01

    Gas chromatography (GC) has in recent times become an important tool for the fatty acid profiling of human blood and plasma. An at-line procedure used in the fatty acid profiling of whole/intact aquatic micro-organisms without any sample preparation was adapted for this work. A direct thermal

  14. Fatty acid profiling of raw human plasma and whole blood using direct thermal desorption combined with gas chromatography–mass spectrometry

    NARCIS (Netherlands)

    Akoto, L.; Vreuls, R.J.J.; Irth, H.; Pel, R.; Stellaard, F.

    2008-01-01

    Gas chromatography (GC) has in recent times become an important tool for the fatty acid profiling of human blood and plasma. An at-line procedure used in the fatty acid profiling of whole/intact aquatic micro-organisms without any sample preparation was adapted for this work. A direct thermal

  15. Desorption of Lipases Immobilized on Octyl-Agarose Beads and Coated with Ionic Polymers after Thermal Inactivation. Stronger Adsorption of Polymers/Unfolded Protein Composites

    Directory of Open Access Journals (Sweden)

    Jose J. Virgen-Ortíz

    2017-01-01

    Full Text Available Lipases from Candida antarctica (isoform B and Rhizomucor miehei (CALB and RML have been immobilized on octyl-agarose (OC and further coated with polyethylenimine (PEI and dextran sulfate (DS. The enzymes just immobilized on OC supports could be easily released from the support using 2% SDS at pH 7, both intact or after thermal inactivation (in fact, after inactivation most enzyme molecules were already desorbed. The coating with PEI and DS greatly reduced the enzyme release during thermal inactivation and improved enzyme stability. However, using OC-CALB/RML-PEI-DS, the full release of the immobilized enzyme to reuse the support required more drastic conditions: a pH value of 3, a buffer concentration over 2 M, and temperatures above 45 °C. However, even these conditions were not able to fully release the thermally inactivated enzyme molecules from the support, being necessary to increase the buffer concentration to 4 M sodium phosphate and decrease the pH to 2.5. The formation of unfolded protein/polymers composites seems to be responsible for this strong interaction between the octyl and some anionic groups of OC supports. The support could be reused five cycles using these conditions with similar loading capacity of the support and stability of the immobilized enzyme.

  16. Effects of soil particle size and organic matter content on thermal desorption of polybrominated diphenyl ether%土壤粒径及有机质对多溴二苯醚热脱附的影响

    Institute of Scientific and Technical Information of China (English)

    傅海辉; 黄启飞; 朱晓华; 何洁; 唐振武; 孟昭福

    2013-01-01

    Under laboratory conditions,the two effect factors of soil particle size and organic matter content were studied in order to give the theory basis PBDEs of thermal desorption from contaminated soils.The results showed that the removal rates of PBDEs from different particle sizes of soils(75,75 ~ 125,125 ~ 250,250 ~425 and 425 ~ 850 μm) contaminated by PBDEs were 49.53%,73.88%,79.39%,83.56%,87.09%,respectively.The total removal rate of PBDEs increased with the particle size increasing,and BDE209 was removed more easily than BDE206,BDE207 and BDE208 from soils.In addition,the PBDEs removal rate from the soil oxidated with H2O2 was higher than that from the original soil with the same PBDEs concentration below 450℃,which showed that soil organic matter may inhibit the thermal desorption of PBDEs.%在实验室条件下,研究了土壤粒径与土壤有机质含量对多溴二苯醚(PBDEs)热脱附的影响,以期为PBDEs污染土壤热脱附修复提供理论依据.实验结果表明,300℃停留30 min条件下,粒径为<75、75~ 125、125~250、250 ~425和425~ 850 μm的土壤中PBDEs去除率分别为49.53%、73.88%、79.39%、83.56%和87.09%,PBDEs总去除率随粒径的增大而增大,土壤BDE209较BDE206、BDE207和BDE208更易于脱除.此外,温度低于450℃时,H2O2氧化部分去除有机质后土壤中PBDEs的去除率较原土高;表明,土壤有机质可能抑制土壤中PBDEs的热脱附.

  17. A novel quantitation approach for maximizing detectable targets for offensive/volatile odorants with diverse functional groups by thermal desorption-gas chromatography-mass spectrometry

    Science.gov (United States)

    Kim, Yong-Hyun; Kim, Ki-Hyun

    2016-07-01

    A multitude of analytical systems are needed to analyze diverse odorants with various functionalities. In this study, an experimental method was developed to assess the maximum covering range of odorants using a single experimental setup consisting of a thermal desorber-gas chromatography-mass spectrometry system. To this end, a total of 20 offensive odorants (aldehyde, ketone, ester, alcohol, aromatic, sulfide, amine, and carboxyl) were selected and tested by a single system. The analytical results of standards and environmental samples were evaluated in a number of respects. In the analysis of the standards, all targets were quantified via Carbopack (C + B + X) tube sampling while operating the thermal desorber at -25 °C. The method detection limits of 18 targets (exception of 2 out of the 20 targets: acetaldehyde and methanethiol) were excellent (mean 0.04 ± 0.03 ppb) in terms of their odor threshold values (74.7 ± 140 ~ 624 ± 1,729 ppb). The analysis of organic fertilizer plant samples at a pig farm (slurry treatment facility, compost facility, and ambient air) confirmed the presence of 18 odorants from 0.03 ppb (dimethyldisulfide, ambient sample) to 522 ppb (methyl ethyl ketone, slurry treatment facility). As such, our method allowed simultaneous quantitation of most key odorants with sufficient reliability and sensitivity.

  18. A novel quantitation approach for maximizing detectable targets for offensive/volatile odorants with diverse functional groups by thermal desorption-gas chromatography-mass spectrometry.

    Science.gov (United States)

    Kim, Yong-Hyun; Kim, Ki-Hyun

    2016-07-11

    A multitude of analytical systems are needed to analyze diverse odorants with various functionalities. In this study, an experimental method was developed to assess the maximum covering range of odorants using a single experimental setup consisting of a thermal desorber-gas chromatography-mass spectrometry system. To this end, a total of 20 offensive odorants (aldehyde, ketone, ester, alcohol, aromatic, sulfide, amine, and carboxyl) were selected and tested by a single system. The analytical results of standards and environmental samples were evaluated in a number of respects. In the analysis of the standards, all targets were quantified via Carbopack (C + B + X) tube sampling while operating the thermal desorber at -25 °C. The method detection limits of 18 targets (exception of 2 out of the 20 targets: acetaldehyde and methanethiol) were excellent (mean 0.04 ± 0.03 ppb) in terms of their odor threshold values (74.7 ± 140 ~ 624 ± 1,729 ppb). The analysis of organic fertilizer plant samples at a pig farm (slurry treatment facility, compost facility, and ambient air) confirmed the presence of 18 odorants from 0.03 ppb (dimethyldisulfide, ambient sample) to 522 ppb (methyl ethyl ketone, slurry treatment facility). As such, our method allowed simultaneous quantitation of most key odorants with sufficient reliability and sensitivity.

  19. Analysis of volatile organic compounds released from the decay of surrogate human models simulating victims of collapsed buildings by thermal desorption-comprehensive two-dimensional gas chromatography-time of flight mass spectrometry.

    Science.gov (United States)

    Agapiou, A; Zorba, E; Mikedi, K; McGregor, L; Spiliopoulou, C; Statheropoulos, M

    2015-07-01

    Field experiments were devised to mimic the entrapment conditions under the rubble of collapsed buildings aiming to investigate the evolution of volatile organic compounds (VOCs) during the early dead body decomposition stage. Three pig carcasses were placed inside concrete tunnels of a search and rescue (SAR) operational field terrain for simulating the entrapment environment after a building collapse. The experimental campaign employed both laboratory and on-site analytical methods running in parallel. The current work focuses only on the results of the laboratory method using thermal desorption coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (TD-GC×GC-TOF MS). The flow-modulated TD-GC×GC-TOF MS provided enhanced separation of the VOC profile and served as a reference method for the evaluation of the on-site analytical methods in the current experimental campaign. Bespoke software was used to deconvolve the VOC profile to extract as much information as possible into peak lists. In total, 288 unique VOCs were identified (i.e., not found in blank samples). The majority were aliphatics (172), aromatics (25) and nitrogen compounds (19), followed by ketones (17), esters (13), alcohols (12), aldehydes (11), sulfur (9), miscellaneous (8) and acid compounds (2). The TD-GC×GC-TOF MS proved to be a sensitive and powerful system for resolving the chemical puzzle of above-ground "scent of death".

  20. Characterisation of the flavour profile from Graciano Vitis vinifera wine variety by a novel dual stir bar sorptive extraction methodology coupled to thermal desorption and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Arbulu, Maria; Sampedro, M Carmen; Sanchez-Ortega, Alicia; Gómez-Caballero, Alberto; Unceta, Nora; Goicolea, M Aranzazu; Barrio, Ramón J

    2013-05-13

    The aim of this work was to develop a new analytical technique for the study of the organoleptic compounds (flavour profile) of the Graciano Vitis vinifera wine variety. The cv. Graciano is a singular variety of red grapes with its origins in La Rioja and Navarra (northern Spain). This variety transfers an intense red colour, aroma and high acidity to musts and provides greater longevity and, consequently, a better capacity for ageing wine. A new dual-stir bar sorptive extraction approach coupled with thermal desorption (TD) and GC-MS has been used to extract the volatile and semivolatile compounds. In this extraction step, the optimal values for the experimental variables were obtained through the Response Surface Methodology (RSM). Full scan chromatogram data were evaluated with two deconvolution software tools, and the results were compared. The volatile and semivolatile components were identified with an MS match ≥80%. As a result, the flavour metabolome of the Graciano Vitis vinifera wine variety was obtained, and 205 metabolites were identified using different databases. These metabolites were grouped into esters, acids, alcohols, nitrogen compounds, furans, lactones, ketones, aldehydes, phenols, terpenes, norisoprenoids, sulphur compounds, acetals and pyrans. The majority of the metabolites observed had already been reported in the literature; however, this work also identified new, previously unreported metabolites in red wines, which may be characteristic of the Graciano variety. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Fast and solvent-free quantitation of boar taint odorants in pig fat by stable isotope dilution analysis-dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry.

    Science.gov (United States)

    Fischer, Jochen; Haas, Torsten; Leppert, Jan; Lammers, Peter Schulze; Horner, Gerhard; Wüst, Matthias; Boeker, Peter

    2014-09-01

    Boar taint is a specific off-odour of boar meat products, known to be caused by at least three unpleasant odorants, with very low odour thresholds. Androstenone is a boar pheromone produced in the testes, whereas skatole and indole originate from the microbial breakdown of tryptophan in the intestinal tract. A new procedure, applying stable isotope dilution analysis (SIDA) and dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry (dynHS-TD-GC/TOFMS) for the simultaneous quantitation of these boar taint compounds in pig fat was elaborated and validated in this paper. The new method is characterised by a simple and solvent-free dynamic headspace sampling. The deuterated compounds d3-androstenone, d3-skatole and d6-indole were used as internal standards to eliminate matrix effects. The method validation performed revealed low limits of detection (LOD) and quantitation (LOQ) with high accuracy and precision, thus confirming the feasibility of the new dynHS-TD-GC/TOFMS approach for routine analysis.

  2. Desorption process of deuterium from zircaloys and their oxides

    Energy Technology Data Exchange (ETDEWEB)

    Nakamichi, Haruo; Kinoshita, Chiken; Hara, Masahiro [Kyushu Univ., Fukuoka (Japan)

    1997-11-01

    It is well known that hydrogen behavior plays an important role on the oxidation process of zircaloys. We have investigated the desorption process of deuterium from three kinds of zircaloys (Zry-2, Zry-4 and high-Fe and Ni-Zry-2) and their oxides using thermal desorption spectrometry (TDS). The purpose of the present paper is to get insight into the effect of alloying elements on the desorption behavior of deuterium from the zircaloys and their oxides. We have also performed in-situ observations through TEM for getting the relation between the desorption process and microstructural evolution. The desorption of D{sub 2} implanted by an ion accelerator occurs in two stages; the first and the second stages appear at around 350 K and around 700 K for the metallic zircaloys, respectively. For their oxide films, on the other hand, the desorption rate of D{sub 2} is much higher than that for the metallic zircaloys. It is found that the desorption rate depends strongly on the kind of zircaloys, especially on the concentration of Fe and Ni. From TEM result, it is found that the first desorption stage for the metallic specimens is correlated to the dissolution of the hydrides. (author)

  3. Laser desorption of NO from a thick C 60 film

    Science.gov (United States)

    Hoger, T.; Marzok, C.; Jongma, R. T.; Zacharias, H.

    2006-09-01

    The desorption of NO molecules from a thick C 60 film is reported. A thermal desorption spectrum indicates two adsorption sites with binding energies of Eb = 0.30 eV and 0.55 eV. For laser desorption the fullerene surface is exposed to NO and excited by 7 ns UV laser pulses. Desorbing NO molecules are recorded state selectively as well as time resolved. The time-of-flight measurement indicates three different desorption pathways. A fast channel shows rovibronic temperatures of Trot( v″ = 0) = 370 K, Trot( v″ = 1) = 390 K and Tvib = 610 K as well as strong rotational-translational coupling. The desorption yield for the fast channel increases linearly with pulse energy with a desorption cross section of σ = (5.1 ± 0.9) × 10 -17 cm 2. Dominating the signal for small J″ values is a slow channel with low rotational and translational temperatures of about 110 K. We assign this peak to a laser-induced thermal desorption. For large pump-probe delays the data deviate from the Maxwellian flux distribution and a third channel appears with extremely late arrival times.

  4. Beryllium Desorption from Sediments

    Science.gov (United States)

    Boschi, V.; Willenbring, J. K.

    2015-12-01

    Beryllium isotopes have provided a useful tool in the field of geochronology and geomorphology over the last 25 years. The amount of cosmogenic meteoric 10Be and native 9Be absorbed to soils often scales with the residence time and chemical weathering of sediments in a landscape, respectively. Thus, the concentrations in river sediment may be used to quantify the denudation of specific watersheds. When deposited in ocean sediment, these concentrations are thought to record the history of denudation on Earth over the last ~10 Ma. The use of both isotopes often relies on the premise of beryllium retention to sediment surfaces in order to preserve a landscape's erosion and weathering signature. Changes in setting, en route from the soil to fluvial system to the ocean, can cause beryllium desorption and may preclude some applications of the 10Be/9Be system. Four mechanisms were tested to determine the desorption potential of beryllium including a reduction in pH, an increase in ionic strength and complexation with soluble organic and inorganic species. These processes have the potential to mobilize beryllium into solution. For example, by both reducing the pH and increasing the ionic strength, competition for adsorption sites increases, potentially liberating beryllium from the sediment surface. In addition, organic and inorganic ligands can complex beryllium causing it to become mobilized. To determine which of these alterations influence beryllium desorption and to quantify the effect, we prepared separate solutions of beryllium bound to minerals and organic compounds and measured beryllium concentrations in solution before and after adjusting the pH, ionic strength, and changing inorganic and organic ligand concentrations. We conclude from our observations that overall, beryllium sorbed to organic compounds was more resistant to desorption relative to mineral-associated beryllium. Among the methods tested, a reduction in pH resulted in the greatest amount of

  5. Au and Al Schottky barrier formation on GaAs (100) surfaces prepared by thermal desorption of a protective arsenic coating

    Energy Technology Data Exchange (ETDEWEB)

    Spindt, C.J.; Yamada, M.; Meissner, P.L.; Miyano, K.E.; Herrera, A.; Spicer, W.E. (Stanford Univ., CA (United States). Stanford Electronics Labs.); Arko, A.J. (Los Alamos National Lab., NM (United States)); Woodall, J.M.; Pettit, G.D. (International Business Machines Corp., Yorktown Heights, NY (United States). Thomas J. Watson Research Center)

    1991-01-01

    Photoelectron spectroscopy has been used as a tool to investigate the initial stages of Schottky barrier formation on GaAs (100) surfaces. This is a popular technique that has been used by many researchers in the past to measure the band bending (or shift) of the valence band and conduction band (a measure of the Schottky barrier shift), while the Fermi level remains fixed at the system ground (i.e., the ground of the spectrometer). Metal deposition on a semiconductor surface can alter the Schottky barrier at the surface and pin the Fermi level near the middle of the energy gap. Extremely clean and crystallographically perfect surfaces are required in this study. Toward this end, a method of protecting the GaAs surface was employed which consists of capping the GaAs surface with a layer of As. Upon introduction into the high vacuum system the As is thermally desorbed, revealing a pure GaAs surface. Our work was motivated by a previous study (Brillson et al) on similarly capped specimens, which suggested that metal overlayers do not pin the Schottky barrier in GaAs. Barrier heights varied by as much as 0.75 eV between Al and Au overlayers. This large energy range is a striking result in view of the fact that a considerable number of prior studies on both (110) and (100) surfaces have found that all metals will pin within a narrow (0.25 eV) range at midgap. We repeated the measurements of Brillson on the identically doped samples used in their study using two extreme range metals of Au and Al as overlayers. We found that the barrier height measurements on low doped n-type samples used in this work and in the previous work are affected by photovoltaic effects, even at room temperature. This was determined from taking spectra at a number of temperatures between 20 K and room temperature and looking for shifts. 16 refs., 7 figs.

  6. Analysis of the Volatile Organic Components in Malus hupenhensis Rehd Leaves by Direct Thermal Desorption Gas Chromatography-mass Spectrometry%湖北海棠叶挥发性成分的 DTD-GC/MS 分析∗

    Institute of Scientific and Technical Information of China (English)

    王宵; 杜业云; 杨志斌; 李晖; 杨柳

    2015-01-01

    The method of direct thermal desorption (DTD)combed with gas chromatography-mass spectrometry (GC/MS)was applied to analyze the volatile organic components in leaves of Malus hupenhensis for the first time,and 46 kinds of volatile organic components were identified.The main chemical components were hydrocarbons,esters,alcohols,ke-tones,vinyl,aldehydes and so on.8 kinds of components can be used as spice additives,5 types can be used for medical purposes,2 kinds can be used as insecticides.This method of analyzing Malus hupenhensis leaves components had good re-peatability,and was simple,efficient,sensitive and environment-friendly.%采用直接热脱附—气相色谱/质谱联用技术(DTD-GC/MS)首次分析了湖北海棠叶挥发性成分,共检测鉴定出有效成分46种,主要包括烷烃类、酯类、醇类、酮类、烯类、醛类等化合物。其中,8种可用作香料添加剂,5种可作医疗用途,2种可用于杀虫剂。采用直接热脱附—气相色谱/质谱法分析湖北海棠叶挥发成分重现性好、操作简单、效率高、绿色环保。

  7. Development of a Method for the Quantitation of Three Thiols in Beer, Hop, and Wort Samples by Stir Bar Sorptive Extraction with in Situ Derivatization and Thermal Desorption-Gas Chromatography-Tandem Mass Spectrometry.

    Science.gov (United States)

    Ochiai, Nobuo; Sasamoto, Kikuo; Kishimoto, Toru

    2015-08-05

    A method for analysis of hop-derived polyfunctional thiols, such as 4-sulfanyl-4-methylpentan-2-one (4S4M2Pone), 3-sulfanylhexan-1-ol (3SHol), and 3-sulfanylhexyl acetate (3SHA), in beer, hop water extract, and wort at nanogram per liter levels was developed. The method employed stir bar sorptive extraction with in situ derivatization (der-SBSE) using ethyl propiolate (ETP), followed by thermal desorption and gas chromatography-tandem mass spectrometry (TD-GC-MS/MS) with selected reaction monitoring (SRM) mode. A prior step involved structural identification of the ETP derivatives of the thiols by TD-GC-quadrupole-time-of-flight mass spectrometry with parallel sulfur chemiluminescence detection (Q-TOF-MS/SCD) after similar der-SBSE. The der-SBSE conditions of the ETP concentration, buffer concentration, salt addition, and extraction time profiles were investigated, and the performance of the method was demonstrated with spiked beer samples. The limits of detection (LODs) (0.19-27 ng/L) are below the odor threshold levels of all analytes. The apparent recoveries at 10-100 ng/L (99-101%) and the repeatabilities [relative standard deviation (RSD) of 1.3-7.2%; n = 6] are also good. The method was successfully applied to the determination of target thiols at nanogram per liter levels in three kinds of beer samples (hopped with Cascade, Citra, and Nelson Sauvin) and the corresponding hop water extracts and wort samples. There was a clear correlation between the determined values and the characteristics of citrus hop aroma for each sample.

  8. Development of a new multi-residue laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry method for the detection and quantification of pesticides and pharmaceuticals in wastewater samples.

    Science.gov (United States)

    Boisvert, Michel; Fayad, Paul B; Sauvé, Sébastien

    2012-11-19

    A new solid phase extraction (SPE) method coupled to a high throughput sample analysis technique was developed for the simultaneous determination of nine selected emerging contaminants in wastewater (atrazine, desethylatrazine, 17β-estradiol, ethynylestradiol, norethindrone, caffeine, carbamazepine, diclofenac and sulfamethoxazole). We specifically included pharmaceutical compounds from multiple therapeutic classes, as well as pesticides. Sample pre-concentration and clean-up was performed using a mixed-mode SPE cartridge (Strata ABW) having both cation and anion exchange properties, followed by analysis by laser diode thermal desorption atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). The LDTD interface is a new high-throughput sample introduction method, which reduces total analysis time to less than 15s per sample as compared to minutes with traditional liquid-chromatography coupled to tandem mass spectrometry (LC-MS/MS). Several SPE parameters were evaluated in order to optimize recovery efficiencies when extracting analytes from wastewater, such as the nature of the stationary phase, the loading flow rate, the extraction pH, the volume and composition of the washing solution and the initial sample volume. The method was successfully applied to real wastewater samples from the primary sedimentation tank of a municipal wastewater treatment plant. Recoveries of target compounds from wastewater ranged from 78% to 106%, the limit of detection ranged from 30 to 122ng L(-1) while the limit of quantification ranged from 90 to 370ng L(-1). Calibration curves in the wastewater matrix showed good linearity (R(2)≥0.991) for all target analytes and the intraday and interday coefficient of variation was below 15%, reflecting a good precision.

  9. Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method.

    Science.gov (United States)

    Lonappan, Linson; Pulicharla, Rama; Rouissi, Tarek; Brar, Satinder K; Verma, Mausam; Surampalli, Rao Y; Valero, José R

    2016-02-12

    Diclofenac (DCF), a prevalent non-steroidal anti-inflammatory drug (NSAID) is often detected in wastewater and surface water. Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a reliable, rapid and sensitive method based on laser diode thermal desorption/atmospheric pressure chemical ionization (LDTD/APCI) coupled with tandem mass spectrometry (MS/MS) has been developed for the quantification of DCF in wastewater and wastewater sludge. An established conventional LC-ESI-MS/MS (liquid chromatography-electrospray ionization-tandem mass spectrometry) method was compared with LDTD-APCI-MS/MS approach. The newly developed LDTD-APCI-MS/MS method reduced the analysis time to 12s in lieu of 12 min for LC-ESI-MS/MS method. The method detection limits for LDTD-APCI-MS/MS method were found to be 270 ng L(-1) (LOD) and 1000 ng L(-1) (LOQ). Furthermore, two extraction procedures, ultrasonic assisted extraction (USE) and accelerated solvent extraction (ASE) for the extraction of DCF from wastewater sludge were compared and ASE with 95.6 ± 7% recovery was effective over USE with 86 ± 4% recovery. The fate and partitioning of DCF in wastewater (WW) and wastewater sludge (WWS) in wastewater treatment plant was also monitored at various stages of treatment in Quebec Urban community wastewater treatment plant. DCF exhibited affinity towards WW than WWS with a presence about 60% of DCF in WW in contrary with theoretical prediction (LogKow=4.51).

  10. Development and validation of a method for air-quality and nuisance odors monitoring of volatile organic compounds using multi-sorbent adsorption and gas chromatography/mass spectrometry thermal desorption system.

    Science.gov (United States)

    Ribes, Alejandra; Carrera, Guillem; Gallego, Eva; Roca, Xavier; Berenguer, M A José; Guardino, Xavier

    2007-01-26

    An analytical method based on thermal desorption (TD) coupled to gas chromatography (GC) and mass spectrometry detection (MS) has been developed and validated for the determination of a wide range of odor nuisance and air-quality volatile organic compounds (VOC) in air. New generation isocyanates, isocyanato- and isothiocyanatocyclohexane, have been included for the first time as target compounds due to their high occurrence in air samples. A dynamic air sampling method to trap gas and vapor on multi-sorbent tubes using portable pump equipment has been also developed. Sorbent tubes were filled with Carbotrap (70mg), Carbopack X (100mg) and Carboxen-569 (90mg). Validation of the TD-GC-MS method showed good selectivity, sensibility and precision according to Compendium Method TO-17 (US Environment Protection Agency) criteria. Limits of detection (signal-to-noise=3, ng in tube) ranges were 0.004-0.03ng (alcanes), 0.001-0.1ng (aromatics), 0.03-14ng (aldehydes), 0.003-7ng (alcohols), 0.003-0.04ng (chlorides), 0.02-0.5ng (esters), 0.002-0.1ng (ketones), 0.01-0.53ng (terpenes), 14-97ng (amides), 0.2-10ng (isocyanates) and 0.001ng (carbon disulfide). The linear dynamic range was over 3-5 orders of magnitude, depending of the VOC. TD-GC-MS analysis was reproducible, with relative standard deviation (n=5) within 20%. VOCs breakthrough examination showed no significant losses when about 2000ng standard was prepared. In order to evaluate the performance of the developed method on real samples, several industrial and urban air samples were analysed. VOCs were found to be stable on the sorbent tubes for at least 1 week when stored at 4 degrees C.

  11. Study of the mechanisms of heavy-ion induced desorption on accelerator-relevant materials; Untersuchung der Mechanismen schwerioneninduzierter Desorption an beschleunigerrelevanten Materialien

    Energy Technology Data Exchange (ETDEWEB)

    Bender, Markus

    2008-02-22

    The ion beam loss induced desorption is a performance limitation for low charge state heavy ion accelerators. If charge exchanged projectile ions get lost onto the beam pipe, desorption of gas is stimulated resulting in a pressure increase inside of the synchrotron and thus, a dramatically reduction of the beam life time. To minimize the amount of desorbed gas an experimental program has been started to measure the desorption yields (released gas molecules per incident ion) of various materials and different projectile ions. The present work is a contribution to the understanding of the physical processes behind the ion beam loss induced desorption. The yield measurements by the pressure rise method have been combined for the rst time with in situ ion beam analysis technologies such as ERDA and RBS. With this unique method the desorption behavior of a sample can be correlated to its surface and bulk properties. The performed experiments with 1,4 MeV/u Xenon-Ions show that the ion induced desorption is mainly a surface effect. Sputtered oxide layers or impurities do not contribute to the desorbed gas significantly. Nevertheless bulk properties play an important role in the desorption strength. Pure metallic samples desorb less gas than isolating materials under swift heavy ion irradiation. From the experimental results it was possible to estimate the desorption yields of various materials under ion bombardment by means of an extended inelastic thermal-spike-model. The extension is the combination of the thermal-spike's temperature map with thermal desorption. Within this model the ion induced desorption can be regarded as the release of adsorbates from a transient overheated spot on the samples surface around the ion impact. Finally a copper substrate with a gold coated surface was developed and proposed as a suitable material for a beam loss collimator with minimum desorption to ensure the performance of GSI's SIS18 in high current beam operation. (orig.)

  12. Measurement of breakthrough volumes of volatile chemical warfare agents on a poly(2,6-diphenylphenylene oxide)-based adsorbent and application to thermal desorption-gas chromatography/mass spectrometric analysis.

    Science.gov (United States)

    Kanamori-Kataoka, Mieko; Seto, Yasuo

    2015-09-04

    To establish adequate on-site solvent trapping of volatile chemical warfare agents (CWAs) from air samples, we measured the breakthrough volumes of CWAs on three adsorbent resins by an elution technique using direct electron ionization mass spectrometry. The trapping characteristics of Tenax(®) TA were better than those of Tenax(®) GR and Carboxen(®) 1016. The latter two adsorbents showed non-reproducible breakthrough behavior and low VX recovery. The specific breakthrough values were more than 44 (sarin) L/g Tenax(®) TA resin at 20°C. Logarithmic values of specific breakthrough volume for four nerve agents (sarin, soman, tabun, and VX) showed a nearly linear correlation with the reciprocals of their boiling points, but the data point of sulfur mustard deviated from this linear curve. Next, we developed a method to determine volatile CWAs in ambient air by thermal desorption-gas chromatography (TD-GC/MS). CWA solutions that were spiked into the Tenax TA(®) adsorbent tubes were analyzed by a two-stage TD-GC/MS using a Tenax(®) TA-packed cold trap tube. Linear calibration curves for CWAs retained in the resin tubes were obtained in the range between 0.2pL and 100pL for sarin, soman, tabun, cyclohexylsarin, and sulfur mustard; and between 2pL and 100pL for VX and Russian VX. We also examined the stability of CWAs in Tenax(®) TA tubes purged with either dry or 50% relative humidity air under storage conditions at room temperature or 4°C. More than 80% sarin, soman, tabun, cyclohexylsarin, and sulfur mustard were recovered from the tubes within 2 weeks. In contrast, the recoveries of VX and Russian VX drastically reduced with storage time at room temperature, resulting in a drop to 10-30% after 2 weeks. Moreover, we examined the trapping efficiency of Tenax TA(®) adsorbent tubes for vaporized CWA samples (100mL) prepared in a 500mL gas sampling cylinder. In the concentration range of 0.2-2.5mg/m(3), >50% of sarin, soman, tabun, cyclohexylsarin, and HD were

  13. Simple sample transfer technique by internally expanded desorptive flow for needle trap devices.

    Science.gov (United States)

    Eom, In-Yong; Pawliszyn, Janusz

    2008-07-01

    Needle trap devices (NTDs) are improving in simplicity and usefulness for sampling volatile organic compounds (VOCs) since their first introduction in early 2000s. Three different sample transfer methods have been reported for NTDs to date. All methods use thermal desorption and simultaneously provide desorptive flow to transfer desorbed VOCs into a GC separation column. For NTDs having 'side holes', GC carrier gas enters a 'side hole' and passes through sorbent particles to carry desorbed VOCs, while for NTD not having a 'side hole', clean air as desorptive flow can be provided through a needle head by a air tight syringe to sweep out desorbed VOCs or water vapor has been reported recently to be used as desorptive flow. We report here a new simple sample transfer technique for NTDs, in which no side holes and an external desorptive flow are required. When an NTD enriched by a mixture of benzene, toluene, ethylbenzene, and xylene (BTEX) or n-alkane mixture (C6-C15) is exposed to the hot zone of GC injector, the expanding air above the packed sorbent transfers the desorbed compounds from the sorbent to the GC column. This internal air expansion results in clean and sharp desorption profiles for BTEX and n-alkane mixture with no carryover. The effect of desorption temperature, desorption time, and overhead volumes was studied. Decane having vapor pressure of approximately 1 Torr at 20 degrees C showed approximately 1% carryover at the moderate thermal desorption condition (0.5 min at 250 degrees C).

  14. Analysis of Volatile Components of Fresh and Cooked Frankincense by Thermal Desorption and GC/MS%热脱附-气相色谱/质谱联用法分析生、炙乳香挥发性成分

    Institute of Scientific and Technical Information of China (English)

    吴岳华; 周围; 张雅珩; 魏荣霞

    2013-01-01

    为了研究天然乳香的挥发性成分及生、炙乳香挥发性成分的异同,为乳香挥发油的工艺优化和品质评估提供科学的依据,同时为固体挥发性成分分析提供新思路,采用热脱附-气相色谱/质谱联用技术直接对自然状态下乳香颗粒的挥发性成分进行分析.结合NIST 08标准谱库检索和Mass WorksTM质谱解析软件的分析结果,在分离出的40余种挥发性成分中,最终确定出20种化学成分.结果表明:生、炙乳香中的挥发性成分主要由单萜、醇及酯类物质构成,其中以醋酸辛酯含量最高,约占挥发性成分的50%;其次为1-辛醇、芳樟醇、乙酸龙脑酯,在生乳香中的含量分别为19.44%、2.27%、2.64%,在炙乳香中的含量分别为9.12%、2.61%、1.33%.%In order to make clear the natural volatile composition of frankincense and the differences between fresh frankincense and cooked frankincense, to provide a scientific basis on improving techniques and evaluating qualities of frankincense volatile oil, and to offer a new method to analyse volatile composition from solid for reference, the volatile components of natural fresh and cooked frankincense were extracted and determined directly by thermal desorption and gas chromatography-mass spectrornetry(GC/MS). More than 40 components are separated and 20 components are identified by comparing their mass spectra with those contained in the NIST mass spectral database and Mass Works?software. The results show that the main components includ terpenes, alcohol and esters et al,n-octyl acetate is the most important volatile components to frankincense. The normalized peak areas exceed 50% both in fresh frankincense and cooked frankincense,followed by 1-octanol, lina-lool and bornyl acetate, the normalized peak areas in fresh frankincense are 19. 44%, 2. 27% and 2. 64%, in cooked frankincense are 9. 12%, 2. 61% and 1. 33%, respectively.

  15. Photon stimulated desorption of and nuclear resonant scattering by noble gas atoms at solid surfaces

    CERN Document Server

    Ikeda, Akihiko

    2015-01-01

    When a noble gas atom approaches a solid surface, it is adsorbed via the Van der Waals force, which is called physisorption. In this thesis, several experimental results concerning physisorbed atoms at surfaces are presented. First, photon stimulated desorption of Xe atoms from a Au substrate using nano-second laser is presented. With the time-of-flight measurements, the translational temperature and the desorption yield of desorbing Xe as a function of laser fluence are obtained. It is discovered that there are non-thermal and thermal desorption pathways. It is discussed that the former path involves a transient formation of the negative ion of Xe. The desorption flux dependence of the thermal pathway is also investigated. We found that at a large desorption fluxes the desorption flow is thermalized due to the post-desorption collisions. The resultant velocity and the temperature of the flow is found to be in good agreement with the theoretical predictions based on the Knudsen layer formation. Lastly, nuclea...

  16. Effect of Ultrasound on Desorption Equilibrium%超声场对氢键缔合体系解吸平衡的影响研究

    Institute of Scientific and Technical Information of China (English)

    秦炜; 原永辉; 戴猷元

    2001-01-01

    Effects of ultrasound on intensification of separation process were investigated through the experiment of desorption equilibrium behavior. Tri-butyl phosphate (TBP) on NKA-Ⅱ resin and phenol on a solvent impregnated resin, CL-TBP resin, were used for desorption processes. The desorption rate was measured with and without ultrasound. Desorption equilibrium was studied under various ultrasonic power densities or thermal infusion. Results showed that the desorption rate with ultrasound was much higher than that with normal thermal infusion. Both ultrasound and thermal infusion broke the desorption equilibrium existed at room temperature. However, after the systems were cooled down, the amount of solute desorbed in the liquid phase in the presence of ultrasound was much higher than that at the temperature corresponding to the same ultrasound power. It is proved that the initial desorption equilibrium was broken as a result of the spot energy effect of ultrasound.``

  17. Hydrogen absorption and desorption in nanocrystalline LaMg{sub 2}Ni

    Energy Technology Data Exchange (ETDEWEB)

    Di Chio, M. [Dipartimento di Chimica IFM and NIS-Centre of Excellence, Universita di Torino, Via P. Giuria, 9-10125 Torino (Italy); Schiffini, L. [Dipartimento di Chimica, Universita di Sassari, Via Vienna, 2-07100 Sassari (Italy); Enzo, S. [Dipartimento di Chimica, Universita di Sassari, Via Vienna, 2-07100 Sassari (Italy); Cocco, G. [Dipartimento di Chimica, Universita di Sassari, Via Vienna, 2-07100 Sassari (Italy); Baricco, M. [Dipartimento di Chimica IFM and NIS-Centre of Excellence, Universita di Torino, Via P. Giuria, 9-10125 Torino (Italy)]. E-mail: marcello.baricco@unito.it

    2007-05-31

    Hydrogen absorption and desorption properties in LaMg{sub 2}Ni compound are presented. Nanostructured phases have been obtained by means of ball milling in order to study the influence of the microstructure on the absorption/desorption properties. The structural and hydriding properties were examined by X-ray diffraction, thermal analysis, hydrogen pressure-composition and thermal desorption measurements. Ball milling of as-cast compound gives a significant refinement of the microstructure. Hydrogenation at 443 K leads to the formation of LaMg{sub 2}NiH{sub 7}, but at higher temperatures (523 K) LaH{sub 2} is produced. Two hours of ball milling promote the formation of LaH{sub 2} under hydrogenation at 443 K. Thermal desorption up to 983 K of hydrogenated samples leads again to parent LaMg{sub 2}Ni phase.

  18. Monomer Adsorption-Desorption Processes

    Institute of Scientific and Technical Information of China (English)

    KE Jian-Hong; LIN Zhen-Quan; CHEN Xiao-Shuang

    2009-01-01

    We propose an adsorption-desorption model for a deposit growth system, in which the adsorption and desorption of particles coexist. By means of the generalized rate equation we investigate the cluster (island) size distribution in the dynamic equilibrium state. The results show that the evolution behaviour of the system depends crucially on the details of the rate kernels. The cluster size distribution can take the ecale-frse power-law form in some cases, while it grows exponentially with size in other cases.

  19. Hydrogen desorption in nanocrystalline MgH{sub 2} thin films at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Ares, J.R., E-mail: joser.ares@uam.e [Dpto. de Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049, Madrid (Spain); Leardini, F.; Diaz-Chao, P.; Bodega, J. [Dpto. de Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049, Madrid (Spain); Koon, D.W. [Physics Department, St Lawrence University, Canton, NY, 13617 (United States); Ferrer, I.J.; Fernandez, J.F.; Sanchez, C. [Dpto. de Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, 28049, Madrid (Spain)

    2010-04-16

    Hydrogen desorption process of Pd-capped magnesium hydride thin films of different thicknesses was investigated. Decomposition of magnesium hydride into magnesium under air exposure is observed in all investigated films. During decomposition no novel crystalline phases are detected. Desorption process was qualitatively analysed and it was concluded that is thermodynamically driven controlled by a nucleation and growth or by an interphase controlled mechanism. Moreover, H-kinetics investigation of desorption process was carried out by thermal desorption spectroscopy. Decomposition of MgH{sub 2} films occurs at T{sub d} {approx} 148 {sup o}C and the process seems to be controlled by a bidimensional interphase mechanism with an activation energy of 135 {+-} 20 kJ/mol H{sub 2}. No significant influence of thickness and crystallite size on desorption temperature is observed and obtained activation energy is similar to that of milled bulk magnesium.

  20. SPS Ion Induced Desorption Experiment

    CERN Multimedia

    Maximilien Brice

    2003-01-01

    This experiment will give a study about the induced desorption from heavy ion (Indium ion run from week 45 in SPS T4-H8 area) impacting LHC type graphite collimator. 4 different samples are located in the 4 chambers 90° one to each other: pure graphite, graphite with copper coating, graphite with NEG coating, 316LN stainless steal (reference).

  1. 气相色谱与热解吸联用技术在室内环境检测领域的应用及进展%Application and Development of Gas Chromatography Hyphenated with Thermal Desorption in the Field of Indoor Environment Testing

    Institute of Scientific and Technical Information of China (English)

    贾祥焱

    2012-01-01

    It is a brief introduction of gas chromatography and the application and development of gas chromatography hyphenated with thermal desorption in the test benzene and TVOC of indoor environment testing,and puts forward outlook and prospect in it.It provides favorable value in the development of gas chromatographic technique in indoor environment testing.%简要介绍了气相色谱法,及其与热解吸联用在民用建筑工程室内环境检测中检测苯、TVOC的应用和进展。并提出了气相色谱与热解吸联用技术的前景与展望,为气相色谱技术在室内环境检测领域的发展提供有利价值。

  2. ENRICHMENT OF TRACE AMOUNTS OF PESTICIDES IN POLLUTED WATER BY A NOVEL TYPE OF SOLID PHASE EXTRACTION ELEMENT FOR THEIR THERMAL DESORPTION GC/MS ANALYSIS%新型固相萃取器用于污染水样中痕量杀虫剂的浓缩及热解吸气相色谱-质谱分析

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A novel type of solid-phase extraction element named"Magic Chemisorber" is developed for sorptive enrichment of dilute analytes from aqueous samples with high extraction efficiencies due to its capacious layer of sorbent polydimethylsiloxane.This extraction element combined with thermal desorption-gas chromatography/mass spectrometry using a pyrolysis-GC/MS system was applied to extract the pesticides from water samples over a concentration range of 10-3 to 103 μg*l-1.The method showed good li-nearity for the tested concentration range with regression coefficients of 0.995 for over 5 decades.Limits of detection at a sub-ng*l-1(ppt)level were achieved and the reproducibility of the measurements was found to be fairly good,with relative standard deviation below 8%.

  3. 氯苯类易挥发有机污染土壤异位低温热脱附实例研究%Case Study On Ex-situ Remediation of Chlorobenzene-Like Volatile Organic Compounds (VOCs) Contaminated Soil With Technique of Low-Temperature Thermal Desorption

    Institute of Scientific and Technical Information of China (English)

    王湘徽; 祝欣; 龙涛; 邓绍坡; 林玉锁; 胡韬

    2016-01-01

    The technique of low⁃temperature thermal desorption was used to remedy chlorobenzene⁃like VOCs contaminated soil. Results show that VOCs were effectively removed after the treatment, with removal rate reaching 85% or more for all the tested VOCs. In field trials, a specialized soil remediation machine KH200 was used to crush the soil and have it mixed with lime in full⁃closed operation to avoid dust pollution. Through raising soil temperature and lowering soil water content, desorption and volatilization of VOC was effectively accelerated. All the findings in the experiment demon⁃strate that the use of the technique of low⁃temperature thermal desorption and the KH200 equipment is a promising ap⁃proach to efficient and low cost remediation of contaminated soils in sites of deserted chemical plants.%针对南京市某大型化工企业退役场地,结合场地修复目标,使用生石灰对场地氯苯类挥发性有机污染物( VOCs)污染土壤进行异位低温热脱附处理。实验室试验结果表明,该方法可有效去除土壤中的VOCs,处理后各污染物去除率均达85%以上。在现场试验中,采用专业土壤修复设备KH200进行土壤破碎和药剂混合,处理过程全封闭运行,可有效降低扬尘等问题。通过投加生石灰提高土壤温度、降低土壤含水量的方法,有效地促进了土壤中VOCs的解吸和挥发,是一种高效率、低成本的土壤修复技术,经过KH200修复设备处理后土壤中各污染物均达到场地修复目标,具备工程应用可行性。

  4. Synthesis and Hydrogen Desorption Properties of Aluminum Hydrides.

    Science.gov (United States)

    Jeong, Wanseop; Lee, Sang-Hwa; Kim, Jaeyong

    2016-03-01

    Aluminum hydride (AlH3 or alane) is known to store maximum 10.1 wt.% of hydrogen at relatively low temperature (hydrogen desorption are still not clear. To understand the desorption properties of hydrogen in alane, thermodynamically stable α-AlH3 was synthesized by employing an ethereal reaction method. The dependence of pathways on phase formation and the properties of hydrogen evolution were investigated, and the results were compared with the ones for γ-AlH3. It was found that γ-AlH3 requires 10 degrees C higher than that of γ-AlH3 to form, and its decomposition rate demonstrated enhanced endothermic stabilities. For desorption, all hydrogen atoms of alane evolved under an isothermal condition at 138 degrees C in less than 1 hour, and the sample completely transformed to pure aluminum. Our results show that the total amount of desorbed hydrogen from α-AlH3 exceeded 9.05 wt.%, with a possibility of further increase. Easy synthesis, thermal stability, and a large amount of hydrogen desorption of alane fulfill the requirements for light-weight hydrogen storage materials once the pathway of hydrogen cycling is provided.

  5. Hydrogen desorption from hydrogen fluoride and remote hydrogen plasma cleaned silicon carbide (0001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    King, Sean W., E-mail: sean.king@intel.com; Tanaka, Satoru; Davis, Robert F. [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695 (United States); Nemanich, Robert J. [Department of Physics, North Carolina State University, Raleigh, North Carolina 27695 (United States)

    2015-09-15

    Due to the extreme chemical inertness of silicon carbide (SiC), in-situ thermal desorption is commonly utilized as a means to remove surface contamination prior to initiating critical semiconductor processing steps such as epitaxy, gate dielectric formation, and contact metallization. In-situ thermal desorption and silicon sublimation has also recently become a popular method for epitaxial growth of mono and few layer graphene. Accordingly, numerous thermal desorption experiments of various processed silicon carbide surfaces have been performed, but have ignored the presence of hydrogen, which is ubiquitous throughout semiconductor processing. In this regard, the authors have performed a combined temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) investigation of the desorption of molecular hydrogen (H{sub 2}) and various other oxygen, carbon, and fluorine related species from ex-situ aqueous hydrogen fluoride (HF) and in-situ remote hydrogen plasma cleaned 6H-SiC (0001) surfaces. Using XPS, the authors observed that temperatures on the order of 700–1000 °C are needed to fully desorb C-H, C-O and Si-O species from these surfaces. However, using TPD, the authors observed H{sub 2} desorption at both lower temperatures (200–550 °C) as well as higher temperatures (>700 °C). The low temperature H{sub 2} desorption was deconvoluted into multiple desorption states that, based on similarities to H{sub 2} desorption from Si (111), were attributed to silicon mono, di, and trihydride surface species as well as hydrogen trapped by subsurface defects, steps, or dopants. The higher temperature H{sub 2} desorption was similarly attributed to H{sub 2} evolved from surface O-H groups at ∼750 °C as well as the liberation of H{sub 2} during Si-O desorption at temperatures >800 °C. These results indicate that while ex-situ aqueous HF processed 6H-SiC (0001) surfaces annealed at <700 °C remain terminated by some surface C–O and

  6. 2,5-Dihydroxybenzoic acid: laser desorption/ionisation as a function of elevated temperature

    Science.gov (United States)

    Wallace, W. E.; Arnould, M. A.; Knochenmuss, R.

    2005-03-01

    The temperature dependence of laser desorption/ionization (LDI) ion yields has been measured for 2,5-dihydroxybenzoic acid (2,5-DHB) single crystals from room temperature to 160 °C using time-of-flight (TOF) mass spectrometry. A steep rise in ion production occurs at 90 °C, achieving a maximum at 120 °C, then decreases sharply to a minimum at 140 °C, and returns to a second maximum at 150 °C. Above 160 °C, useful information could not be obtained because of rapid volatilization of the sample into the vacuum. The overall trend in ion production, but not some of the details, is well described by a recent two-step theory of the laser desorption/ionization process, which takes into account the temperature-dependent effects of plume expansion. Measuring the background vacuum composition with a quadrupole mass spectrometer residual gas analyzer (RGA) showed an increase in thermal desorption of 2,5-DHB starting at 90 °C and maximizing at 130 °C. The increased neutral production by thermal desorption is believed to be the cause of the decrease in LDI ion production due to reduced pooling probabilities for laser-excited 2,5-DHB molecules. Thermal dehydration, condensation, and decarboxylation increase the volume of gas released at high temperatures which also serve to decrease LDI ion production at elevated temperatures. Lastly, to confirm the mass spectrometry results, the thermal desorption of 2,5-DHB single crystals under vacuum was measured using a quartz-crystal microbalance (QCM). The onset of desorption was found to occur at 90 °C and the maximum desorption rate was found at 135 °C.

  7. Magnesium growth in magnesium deuteride thin films during deuterium desorption

    Energy Technology Data Exchange (ETDEWEB)

    Checchetto, R., E-mail: riccardo.checchetto@unitn.it [Dipartimento di Fisica and CNISM, Università di Trento, Via Sommarive 14, I-38123 Trento (Italy); Miotello, A. [Dipartimento di Fisica and CNISM, Università di Trento, Via Sommarive 14, I-38123 Trento (Italy); Mengucci, P.; Barucca, G. [Dipartimento di Fisica e Ingegneria dei Materiali e del Territorio, Università Politecnica delle Marche, I-60131 Ancona (Italy)

    2013-12-15

    Highlights: ► Highly oriented Pd-capped magnesium deuteride thin films. ► The MgD{sub 2} dissociation was studied at temperatures not exceeding 100 °C. ► The structure of the film samples was analyzed by XRD and TEM. ► The transformation is controlled by the re-growth velocity of the Mg layers. ► The transformation is thermally activated, activation energy value of 1.3 ± 0.1 eV. -- Abstract: Pd- capped nanocrystalline magnesium thin films having columnar structure were deposited on Si substrate by e-gun deposition and submitted to thermal annealing in D{sub 2} atmosphere to promote the metal to deuteride phase transformation. The kinetics of the reverse deuteride to metal transformation was studied by Thermal Desorption Spectroscopy (TDS) while the structure of the as deposited and transformed samples was analyzed by X-rays diffraction and Transmission Electron Microscopy (TEM). In Pd- capped MgD{sub 2} thin films the deuteride to metal transformation begins at the interface between un-reacted Mg and transformed MgD{sub 2} layers. The D{sub 2} desorption kinetics is controlled by MgD{sub 2}/Mg interface effects, specifically the re-growth velocity of the Mg layers. The Mg re-growth has thermally activated character and shows an activation energy value of 1.3 ± 0.1 eV.

  8. Catalitic effect of Co on hydrogen desorption form nanostucturated magnesium hydride

    Directory of Open Access Journals (Sweden)

    Matović Ljiljana Lj.

    2008-01-01

    Full Text Available To study the influence of 3d transition metal addition on desorption kinetics of MgH2 ball milling of MgH2-Co blends was performed under Ar. Microstructural and morphological characterization, performed by XRD and SEM, show a huge correlation with thermal stability and hydrogen desorption properties investigated by DSC. A complex desorption behavior is correlated with the dispersion of the metal additive particles on hydride matrix. The activation energy for H2 desorption from MgH2-Co composite was calculated from both non-isothermal and isothermal methods to be 130 kJ/mol which means that mutually diffusion and nucleation and growth of new phase control the dehydration process.

  9. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    Science.gov (United States)

    Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang

    2016-08-01

    Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition) at the atmosphere-soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  10. Improved hydrogen desorption from lithium hydrazide by alkali metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Liang, E-mail: liangzeng@hiroshima-u.ac.jp [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Miyaoka, Hiroki [Institute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan)

    2013-12-15

    Highlights: •LiH can dramatically improve the hydrogen desorption properties of LiNHNH{sub 2}. •KH doping had positive effect in promoting the hydrogen desorption properties of LiNHNH{sub 2}–LiH mixture. •The reaction mechanism between LiNHNH{sub 2} and LiH was studied and discussed. -- Abstract: Lithium hydrazide (LiNHNH{sub 2}), which is a white solid with 8.0 mass% of theoretical hydrogen content, was synthesized from a reaction between anhydrous hydrazine and n-butyllithium in diethyl ether. The thermodynamic properties of this compound and its detailed decomposition pathways had been investigated in our previous work. However, a number of undesired gaseous products such as hydrazine (N{sub 2}H{sub 4}) and ammonia (NH{sub 3}) were generated during the thermal decomposition of LiNHNH{sub 2}. In this work, alkali metal hydride was used to suppress the impurities in the desorbed hydrogen and improved the hydrogen desorption properties. The reaction mechanism between LiNHNH{sub 2} and LiH was also studied and discussed in this paper.

  11. Laser-induced acoustic desorption (LIAD) mass spectrometry.

    Science.gov (United States)

    Dow, Alex M; Wittrig, Ashley R; Kenttämaa, Hilkka I

    2012-01-01

    Large thermally labile molecules were not amenable to mass spectrometric analysis until the development of atmospheric pressure evaporation/ionization methods, such as electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI), since attempts to evaporate these molecules by heating induces degradation of the sample. While ESI and MALDI are relatively soft desorption/ionization techniques, they are both limited to preferential ionization of acidic and basic analytes. This limitation has been the driving force for the development of other soft desorption/ionization techniques. One such method employs laser-induced acoustic desorption (LIAD) to evaporate neutral sample molecules into mass spectrometers. LIAD utilizes acoustic waves generated by a laser pulse in a thin metal foil. The acoustic waves travel through the foil and cause desorption of neutral molecules that have been deposited on the opposite side of the foil. One of the advantages of LIAD is that it desorbs low-energy molecules that can be ionized by a variety of methods, thus allowing the analysis of large molecules that are not amenable to ESI and MALDI. This review covers the generation of acoustic waves in foils via a laser pulse, the parameters affecting the generation of acoustic waves, possible mechanisms for desorption of neutral molecules, as well as the various uses of LIAD by mass spectrometrists. The conditions used to generate acoustic or stress waves in solid materials consist of three regimes: thermal, ablative, and constrained. Each regime is discussed, in addition to the mechanisms that lead to the ablation of the metal from the foil and generation of acoustic waves for two of the regimes. Previously proposed desorption mechanisms for LIAD are presented along with the flaws associated with some of them. Various experimental parameters, such as the exact characteristics of the laser pulse and foil used, are discussed. The internal and kinetic energy of the neutral

  12. Surface oxidation and water desorption of CdS

    Institute of Scientific and Technical Information of China (English)

    陈正石; 李庆霖; 金振声

    1996-01-01

    The surface oxidation and HP desorption of powder CdS were studied by means of X-ray photoetectron spectroscopy (XPS), quadrupole mass spectrometry (QMS) and in-situ FTIR. The results show that with the changes of surface composition and the elongation of store time of CdS there are four types of H2O thermally desorbed at different temperatures. It has also been found that through high-temperature air treatment for a short time the oxidized surface layer of CdS can prevent O2 and H2O in air from further attacking the inner CdS molecules.

  13. Effects of surface coordination on the temperature-programmed desorption of oxalate from goethite

    Energy Technology Data Exchange (ETDEWEB)

    Boily, Jean F.; Szanyi, Janos; Felmy, Andrew R.

    2007-11-15

    The temperature-programmed desorption (TPD) of weakly-bound, hydrogen-bonded and metal-bonded oxalate complexes at the goethite surface was investigated in the 300-900 K range with concerted Fourier Transform Infrared (FTIR) measurements (TPD-FTIR). These reactions took place with the concomitant dehydroxylation reaction of goethite to hematite and decarbonation of bulk-occluded carbonate. The measurements revealed three important stages of desorption. Stage I (300-440 K) corresponds to the desorption of weakly-and/or un-bound oxalate molecules in the goethite powder with a thermal decomposition reaction pathway characteristic of oxalic acid. Stage II (440-520 K) corresponds to a thermally-driven dehydration of hydrogen-bonded surface complexes, leading to a partial desorption via oxalic acid thermal decomposition pathways and to a partial conversion to metal-bonded surface complexes. This latter mechanism led to the increase in FTIR bands characteristic of these complexes. Finally, Stage III (520-660 K) corresponds to the thermal decomposition of the metal-bonded oxalate complex, proceeding through a 2 electron reduction pathway.

  14. A photoluminescence study of indium desorption from strained Ga sub 1-x In sub x As/GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Emeny, M.T.; Whitehouse, C.R. (Royal Signals and Radar Establishment, Great Malvern (UK)); Howard, L.K.; Lambkin, J.D. (Strained Layer Structures Group, Univ. of Surrey, Guildford (UK)); Homewood, K.P. (Dept. of Electronic and Electrical Engineering, Univ. of Surrey, Guildford (UK))

    1991-05-01

    In this paper we present detailed measurements of the thermal desorption rates of indium from strained GaInAs grown off a GaAs substrate. We have made these measurements by monitoring the photoluminescence (PL) of the groundstate emission from strained quantum wells. We show that this method can be an accurate and highly sensitive technique for measuring desorption rates. The measurements have been made as a function of composition and arsenic overpressure. A simple model for the indium incorporation is developed and an activation energy for the desorption process has been obtained. (orig.).

  15. Infrared laser desorption/ionization on silicon.

    Science.gov (United States)

    Bhattacharya, Sucharita H; Raiford, Timothy J; Murray, Kermit K

    2002-05-01

    Laser desorption/ionization from a single-crystal silicon surface was performed using a laser operating in the 3-microm region of the mid-infrared. Analyte molecules up to 6 kDa were ionized with no added matrix. As with ultraviolet desorption/ionization from porous silicon (DIOS), IR laser desorption from silicon does not produce matrix ions that can interfere with analysis of low-mass analytes. However, in contrast to UV DIOS, silicon porosity or roughness is not required for ionization using an IR laser. Mass spectra were obtained in the wavelength range between 2.8 and 3.5 microm, which is consistent with energy absorption by a hydrogen-bonded OH group. A mechanism based on desorption of adsorbed solvent molecules is postulated.

  16. Survival of HCl( v=2) in trapping-desorption from MgO(100)

    Science.gov (United States)

    Korolik, M.; Suchan, M. M.; Johnson, M. J.; Arnold, D. W.; Reisler, H.; Wittig, C.

    2000-08-01

    An HCl molecular beam incident on MgO(100) is photoexcited to v=2, J=1 by using a pulsed parametric oscillator. At a translational energy of 0.11 eV, incident HCl is adsorbed. Thermal desorption yields v=2 molecules whose rotational and translational degrees of freedom are equilibrated at the surface temperature. Surface residence times for v=2 might be as long as 1 μs. At 180 K, it is concluded that a large fraction of surface-bound v=2 molecules reenter the gas phase, while at 120 K, deactivation exceeds desorption by an order of magnitude. Deactivation probably takes place at steps.

  17. Adsorption, desorption and bioregeneration in the treatment of 2-chlorophenol with activated carbon.

    Science.gov (United States)

    Aktaş, Ozgür; Ceçen, Ferhan

    2007-03-22

    This study aims to clarify the effect of activated carbon type on the extent of adsorbability, desorbability, and bioregenerability in the treatment of 2-chlorophenol. Four different activated carbon types; thermally activated and chemically activated powdered carbons (PAC), and their granular countertypes (GAC) with similar physical characteristics were used. Thermally activated carbons adsorbed 2-chlorophenol much better than chemically activated ones. However, adsorption was more reversible in the case of chemically activated ones. The use of powdered and granular activated carbon countertypes resulted in comparable adsorption and desorption characteristics. For each activated carbon type, 2-chlorophenol exhibited higher adsorbability and lower desorbability than phenol. Biodegradation of 2-chlorophenol took place very slowly when it was used as the sole carbon source in acclimated and non-acclimated activated sludges. Bioregeneration occurred only via desorption due to an initial concentration gradient and no further desorption took place due to low biodegradability. Bioregeneration of activated carbon loaded with 2-chlorophenol was not a suitable option when 2-chlorophenol was the only carbon source. It is suggested to remove 2-chlorophenol via adsorption onto activated carbon rather than applying biological treatment. Also in such cases, the use of thermally activated carbons with higher adsorption and lower desorption capacities is recommended rather than chemically activated carbons.

  18. Thermal Desorption-Gas Chromatography or Gas Chromatograph-Mass Spectrometry for Analysis of Semi-Volatile Compounds on Atmospheric Particulate Matters%热解析-气相色谱或气相色谱-质谱法分析大气可吸入颗粒物中的半挥发性有机化合物

    Institute of Scientific and Technical Information of China (English)

    孟虎; 赵景红; 段春凤; 郝亮; 关亚风

    2014-01-01

    A thermal desorption ( TD) device was developed and coupled to gas chromatography ( GC) or gas chromatography-mass spectrometry ( GC-MS ) for the qualitative and quantitative analysis of semi-volatile organic compounds on atmospheric particulate matters ( PM ) . The TD was operated by direct heating and placed on the GC injector, leading to high heating rate and easy transfer of analytes to GC without focusing of analytes by cold trap. For establishing the TD-GC method, the materials used for supporting PM samples, temperature and time of thermal desorption, and types of sample injection were investigated for detection of sixteen polycyclic aromatic hydrocarbons ( PAHs) and nine n-alkanes. The limits of detection of the proposed TD-GC method were in the range of 0. 014-0. 093 ng for PAHs, and 0. 016-0. 026 ng for n-alkanes, respectively, with the correlation coefficients of correlation above 0. 9975. The TD-GC method was applied to the determination of trace PAHs and n-alkanes on PM10 samples from three cities. The recoveries were in the range of 95%-135% ( PAHs) and 95%-115% ( n-alkanes) , respectively. Finally, the TD was coupled to GC-MS for comparison of the contents of PAHs and n-alkanes on PMx with different particulate size ( x=10 , 5, 2, 1, 0. 5, 0. 25, 0. 1).%研制了一种热解析装置,并与气相色谱或气相色谱-质谱联用,定性定量分析了大气可吸入颗粒物中的半挥发性有机物。装置为直热式加热,升温速率快;直接安装在色谱进样器上方,无需冷阱聚焦。将热解析装置与气相色谱联用,优化了样品承载体材质、热解析条件和进样模式,并用于16种多环芳烃和9种正构烷烃的检测。结果表明,热解析-气相色谱方法对多环芳烃和正构烷烃的检出限分别为0.014~0.093 ng和0.016~0.026 ng,线性相关系数大于0.9975;用于3个城市PM10中的痕量多环芳烃和正构烷烃的定量测定,回收率分别在95%~135%(多环芳烃)和95%~115%(正构烷

  19. 搅拌棒萃取-热脱附/气质联用法测定水中2-MIB和土臭素%Determination of 2-Methylisoborneol and Geosmin in Water Using Stir Bar Sorptive Extraction-Thermal Desorption/Gas Chromatography Coupled with Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    范苓; 张晓赟; 秦宏兵; 顾海东

    2013-01-01

    A method using stir bar sorptive extraction ( SBSE)-thermal desorption ( TD)/gas chromatogra-phy coupled with mass spectrometry ( GCMS) was developed to determinate ultra-trace level of 2-methylisoborneol (2-MIB) and geosmin in water .SBSE and TD parameters were optimized through blank spiked sample .The method showed good linearity ( r>0 .999 ) over concentration range from 1 ng/L to 200 ng/L and high sensitivity ( the MDL of 2-MIB and geosmin were 0 .31 ng/L and 0 .15 ng/L respectively ) .The spiked recovery of blank and real samples ranged from 82 .4%to 116%with RSD <10%.%采用搅拌棒萃取-热脱附/气质联用法测定水中2-甲基异莰醇和土臭素,优化了搅拌棒萃取和热脱附进样的条件。试验表明:两种目标化合物在1.00 ng/L~200 ng/L范围内线性良好,2-甲基异莰醇的相关系数为0.9993,土臭素的相关系数为0.9997,方法检出限分别为0.31 ng/L和0.15 ng/L;空白和实际样品的加标回收率为82.4%~116%,测定结果的RSD<10%。

  20. Desorption of 137Cs+ from mosses

    Directory of Open Access Journals (Sweden)

    OLGICA NEDIC

    2002-09-01

    Full Text Available Mosses are biomonitors that accumulate large amounts of various pollutants, including radionuclides. In this work we investigated the possibility of 137Cs extraction from mosses, as well as the significance of species specificity on the efficiency of 137Cs desorption. Salt and acid solutions were used as extraction media. It was shown that a 5 % solution of both ammonium oxalate and phosphoric acid was able to desorb 81.8 % of 137Cs+ from Homalothecium sericeum, which was 39.9 % more than desorption from water. At the same time, most of the desorbed 137Cs+ was incorporated in crystals that precipitated from the solution. An interspecies difference in respect to 137Cs+ desorption was noticed.

  1. Adsorption and Desorption of Methiopyrsulfuron in Soils

    Institute of Scientific and Technical Information of China (English)

    WU Chun-Xian; WANG Jin-Jun; ZHANG Su-Zhi; ZHANG Zhong-Ming

    2011-01-01

    Methiopyrsulfuron is a new low-rate sulfonylurea herbicide for weed control in wheat; however, there is a lack of published information on its behavior in soils. In this study, methiopyrsulfuron adsorption and desorption were measured in seven soils sampled from Heilongjiang, Shandong, Jiangxi, Sichuan, Anhui, and Chongqing provinces of China using a batch equilibrium method. The Freundlich equation was used to described its adsorption and desorption. Adsorption isotherms were nonlinear with the values of Kf-ads, the Freundlich empirical constant indicative of the adsorption capacity,ranging from 0.75 to 2.46, suggesting that little of this herbicide was adsorbed by any of the seven soils. Soil pH and organic matter content (OM) were the main factors influencing adsorption; adsorption was negatively correlated with pH and positively correlated with OM. Methiopyrsulfuron desorption was hysteretic on the soils with high OM content and low pH.

  2. Ionic Adsorption and Desorption of CNT Nanoropes

    Directory of Open Access Journals (Sweden)

    Jun-Jun Shang

    2016-09-01

    Full Text Available A nanorope is comprised of several carbon nanotubes (CNTs with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment.

  3. Water desorption from nanostructured graphite surfaces.

    Science.gov (United States)

    Clemens, Anna; Hellberg, Lars; Grönbeck, Henrik; Chakarov, Dinko

    2013-12-21

    Water interaction with nanostructured graphite surfaces is strongly dependent on the surface morphology. In this work, temperature programmed desorption (TPD) in combination with quadrupole mass spectrometry (QMS) has been used to study water ice desorption from a nanostructured graphite surface. This model surface was fabricated by hole-mask colloidal lithography (HCL) along with oxygen plasma etching and consists of a rough carbon surface covered by well defined structures of highly oriented pyrolytic graphite (HOPG). The results are compared with those from pristine HOPG and a rough (oxygen plasma etched) carbon surface without graphite nanostructures. The samples were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The TPD experiments were conducted for H2O coverages obtained after exposures between 0.2 and 55 langmuir (L) and reveal a complex desorption behaviour. The spectra from the nanostructured surface show additional, coverage dependent desorption peaks. They are assigned to water bound in two-dimensional (2D) and three-dimensional (3D) hydrogen-bonded networks, defect-bound water, and to water intercalated into the graphite structures. The intercalation is more pronounced for the nanostructured graphite surface in comparison to HOPG surfaces because of a higher concentration of intersheet openings. From the TPD spectra, the desorption energies for water bound in 2D and 3D (multilayer) networks were determined to be 0.32 ± 0.06 and 0.41 ± 0.03 eV per molecule, respectively. An upper limit for the desorption energy for defect-bound water was estimated to be 1 eV per molecule.

  4. 5th International Workshop on Desorption Induced by Electronic Transitions

    CERN Document Server

    Jennison, Dwight R; Stechel, Ellen B; DIET V; Desorption induced by electronic transitions

    1993-01-01

    This volume in the Springer Series on Surface Sciences presents a recent account of advances in the ever-broadening field of electron-and photon-stimulated sur­ face processes. As in previous volumes, these advances are presented as the proceedings of the International Workshop on Desorption Induced by Electronic Transitions; the fifth workshop (DIET V) was held in Taos, New Mexico, April 1-4, 1992. It will be abundantly clear to the reader that "DIET" is not restricted to desorption, but has for several years included photochemistry, non-thermal surface modification, exciton self-trapping, and many other phenomena that are induced by electron or photon bombardment. However, most stimulated surface processes do share a common physics: initial electronic excitation, localization of the excitation, and conversion of electronic energy into nuclear kinetic energy. It is the rich variation of this theme which makes the field so interesting and fruitful. We have divided the book into eleven parts in orde...

  5. Development of a thermal desorption modulator for gas chromatography

    NARCIS (Netherlands)

    Geus, H.J.; Boer, de J.; Brinkman, U.A.Th.

    1997-01-01

    The separation space in gas chromatography can be enhanced dramatically by the comprehensive coupling of two independent separation dimensions. An interface between the two columns must accumulate analytes eluting from the first dimension, focus them and at the appropriate moment transfer them to th

  6. Electronic Desorption of gas from metals

    Energy Technology Data Exchange (ETDEWEB)

    Molvik, A W; Kollmus, H; Mahner, E; Covo, M K; Bender, M; Bieniosek, F M; Kramer, A; Kwan, J; Prost, L; Seidl, P A; Westenskow, G

    2006-11-02

    During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  7. Quantum theory of laser-stimulated desorption

    Science.gov (United States)

    Slutsky, M. S.; George, T. F.

    1978-01-01

    A quantum theory of laser-stimulated desorption (LSDE) is presented and critically analyzed. It is shown how LSDE depends on laser-pulse characteristics and surface-lattice dynamics. Predictions of the theory for a Debye model of the lattice dynamics are compared to recent experimental results.

  8. A microsystems enabled field desorption source.

    Energy Technology Data Exchange (ETDEWEB)

    Hertz, Kristin L.; Resnick, Paul James; Schwoebel, Paul R. (University of New Mexico, Albuquerque, NM); Holland, Christopher E. (SRI International, Menlo Park, CA); Chichester, David L. (Idaho National Laboratory, Idaho Falls, ID)

    2010-07-01

    Technologies that have been developed for microelectromechanical systems (MEMS) have been applied to the fabrication of field desorption arrays. These techniques include the use of thick films for enhanced dielectric stand-off, as well as an integrated gate electrode. The increased complexity of MEMS fabrication provides enhanced design flexibility over traditional methods.

  9. Product desorption limitations in selective photocatalytic oxidation

    NARCIS (Netherlands)

    Renckens, T.J.A.; Almeida, A.R.; Damen, M.R.; Kreutzer, M.T.; Mul, G.

    2010-01-01

    The rate of photocatalytic processes can be significantly improved if strongly bound products rapidly desorb to free up active sites. This paper deals with the rate of desorption of cyclohexanone, the product of the liquid-phase photo-oxidation of cyclohexane. Dynamic step-response and pulse-respons

  10. 热降解辅助表面解吸常压化学电离质谱对阿莫西林的分析%Analysis of amoxicillin by surface desorption atmospheric pressure chemical ionization mass spectrometry aided with thermal degradation

    Institute of Scientific and Technical Information of China (English)

    陈荣; 邓慧宇; 石俊

    2012-01-01

    To establish a novel approach to the high throughput screening of amoxicillin by direct surface desorption atmospheric pressure chemical ionization -mass spectrometry aided with thermal degradation(TD -SDAP-CI - MS). Methods; Water in the air act as the reactive reagent responsible for the generation of ions in the positive corona discharge. The rapid screening effectiveness of the combination of TD and SDAPGI was demonstrated by application to comparing the total ion current mass spectrum of degradation ingredient ions to ion current mass spectrum of amoxicillin capsules which were observed in full scan mass spectrometry (MS) mode. Collision -induced dissociation of protonated molecules gave characteristic product - ion mass spectra and provided further identification of amoxicillin degradation ingredients. Results: The high throughput screening of amoxicillin was realized by mass spectrum without sample pretreatment and separation step. Conclusions: A single sample analysis is completed in less than 30 seconds. The data show TD - SDAPCI - MS is a convenient tool for high throughtout screening of unstable amoxicillin.%目的:建立一种阿莫西林热降解辅助表面解吸常压化学电离质谱(TD - SDAPCI - MS)快速检测新方法.方法:利用阿莫西林抗生素的易降解并产生特定降解产物的特性,以潮湿空气作为试剂,通过电晕放电产生大量试剂离子,对阿莫西林抗生素总离子流质谱图与特征降解产物离子流图进行比对.并通过串联质谱对阿莫西林抗生素产生的特征降解产物进行了确认.结果:无需样品预处理,实现一级质谱法对阿莫西林抗生素的高通量筛选.结论:单个样品检测不超过30 s,可实现不稳定抗生素阿莫西林的高通量筛选.

  11. 吸附-热解吸法与气相色谱-质谱法联用测定蚊香烟雾中的有机化合物%Determination of Organic Compounds in the Smog of Mosquito-Repellent Incense by Adsorption-Thermal Desorption-GC/MS

    Institute of Scientific and Technical Information of China (English)

    刘秀华; 钟志京; 孟丹; 丁兰岚; 田军华

    2012-01-01

    利用吸附-热解吸法与气相色谱-质谱法联用,对两种固体蚊香烟气中的有机成分进行定性和半定量分析.在两种固体蚊香烟气中共检测出52种挥发性成分,包括酚类、醇类、醛类以及脂肪烃和芳香烃等多种化合物,其中的部分化合物对人体有毒害作用.蚊香A烟气中含量较多的成分为右旋烯丙菊酯(30.06%)、1,6-脱水-β-D-吡喃葡萄糖(19.4%)和甘菊环(13.9%)等;蚊香B烟气中含量较多的成分为1,6-脱水-β-D-吡喃葡萄糖(24.4%)、甘菊环(14.4%)和正十四烷(5.91%)等.%The organic components in the smog of mosquito-repellent incense were analyzed qualitatively and semi-quantitatively by adsorption-thermal desorption with gas chromatog-raphy-mass spectrometry. 52 kinds of compounds are identified in two kinds of solid mosquito-repellent incenses, including phenolic compounds, alcohols, aldehydes, aliphatic hydrocarbons, aromatic hydrocarbons and so on. Some compounds are poisonous to people's health. The principal components in the smog of mosquito-repellent incense A are allethrin (30.06%), l,6-Anhydro-β-D-glucopyranose(19. 4%), azulene(13. 9%) , while the principal components are 1,6-Anhydro-β-D-glucopyranose(24. 4%), azulene(14. 4%), tetrade-cane(5. 91%) for the mosquito-repellent incense B.

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

    OpenAIRE

    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 accoun...

  13. Residence time dependent desorption of Staphylococcus epidermidis from hydrophobic and hydrophilic substrata

    NARCIS (Netherlands)

    Boks, Niels P.; Kaper, Hans J.; Norde, Willem; Busscher, Henk J.; van der Mei, Henny C.

    2008-01-01

    Adhesion and desorption are simultaneous events during bacterial adhesion to surfaces. although desorption is far less studied than adhesion. Here, desorption of Staphylococcus epidermidis from substratum surfaces is demonstrated to be residence time dependent. Initial desorption rate coefficients

  14. Residence time dependent desorption of Staphylococcus epidermidis from hydrophobic and hydrophilic substrata

    NARCIS (Netherlands)

    Boks, Niels P.; Kaper, Hans J.; Norde, Willem; Busscher, Henk J.; van der Mei, Henny C.

    2008-01-01

    Adhesion and desorption are simultaneous events during bacterial adhesion to surfaces. although desorption is far less studied than adhesion. Here, desorption of Staphylococcus epidermidis from substratum surfaces is demonstrated to be residence time dependent. Initial desorption rate coefficients w

  15. Helium Retention and Desorption Behaviour of Reduced Activation Ferritic/Martenstic Steel

    Science.gov (United States)

    Wang, Pinghuai; Nobuta, Yuji; Hino, Tomoaki; Yamauchi, Yuji; Chen, Jiming; Xu, Zengyu; Li, Xiongwei; Liu, Shi

    2009-04-01

    The reduced activation ferritic/martenstic steel CLF-1 prepared by the Southwestern Institute of Physics in China was irradiated by helium ions with an energy of 5 keV at room temperature using an electron cyclotron resonance (ECR) ion irradiation apparatus. After the irradiation, the helium retention and desorption were investigated using a technique of thermal desorption spectroscopy (TDS). The experiment was conducted with both the normal and welded samples. Blisters were observed after the helium ion irradiation, and the surface density of blisters in the welded samples was lower than that in the non-welded samples. Three desorption peaks were observed in both the non-welded and welded samples. These desorption peaks corresponded to those of blister ruptures and the helium release from the inner bubbles and the defects. The amount of helium retained in the welded samples was approximately the same as that in the non-welded samples, which was much less than other reduced activation materials, such as vanadium alloy and SiC/SiC composites.

  16. Direct measurement of desorption and diffusion energies of O and N atoms physisorbed on amorphous surfaces

    CERN Document Server

    Minissale, Marco; Dulieu, François

    2016-01-01

    Physisorbed atoms on the surface of interstellar dust grains play a central role in solid state astrochemistry. Their surface reactivity is one source of the observed molecular complexity in space. In experimental astrophysics, the high reactivity of atoms also constitutes an obstacle to measuring two of the fundamental properties in surface physics, namely desorption and diffusion energies, and so far direct measurements are non-existent for O and N atoms. We investigated the diffusion and desorption processes of O and N atoms on cold surfaces in order to give boundary conditions to astrochemical models. Here we propose a new technique for directly measuring the N- and O-atom mass signals. Including the experimental results in a simple model allows us to almost directly derive the desorption and diffusion barriers of N atoms on amorphous solid water ice (ASW) and O atoms on ASW and oxidized graphite. We find a strong constraint on the values of desorption and thermal diffusion energy barriers. The measured b...

  17. Helium Retention and Desorption Behaviour of Reduced Activation Ferritic/Martenstic Steel

    Institute of Scientific and Technical Information of China (English)

    WANG Pinghuai; NOBUTA Yuji; HINO Tomoaki; YAMAUCHI Yuji; CHEN Zilning; XU Zengyu; LI Xiongwei; LIU Shi

    2009-01-01

    The reduced activation ferritic/martenstic steel CLF-1 prepared by the Southwest-ern Institute of Physics in China was irradiated by helium ions with an energy of 5 keV at room temperature using an electron cyclotron resonance (ECR) ion irradiation apparatus. After the irradiation, the helium retention and desorption were investigated using a technique of thermal desorption spectroscopy (TDS). The experiment was conducted with both the normal and welded samples. Blisters were observed after the helium ion irradiation, and the surface density of blisters in the welded samples was lower than that in the non-welded samples. Three desorption peaks were observed in both the non-welded and welded samples. These desorption peaks corresponded to those of blister ruptures and the helium release from the inner bubbles and the defects. The amount of helium retained in the welded samples was approximately the same as that in the non-welded samples, which was much less than other reduced activation materials, such as vanadium alloy and SiC/SiC composites.

  18. Desorption of Water from Distinct Step Types on a Curved Silver Crystal

    Directory of Open Access Journals (Sweden)

    Jakrapan Janlamool

    2014-07-01

    Full Text Available We have investigated the adsorption of H2O onto the A and B type steps on an Ag single crystal by temperature programmed desorption. For this study, we have used a curved crystal exposing a continuous range of surface structures ranging from [5(111 × (100] via (111 to [5(111 × (110]. LEED and STM studies verify that the curvature of our sample results predominantly from monoatomic steps. The sample thus provides a continuous array of step densities for both step types. Desorption probed by spatially-resolved TPD of multilayers of H2O shows no dependence on the exact substrate structure and thus confirms the absence of thermal gradients during temperature ramps. In the submonolayer regime, we observe a small and linear dependence of the desorption temperature on the A and B step density. We argue that such small differences are only observable by means of a single curved crystal, which thus establishes new experimental benchmarks for theoretical calculation of chemically accurate binding energies. We propose an origin of the observed behavior based on a “two state” desorption model.

  19. Plutonium sorption and desorption behavior on bentonite.

    Science.gov (United States)

    Begg, James D; Zavarin, Mavrik; Tumey, Scott J; Kersting, Annie B

    2015-03-01

    Understanding plutonium (Pu) sorption to, and desorption from, mineral phases is key to understanding its subsurface transport. In this work we study Pu(IV) sorption to industrial grade FEBEX bentonite over the concentration range 10(-7)-10(-16) M to determine if sorption at typical environmental concentrations (≤10(-12) M) is the same as sorption at Pu concentrations used in most laboratory experiments (10(-7)-10(-11) M). Pu(IV) sorption was broadly linear over the 10(-7)-10(-16) M concentration range during the 120 d experimental period; however, it took up to 100 d to reach sorption equilibrium. At concentrations ≥10(-8) M, sorption was likely affected by additional Pu(IV) precipitation/polymerization reactions. The extent of sorption was similar to that previously reported for Pu(IV) sorption to SWy-1 Na-montmorillonite over a narrower range of Pu concentrations (10(-11)-10(-7) M). Sorption experiments with FEBEX bentonite and Pu(V) were also performed across a concentration range of 10(-11)-10(-7) M and over a 10 month period which allowed us to estimate the slow apparent rates of Pu(V) reduction on a smectite-rich clay. Finally, a flow cell experiment with Pu(IV) loaded on FEBEX bentonite demonstrated continued desorption of Pu over a 12 day flow period. Comparison with a desorption experiment performed with SWy-1 montmorillonite showed a strong similarity and suggested the importance of montorillonite phases in controlling Pu sorption/desorption reactions on FEBEX bentonite.

  20. Lead sorption-desorption from organic residues.

    Science.gov (United States)

    Duarte Zaragoza, Victor M; Carrillo, Rogelio; Gutierrez Castorena, Carmen M

    2011-01-01

    Sorption and desorption are mechanisms involved in the reduction of metal mobility and bioavailability in organic materials. Metal release from substrates is controlled by desorption. The capacity of coffee husk and pulp residues, vermicompost and cow manure to adsorb Pb2+ was evaluated. The mechanisms involved in the sorption process were also studied. Organic materials retained high concentrations of lead (up to 36,000 mg L(-1)); however, the mechanisms of sorption varied according to the characteristics of each material: degree of decomposition, pH, cation exchange capacity and percentage of organic matter. Vermicompost and manure removed 98% of the Pb from solution. Lead precipitated in manure and vermicompost, forming lead oxide (PbO) and lead ferrite (PbFe4O7). Adsorption isotherms did not fit to the typical Freundlich and Langmuir equations. Not only specific and non-specific adsorption was observed, but also precipitation and coprecipitation. Lead desorption from vermicompost and cow manure was less than 2%. For remediation of Pb-polluted sites, the application of vermicompost and manure is recommended in places with alkaline soils because Pb precipitation can be induced, whereas coffee pulp residue is recommended for acidic soils where Pb is adsorbed.

  1. Plasma Desorption Mass Spectrometry analysis of HCOOH ice

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, D.P.P.; Rocco, M.L.M. [Departamento de Fisico-Quimica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, Cidade Universitaria, Ilha do Fundao, 21949-900 Rio de Janeiro, RJ (Brazil); Boechat-Roberty, H.M. [Observatorio do Valongo, Universidade Federal do Rio de Janeiro, Ladeira Pedro Antonio, 43, Centro, Rio de Janeiro, RJ (Brazil); Iza, P.; Martinez, R. [Departamento de Fisica, Pontificia Universidade Catolica do Rio de Janeiro, 22543-900 Rio de Janeiro (Brazil); Homem, M.G.P. [Laboratorio Nacional de Luz Sincrotron (LNLS), Box 6192, 13084-971 Campinas, SP (Brazil); Silveira, E.F. da [Departamento de Fisica, Pontificia Universidade Catolica do Rio de Janeiro, 22543-900 Rio de Janeiro (Brazil)], E-mail: enio@vdg.fis.puc-rio.br

    2007-03-15

    Planetary magnetospheres, in which outer planet satellites orbit, are bombarded by energetic particles inducing chemical and physical changes in their icy surfaces. The existing condensed gases react to form new products, which then undergo thermal evolution from the natural day/night cycles of these satellites. Plasma irradiation of ice causes phase changes, e.g., water ice from crystalline to amorphous over short timescales. When ice is recrystallized by heating, the surface layers retain some disorder, which promote reactions among adsorbed molecules such as H{sub 2}O, CO{sub 2}, CH{sub 2}CO, HCOOH and theirs radiolysis products. In this work, chemical reactions involving formic acid condensed at 56 K are analyzed by using Plasma Desorption Mass Spectrometry-time-of-flight ({sup 252}Cf-PDMS-TOF). Mass spectra of positive and negative desorbed ions were obtained, giving information on the structure and abundance of the molecules on the ice; the expected cations and anions generated by the HCOOH dissociation have been observed. Furthermore, several series of cluster ions were also detected, all exhibiting the structure X{sub n}Y{sub m}R{sup {+-}}, where X and Y are the neutral ice molecules, such as HCOOH or H{sub 2}O, and R{sup {+-}} is either an atomic or a molecular ion, such as H{sup +}, H{sub 3}O{sup +} or COOH{sup -}. In general, the desorption yields of the observed positive and negative ions are characterized by a decreasing exponential function as the emitted ion mass increases; however, the (HCOOH){sub n}OH{sup -} series presents its maximum at n = 8.

  2. New Activated Carbon with High Thermal Conductivity and Its Microwave Regeneration Performance

    Institute of Scientific and Technical Information of China (English)

    GU Xuexian; SU Zhanjun; XI Hongxia

    2016-01-01

    Using a walnut shell as a carbon source and ZnCl2 as an activating agent, we resolved the temperature gradient problems of activated carbon in the microwave desorption process. An appropriate amount of silicon carbide was added to prepare the composite activated carbon with high thermal conductivity while developing VOC adsorption-microwave regeneration technology. The experimental results show that the coefficient of thermal conductivity of SiC-AC is three times as much as those of AC and SY-6. When microwave power was 480 W in its microwave desorption , the temperature of the bed thermal desorption was 10℃ to 30℃below that of normal activated carbon prepared in our laboratory. The toluene desorption activation energy was 16.05 kJ∙mol-1, which was 15% less than the desorption activation energy of commercial activated carbon. This study testified that the process could maintain its high adsorption and regeneration desorption performances.

  3. Evidence for a CO Desorption Front in the Outer AS 209 Disk

    Science.gov (United States)

    Huang, Jane; Öberg, Karin I.; Andrews, Sean M.

    2016-05-01

    Millimeter observations of CO isotopologues are often used to make inferences about protoplanetary disk gas density and temperature structures. The accuracy of these estimates depends on our understanding of CO freezeout and desorption from dust grains. Most models of these processes indicate that CO column density decreases monotonically with distance from the central star due to a decrease in gas density and freezeout beyond the CO snowline. We present ALMA Cycle 2 observations of 12CO, 13CO, and C18O J=2-1 emission that instead suggest CO enhancement in the outer disk of T Tauri star AS 209. Most notably, the C18O emission consists of a central peak and a ring at a radius of ˜ 1\\prime \\prime (120 au), well outside the expected CO snowline. We propose that the ring arises from the onset of CO desorption near the edge of the millimeter dust disk. CO desorption exterior to a CO snowline may occur via non-thermal processes involving cosmic rays or high-energy photons, or via a radial thermal inversion arising from dust migration.

  4. Evidence for a CO desorption front in the outer AS 209 disk

    CERN Document Server

    Huang, Jane; Andrews, Sean M

    2016-01-01

    Millimeter observations of CO isotopologues are often used to make inferences about protoplanetary disk gas density and temperature structures. The accuracy of these estimates depends on our understanding of CO freezeout and desorption from dust grains. Most models of these processes indicate that CO column density decreases monotonically with distance from the central star due to a decrease in gas density and freezeout beyond the CO snowline. We present ALMA Cycle 2 observations of $^{12}$CO, $^{13}$CO, and C$^{18}$O $J=2-1$ emission that instead suggest CO enhancement in the outer disk of T Tauri star AS 209. Most notably, the C$^{18}$O emission consists of a central peak and a ring at a radius of $\\sim1''$ (120 AU), well outside the expected CO snowline. We propose that the ring arises from the onset of CO desorption near the edge of the millimeter dust disk. CO desorption exterior to a CO snowline may occur via non-thermal processes involving cosmic rays or high-energy photons, or via a radial thermal inv...

  5. Optical breathing of nano-porous antireflective coatings through adsorption and desorption of water.

    Science.gov (United States)

    Nielsen, Karsten H; Kittel, Thomas; Wondraczek, Katrin; Wondraczek, Lothar

    2014-10-13

    We report on the direct consequences of reversible water adsorption on the optical performance of silica-based nanoporous antireflective (AR) coatings as they are applied on glass in photovoltaic and solar thermal energy conversion systems. In situ UV-VIS transmission spectroscopy and path length measurements through high-resolution interferometric microscopy were conducted on model films during exposure to different levels of humidity and temperature. We show that water adsorption in the pores of the film results in a notable increase of the effective refractive index of the coating. As a consequence, the AR effect is strongly reduced. The temperature regime in which the major part of the water can be driven-out rapidly lies in the range of 55°C and 135°C. Such thermal desorption was found to increase the overall transmission of a coated glass by ~ 1%-point. As the activation energy of isothermal desorption, we find a value of about 18 kJ/mol. Within the experimental range of our data, the sorption and desorption process is fully reversible, resulting in optical breathing of the film. Nanoporous AR films with closed pore structure or high hydrophobicity may be of advantage for maintaining AR performance under air exposure.

  6. Optical breathing of nano-porous antireflective coatings through adsorption and desorption of water

    Science.gov (United States)

    Nielsen, Karsten H.; Kittel, Thomas; Wondraczek, Katrin; Wondraczek, Lothar

    2014-10-01

    We report on the direct consequences of reversible water adsorption on the optical performance of silica-based nanoporous antireflective (AR) coatings as they are applied on glass in photovoltaic and solar thermal energy conversion systems. In situ UV-VIS transmission spectroscopy and path length measurements through high-resolution interferometric microscopy were conducted on model films during exposure to different levels of humidity and temperature. We show that water adsorption in the pores of the film results in a notable increase of the effective refractive index of the coating. As a consequence, the AR effect is strongly reduced. The temperature regime in which the major part of the water can be driven-out rapidly lies in the range of 55°C and 135°C. Such thermal desorption was found to increase the overall transmission of a coated glass by ~ 1%-point. As the activation energy of isothermal desorption, we find a value of about 18 kJ/mol. Within the experimental range of our data, the sorption and desorption process is fully reversible, resulting in optical breathing of the film. Nanoporous AR films with closed pore structure or high hydrophobicity may be of advantage for maintaining AR performance under air exposure.

  7. Kinetic Monte Carlo simulations of temperature programed desorption of O/Rh(111).

    Science.gov (United States)

    Franz, T; Mittendorfer, F

    2010-05-21

    We present a kinetic Monte Carlo simulation based on ab initio calculations for the thermal desorption of oxygen from a Rh(111) surface. Several models have been used for the parametrization of the interaction between the adsorbed atoms. We find that models based on a parametrization with only pairwise interactions have a relatively large error in the predicted adsorption energies. This error can be significantly reduced by including three- and four-body interactions. In addition, we find that a significant amount of atoms adsorb in a second adsorption site - the hcp-hollow site - at an elevated temperature. Consequently, only a many-body multisite model of the oxygen interactions yields appropriate desorption spectra for the full coverage range, while more simple models only capture the correct shape in the low-coverage case. Our parametrization allows us to predict the adsorption energies of an arbitrary configuration of adsorbates with a mean average error of less than 6 meV/atom.

  8. Large Scale Nanoparticle Screening for Small Molecule Analysis in Laser Desorption Ionization Mass Spectrometry.

    Science.gov (United States)

    Yagnik, Gargey B; Hansen, Rebecca L; Korte, Andrew R; Reichert, Malinda D; Vela, Javier; Lee, Young Jin

    2016-09-20

    Nanoparticles (NPs) have been suggested as efficient matrixes for small molecule profiling and imaging by laser-desorption ionization mass spectrometry (LDI-MS), but so far there has been no systematic study comparing different NPs in the analysis of various classes of small molecules. Here, we present a large scale screening of 13 NPs for the analysis of two dozen small metabolite molecules. Many NPs showed much higher LDI efficiency than organic matrixes in positive mode and some NPs showed comparable efficiencies for selected analytes in negative mode. Our results suggest that a thermally driven desorption process is a key factor for metal oxide NPs, but chemical interactions are also very important, especially for other NPs. The screening results provide a useful guideline for the selection of NPs in the LDI-MS analysis of small molecules.

  9. Kinetics of hydrogen desorption from MgH2 and AlH3 hydrides

    Science.gov (United States)

    Terent'ev, P. B.; Gerasimov, E. G.; Mushnikov, N. V.; Uimin, M. A.; Maikov, V. V.; Gaviko, V. S.; Golovatenko, V. D.

    2015-12-01

    Kinetic parameters of the process of thermal decomposition of the MgH2 hydride (obtained by the method of the mechanoactivation of magnesium in a hydrogen atmosphere) and of the commercial AlH3 hydride have been studied upon the rapid heating in the range of temperatures of 150-510°C at hydrogen pressures of 0-2 atm. The time dependences of the amount of hydrogen released by the metal hydrides at different temperatures and pressures have been determined. It has been shown that the activation energies of the hydrogen desorption are 135 kJ/mol for MgH2 and 107 kJ/mol for AlH3. The maximum rates of hydrogen desorption from the investigated metal hydrides have been established, and the temperatures and initial pressures that ensure the maximum rate and maximum volume of the hydrogen release have been determined.

  10. Experimental study on effects of CBM temperature-rising desorption

    Institute of Scientific and Technical Information of China (English)

    MA Dong-min; LIN Ya-bing

    2012-01-01

    To study the effects of CBM (coal bed methane) temperature-rising desorption,isothermal adsorption/desorption experiments on three ranks (anthracite,coking coal and lignite) of coal at different temperatures were designed based on the traditional CBM decompression desorption.The experimental results indicate that temperature-rising desorption is more effective in high-rank coal,and ever-increasing temperature of high-rank coal reservoir can reduce the negative effects of coal matrix shrinkage in the process of production and improve the permeability of the coal reservoir as well.It is also revealed that the technique of temperature-rising desorption applied in higher-rank coal reservoir can enhance CBM recovery ratio.This study provided theoretical support for the application of temperature-rising desorption technique in practical discharging and mining projects,which can effectively tackle the gas production bottleneck problem.

  11. The effect of selective desorption mechanisms during interstellar ice formation

    CERN Document Server

    Kalvans, Juris

    2015-01-01

    Major components of ices on interstellar grains in molecular clouds - water and carbon oxides - occur at various optical depths. This implies that selective desorption mechanisms are at work. An astrochemical model of a contracting low-mass molecular cloud core is presented. Ice was treated as consisting of the surface and three subsurface layers (sublayers). Photodesorption, reactive desorption, and indirect reactive desorption were investigated. The latter manifests itself through desorption from H+H reaction on grains. Desorption of shallow subsurface species was included. Modeling results suggest the existence of a "photon-dominated ice" during the early phases of core contraction. Subsurface ice is chemically processed by interstellar photons, which produces complex organic molecules. Desorption from the subsurface layer results in high COM gas-phase abundances at Av = 2.4...10mag. This may contribute towards an explanation for COM observations in dark cores. It was found that photodesorption mostly gove...

  12. Nonisothermal desorption of droplets of complex compositions

    Directory of Open Access Journals (Sweden)

    Nakoryakov Vladimir E.

    2012-01-01

    Full Text Available This paper presents the process of nonstationary evaporation of aqueous solutions of LiBr-H2O, CaCl2-H2O, NaCl-H2O droplets on a horizontal heating surface. The following typical stages of heat and mass transfer depending on wall temperature have been considered: evaporation below boiling temperature and nucleate boiling. The significant decrease in desorption intensity with a rise of initial mass concentration of salt has been observed. Formation of a surface crystallization front at evaporation of a droplet has been detected. We have developed the experimental method for direct measurements of the mass of evaporating droplet.

  13. Displacement desorption test of coalbed methane and its mechanism exploring

    Institute of Scientific and Technical Information of China (English)

    ZHANG Suian; HUO Yongzhong; YE Jianping; TANG Shuheng; MA Dongmin

    2005-01-01

    Through the test of CH4 displaced by CO2 using the coal sample as the adsorbent, this paper has found the coalbed methane (CBM) displacement desorption phenomenon under the natural conditions and CBM mining conditions. With the help of the adsorption theory of the modern physical chemistry and interfacial chemistry, the CBM competitive adsorption and displacement desorption mechanism are intensively discussed, and a new path for studying the CBM desorption mechanism in the CBM exploitation process is explored.

  14. Kinetic isotope effect for H2 and D2 quantum molecular sieving in adsorption/desorption on porous carbon materials.

    Science.gov (United States)

    Zhao, Xuebo; Villar-Rodil, Silvia; Fletcher, Ashleigh J; Thomas, K Mark

    2006-05-25

    Adsorption and desorption of H(2) and D(2) from porous carbon materials, such as activated carbon at 77 K, are usually fully reversible with very rapid adsorption/desorption kinetics. The adsorption and desorption of H(2) and D(2) at 77 K on a carbon molecular sieve (Takeda 3A), where the kinetic selectivity was incorporated by carbon deposition, and a carbon, where the pore structure was modified by thermal annealing to give similar pore structure characteristics to the carbon molecular sieve substrate, were studied. The D(2) adsorption and desorption kinetics were significantly faster (up to x1.9) than the corresponding H(2) kinetics for specific pressure increments/decrements. This represents the first experimental observation of kinetic isotope quantum molecular sieving in porous materials due to the larger zero-point energy for the lighter H(2), resulting in slower adsorption/desorption kinetics compared with the heavier D(2). The results are discussed in terms of the adsorption mechanism.

  15. Substrate-Enhanced Micro Laser Desorption Ionization Mass Spectrometry Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Aerodyne Research, Inc. and the University of Massachusetts at Amherst will collaborate to develop laser desorption ionization (LDI) mass spectrometric analysis of...

  16. Testosterone sorption and desorption: Effects of soil particle size

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Yong, E-mail: yqi01@unomaha.edu [Civil Engineering Dept., University of Nebraska-Lincoln at Omaha Campus, Omaha, NE 68182 (United States); Zhang, Tian C. [Civil Engineering Dept., University of Nebraska-Lincoln at Omaha Campus, Omaha, NE 68182 (United States); Ren, Yongzheng [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2014-08-30

    Graphical abstract: - Highlights: • Smaller soil particles have higher sorption and lower desorption rates. • The sorption capacity ranks as clay > silt > sand. • Small particles like clays have less potential for desorption. • Colloids (clays) have high potential to facilitate the transport of hormones in soil–water environments. - Abstract: Soils contain a wide range of particles of different diameters with different mobility during rainfall events. Effects of soil particles on sorption and desorption behaviors of steroid hormones have not been investigated. In this study, wet sieve washing and repeated sedimentation methods were used to fractionate the soils into five ranges. The sorption and desorption properties and related mechanisms of testosterone in batch reactors filled with fractionated soil particles were evaluated. Results of sorption and desorption kinetics indicate that small soil particles have higher sorption and lower desorption rates than that of big ones. Thermodynamic results show the sorption processes are spontaneous and exothermal. The sorption capacity ranks as clay > silt > sand, depending mainly on specific surface area and surface functional groups. The urea control test shows that hydrogen bonding contributes to testosterone sorption onto clay and silt but not on sand. Desorption tests indicate sorption is 36–65% irreversible from clay to sand. Clays have highest desorption hysteresis among these five soil fractions, indicating small particles like clays have less potential for desorption. The results provide indirect evidence on the colloid (clay)-facilitated transport of hormones (micro-pollutants) in soil environments.

  17. UV-Vis diagnostics of the pmma-c 60 composite system and the kinetics of its thermal decomposition

    OpenAIRE

    Bogdanov, A. A.; VOZNYAKOVSKII A.P.; POZDNYAKOV A.O.

    2014-01-01

    The influence of polymer-fullerene interactions and fullerene aggregation on the thermal stability of polymethyl-methacrylate-fullerene C 60 nanocomposite has been studied by means of thermal desorption mass-spectrometry and the UV-Vis absorption spectroscopy.

  18. UV-VIS DIAGNOSTICS OF THE PMMA-C 60 COMPOSITE SYSTEM AND THE KINETICS OF ITS THERMAL DECOMPOSITION

    OpenAIRE

    Bogdanov, A A; VOZNYAKOVSKII A.P.; POZDNYAKOV A.O.

    2014-01-01

    The influence of polymer-fullerene interactions and fullerene aggregation on the thermal stability of polymethyl-methacrylate-fullerene C 60 nanocomposite has been studied by means of thermal desorption mass-spectrometry and the UV-Vis absorption spectroscopy.

  19. CO and N$_2$ desorption energies from water ice

    CERN Document Server

    Fayolle, Edith C; Loomis, Ryan; Bergner, Jennifer; Graninger, Dawn M; Rajappan, Mahesh; Öberg, Karin I

    2015-01-01

    The relative desorption energies of CO and N$_2$ are key to interpretations of observed interstellar CO and N$_2$ abundance patterns, including the well-documented CO and N$_2$H$^+$ anti-correlations in disks, protostars and molecular cloud cores. Based on laboratory experiments on pure CO and N$_2$ ice desorption, the difference between CO and N$_2$ desorption energies is small; the N$_2$-to-CO desorption energy ratio is 0.93$\\pm$0.03. Interstellar ices are not pure, however, and in this study we explore the effect of water ice on the desorption energy ratio of the two molecules. We present temperature programmed desorption experiments of different coverages of $^{13}$CO and $^{15}$N$_2$ on porous and compact amorphous water ices and, for reference, of pure ices. In all experiments, $^{15}$N$_2$ desorption begins a few degrees before the onset of $^{13}$CO desorption. The $^{15}$N$_2$ and $^{13}$CO energy barriers are 770 and 866 K for the pure ices, 1034-1143 K and 1155-1298 K for different sub-monolayer co...

  20. Integrated field emission array for ion desorption

    Energy Technology Data Exchange (ETDEWEB)

    Resnick, Paul J; Hertz, Kristin L.; Holland, Christopher; Chichester, David

    2016-08-23

    An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

  1. Methane desorption from a coal-bed

    Energy Technology Data Exchange (ETDEWEB)

    A.D. Alexeev; E.P. Feldman; T.A. Vasilenko [National Academy of Sciences of Ukraine, Donetsk (Ukraine). Donetsk Institute for Physics of Mining Processes

    2007-11-15

    We study the desorption of methane from a coal-bed. A model taking into account both methane diffusion in coal-blocks and its filtration through the system of open pores and cracks is developed. Methane pressure in the coal-bed is found for an arbitrary instant of time. Dependency of the rate of methane release upon the block size, open and closed porosity, viscosity, solubility, bed pressure and temperature is established. We derive the effective coefficient of diffusion of methane in blocks containing closed pores filled with gaseous methane. It is shown that at a hindered diffusion methane is distinctly divided into the 'quick' and the 'slow' one. 25 refs., 5 figs.

  2. Integrated field emission array for ion desorption

    Energy Technology Data Exchange (ETDEWEB)

    Resnick, Paul J; Hertz, Kristin L; Holland, Christopher; Chichester, David; Schwoebel, Paul

    2013-09-17

    An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

  3. Integrated field emission array for ion desorption

    Science.gov (United States)

    Resnick, Paul J; Hertz, Kristin L; Holland, Christopher; Chichester, David; Schwoebel, Paul

    2013-09-17

    An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

  4. Copper desorption from Gelidium algal biomass.

    Science.gov (United States)

    Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

    2007-04-01

    Desorption of divalent copper from marine algae Gelidium sesquipedale, an algal waste (from agar extraction industry) and a composite material (the algal waste immobilized in polyacrylonitrile) was studied in a batch system. Copper ions were first adsorbed until saturation and then desorbed by HNO(3) and Na(2)EDTA solutions. Elution efficiency using HNO(3) increases as pH decreases. At pH=1, for a solid to liquid ratio S/L=4gl(-1), elution efficiency was 97%, 95% and 88%, the stoichiometric coefficient for the ionic exchange, 0.70+/-0.02, 0.73+/-0.05 and 0.76+/-0.06 and the selectivity coefficient, 0.93+/-0.07, 1.0+/-0.3 and 1.1+/-0.3, respectively, for algae Gelidium, algal waste and composite material. Complexation of copper ions by EDTA occurs in a molar proportion of 1:1 and the elution efficiency increases with EDTA concentration. For concentrations of 1.4, 0.88 and 0.57 mmoll(-1), the elution efficiency for S/L=4gl(-1), was 91%, 86% and 78%, respectively, for algae Gelidium, algal waste and composite material. The S/L ratio, in the range 1-20gl(-1), has little influence on copper recovery by using 0.1M HNO(3). Desorption kinetics was very fast for all biosorbents. Kinetic data using HNO(3) as eluant were well described by the mass transfer model, considering the average metal concentration in the solid phase and the equilibrium relationship given by the mass action law. The homogeneous diffusion coefficient varied between 1.0 x 10(-7)cm(2)s(-1) for algae Gelidium and 3.0 x 10(-7)cm(2)s(-1) for the composite material.

  5. Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle; Zhou, Jia; Ahmed, Musahid; Gasper, Gerald; Pleticha, F. Douglas; Hanley, Luke

    2011-03-14

    The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.

  6. Desorption and Degradation of Organic Contaminants in Soil by Microwave Radiation

    Science.gov (United States)

    Jeong, S.; Kim, H.

    2011-12-01

    Many military bases located in the down towns of South Korea are asked to move outside of the urban areas due to the growth of the cities. During the past 60 years, many military bases of South Korea have been operated and according to that, parts of the soil have been polluted with organic contaminants such as total petroleum hydrocarbons (TPH), solvents, etc. In the case of South Korea, rapid remediation of the contaminated soil is required for efficient development of land. Thermal desorption is one of the most efficient and rapid remediation methods for polluted soil to clean up, but the fact is it consumes a lot of energy. In this study, desorption and degradation of organic contaminants in soil using microwave radiation is investigated in order to energy efficient and rapid remediation technique development. Polluted soil collected from a military base was remediated in the laboratory using a home made microwave reactor. In order to study uncontaminated soil was also intentionally contaminated with diesel, TCE, and phenanthrene, respectively, for a month and used for experiments. Contaminated soil places within stainless steel reactor and microwave radiates with nitrogen gas. Emitted gas from the reactor was collected with methanol or acetonitrile solution every 3 minute for 15 minutes, and analyzed with GC, HPLC, GC/MS, respectively. The TPH contaminated soil from military base desorbed initially light hydrocarbon (retention time reaction, iron powder, graphite will be added to the contaminated soil and desorption and degradation properties of this soil during microwave radiation will be studied.

  7. Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

    2015-10-05

    Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

  8. Variable Temperature Infrared Spectroscopy Investigations of Benzoic Acid Desorption from Sodium and Calcium Montmorillonite Clays.

    Science.gov (United States)

    Nickels, Tara M; Ingram, Audrey L; Maraoulaite, Dalia K; White, Robert L

    2015-12-01

    Processes involved in thermal desorption of benzoic acid from sodium and calcium montmorillonite clays are investigated by using variable temperature diffuse reflection Fourier transform infrared spectroscopy (DRIFTS). By monitoring the temperature dependence of infrared absorbance bands while heating samples, subtle changes in molecular vibrations are detected and employed to characterize specific benzoic acid adsorption sites. Abrupt changes in benzoic acid adsorption site properties occur for both clay samples at about 125 °C. Difference spectra absorbance band frequency variations indicate that adsorbed benzoic acid interacts with interlayer cations through water bridges and that these interactions can be disrupted by the presence of organic anions, in particular, benzoate.

  9. Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

    Science.gov (United States)

    Yakshinskiy, B. V.; Madey, T. E.

    2003-01-01

    We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

  10. Adsorption-Desorption Characteristics of Chlorimuron-Ethyl in Soils

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The adsorption-desorption characteristics of chlorimuron-ethyl in soils were investigated to provide the basic data for evaluating the safety in field and the risk to water resource. The adsorption-desorption experiment was conducted by the batch equilibration and HPLC techniques; furthermore, data were analyzed with 5 mathematic models to describe the characteristics and mechanism of adsorption-desorption and translocation of the herbicide in soils. The results showed that the adsorption-desorption isotherms of chlorimuron-ethyl fitted for the Freundlich model well, and the physical reaction presents the main contribution during the adsorption-desorption process. The adsorption values (Kads-f) of chlorimuron-ethyl in 8 types of soil ranged from 0.798 to 6.891. The isotherms of 2# (Jiangxi clay) and 3# (Jiangxi sand loam)soils belong to the S-type curve, while the isotherms of another 6 type soils belong to the L-type isotherm. The results of desorption indicated that the hysteresis phenomena appeared during the desorption process, and the hysteresis coefficients(H) of the herbicides in 8 soils varied from 0.259-0.980. Furthermore, Kads-f and desorption values (Kdes-f) increased with the OM (%) and the clay content increasing, while the values decreased with the soils pH increasing. The H values decreased with the OM and the clay content increasing, and increased with the soils pH increasing. It can be concluded that the low adsorption abilities of chlorimuron-ethyl in test soils and un-reversible adsorption existed in the process, which will induce the great translocation of the herbicide after application in field. It can be transported to ground or groundwater causing risk to environments. The physical and chemical properties of soils, including the OM, the clay content, and the pH of soil were the dominating factors during the adsorption-desorption.

  11. 24-HOUR DIFFUSIVE SAMPLING OF 1,3-BUTADIENE IN AIR ONTO CARBONPAK X SOLID ADSORBENT WITH THEMAL DESORPTION/GC/MS ANALYSIS - FEASIBILITY STUDIES

    Science.gov (United States)

    Diffusive sampling of 1,3-butadiene for 24 hours onto the graphitic adsorbent Carbopack X contained in a stainless steel tube badge (6.3 mm OD, 5 mm ID, and 90 mm in length) with analysis by thermal desorption/GC/MS has been evaluated in controlled tests. A test matrix of 42 tr...

  12. Temperature programmed desorption of weakly bound adsorbates on Au(111)

    Science.gov (United States)

    Engelhart, Daniel P.; Wagner, Roman J. V.; Meling, Artur; Wodtke, Alec M.; Schäfer, Tim

    2016-08-01

    We have performed temperature programmed desorption (TPD) experiments to analyze the desorption kinetics of Ar, Kr, Xe, C2H2, SF6, N2, NO and CO on Au(111). We report desorption activation energies (Edes), which are an excellent proxy for the binding energies. The derived binding energies scale with the polarizability of the molecules, consistent with the conclusion that the surface-adsorbate bonds arise due to dispersion forces. The reported results serve as a benchmark for theories of dispersion force interactions of molecules at metal surfaces.

  13. Hydrogen Desorption from Mg Hydride: An Ab Initio Study

    Directory of Open Access Journals (Sweden)

    Simone Giusepponi

    2012-07-01

    Full Text Available Hydrogen desorption from hydride matrix is still an open field of research. By means of accurate first-principle molecular dynamics (MD simulations an Mg–MgH2 interface is selected, studied and characterized. Electronic structure calculations are used to determine the equilibrium properties and the behavior of the surfaces in terms of structural deformations and total energy considerations. Furthermore, extensive ab-initio molecular dynamics simulations are performed at several temperatures to characterize the desorption process at the interface. The numerical model successfully reproduces the experimental desorption temperature for the hydride.

  14. Desorption kinetics of benzene in a sandy soil in the presence of powdered activated carbon.

    Science.gov (United States)

    Choi, J-W; Kim, S-B; Kim, D-J

    2007-02-01

    Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption-desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q (irr)) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption-desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q (irr)) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4-40 times) rate constant for rapid process (k (1)) than that for slow process (k (2)), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.

  15. Salt Tolerance of Desorption Electrospray Ionization (DESI)

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Ayanna U. [Purdue University; Talaty, Nari [Purdue University; Cooks, R G [Purdue University; Van Berkel, Gary J [ORNL

    2007-01-01

    Suppression of ion intensity in the presence of high salt matrices is common in most mass spectrometry ionization techniques. Desorption electrospray ionization (DESI) is an ionization method that exhibits salt tolerance, and this is investigated. DESI analysis was performed on three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl weight by volume from seven different surfaces. At physiological concentrations individual drugs in each mixture were observed with each surface. Collision-induced dissociation (CID) was used to provide additional confirmation for select compounds. Multiple stage experiments, to MS5, were performed for select compounds. Even in the absence of added salt, the benzodiazepine containing mixture yielded sodium and potassium adducts of carbamazepine which masked the ions of interest. These adducts were eliminated by adding 0.1% 7M ammonium acetate to the standard methanol:water (1:1) spray solvent. Comparison of the salt tolerance of DESI with that of electrospray ionization (ESI) demonstrated much better signal/noise characteristics for DESI in this study. The salt tolerance of DESI was also studied by performing limit of detection and dynamic range experiments. Even at a salt concentration significantly above physiological concentrations, select surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution.

  16. Tailoring the hydrogen desorption thermodynamics of V{sub 2}H by alloying additives

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Sanjay, E-mail: sanjay.barc@gmail.com [Fusion Reactor Materials Section, BARC, Mumbai (India); Tiwari, G.P. [R.A. Institute of Technology, Vidya Nagri, Nerul 400709, Navi Mumbai (India); Krishnamurthy, N. [Fusion Reactor Materials Section, BARC, Mumbai (India)

    2015-10-05

    Highlights: • Decomposition of VH{sub 2} is three step process. • Electronic structure and H solubility are correlated. • Addition of hydride forming metal enhance the thermal stability of V{sub 2}H. • Lattices strain energy could decrease thermal stability of V{sub 2}H. - Abstract: Vanadium could be a potential candidate for on board hydrogen storage application because of its high gravimetric hydrogen storage capacity (∼3.8 mass%) which is even better then the most widely explored AB{sub 5}, AB{sub 2} & AB intermetallic compounds. Hydrogen absorption of vanadium takes place at ambient temperature and pressure with fast kinetics. The vanadium hydride (VH{sub 2}) releases hydrogen in two steps: (1) VH{sub 2}(γ){sub (s)} ↔ ½ V{sub 2}H(β){sub (s)} and (2) V{sub 2}H(β){sub (s)} ↔ 2V{sub (s)} + ½ H{sub 2(g)}. First step is achievable at the ambient temperature and pressure conditions while, the second step requires high temperature (590 K). Thus only half of the total hydrogen storage capacity is available for use on subsequent absorption–desorption cycles at the ambient temperature. The usable hydrogen storage capacity of VH{sub 2} at ambient conditions could be enhanced by tailoring the thermodynamics and kinetics of second step of hydrogen desorption reaction. This could be possible by selecting suitable alloy additives. The present study deals with the selection criteria of alloy additives based on the electronic consideration to tailor the hydrogen desorption thermodynamics and kinetics of V{sub 2}H.

  17. Microstructure and He desorption behaviors of He charged FeCrNi-based films fabricated by direct current magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Song, L. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Wang, X.P., E-mail: xpwang@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Liu, F. [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei 230031 (China); Gao, Y.X. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Zhang, T., E-mail: zhangtao@issp.ac.cn [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China); Luo, G.N. [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei 230031 (China); Fang, Q.F.; Liu, C.S. [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, P.O. Box 1129, Hefei 230031 (China)

    2015-08-31

    He-charged FeCrNi-based films were prepared at different temperatures in a mixed atmosphere of He and Ar by direct-current magnetron sputtering method. X-ray diffraction and energy dispersive spectrometry analysis confirmed the typical austenitic structure of the deposited FeCrNi films and the compositions were in good accordance with 304 stainless steel target. Cross-sectional scanning electron microscopy images revealed the dense columnar nanocrystalline structure of the fabricated FeCrNi films. Nanoindentation measurements showed that the film fabricated at 300 °C exhibited the highest hardness value of 11.5 GPa. He desorption from FeCrNi-based films was traced by thermal desorption spectroscopy; the relatively low He desorption temperature range (150 °C–450 °C) implied that the charged He atoms were mainly located in interstitial sites of FeCrNi-based films. - Highlights: • He-charged columnar nanocrystalline FeCrNi films were prepared by DC magnetron sputtering. • Substrate temperature of 300 °C and He/Ar ratio 1:1 were the best sputtering parameters. • Compact and uniform microstructure obtained at 300 °C resulted in stable, high hardness. • Two He atoms' absorption/desorption mechanisms were revealed by TDS.

  18. Adsorption and desorption kinetics of carbofuran in acid soils.

    Science.gov (United States)

    Bermúdez-Couso, Alipio; Fernández-Calviño, David; Pateiro-Moure, Miriam; Nóvoa-Muñoz, Juan Carlos; Simal-Gándara, Jesús; Arias-Estévez, Manuel

    2011-06-15

    Carbofuran adsorption and desorption were investigated in batch and stirred flow chamber (SFC) tests. The carbofuran adsorption capacity of the soils was found to be low and strongly dependent on their clay and organic carbon contents. Carbofuran sorption was due mainly (>80%) to fast adsorption processes governed by intraparticle diffusion. The adsorption kinetic constant for the pesticide ranged from 0.047 to 0.195 min(-1) and was highly correlated with constant n in the Freundlich equation (r=0.965, Pcarbofuran desorption to be highly variable and negatively correlated with eCEC and the clay content. The SFC tests showed that soil organic carbon (C) plays a key role in the irreversibility of carbofuran adsorption. Carbofuran desorption increased rapidly at C contents below 4%. The desorption kinetic constant for the compound (0.086-0.195 min(-1)) was generally higher than its adsorption kinetic constant; therefore, carbofuran is more rapidly desorbed than it is adsorbed in soil.

  19. ACTIVATION ENERGY OF DESORPTION OF DIBENZOFURAN ON ACTIVATED CARBONS

    Institute of Scientific and Technical Information of China (English)

    LI Xiang; LI Zhong; XI Hongxia; LUO Lingai

    2004-01-01

    Three kinds of commercial activated carbons, such as Norit RB1, Monolith and Chemviron activated carbons, were used as adsorbents for adsorption of dibenzofuran. The average pore size and specific surface area of these activated carbons were measured. Temperature Programmed Desorption (TPD) experiments were conducted to measure the TPD curves of dibenzofuran on the activated carbons, and then the activation energy for desorption of dibenzofuran on the activated carbons was estimated. The results showed that the Chemviron and the Norit RB1 activated carbon maintained higher specific surface area and larger micropore pore volume in comparison with the Monolith activated carbon, and the activation energy for the desorption of dibenzofuran on these two activated carbons was higher than that on the Monolith activated carbon. The smaller the pore of the activated carbon was, the higher the activated energy of dibenzofuran desorption was.

  20. Thermogravimetric desorption and de novo tests I: method development and validation.

    Science.gov (United States)

    Tsytsik, Palina; Czech, Jan; Carleer, Robert; Reggers, Guy; Buekens, Alfons

    2008-08-01

    Thermogravimetric analysis (TGA) has been combined with evolved gas analysis (EGA) with the purpose of simulating the thermal behaviour of filter dust samples under inert (desorption) and de novo test oxidising conditions. Emphasis is on studying de novo formation of dioxins, surrogates and precursors arising from filter dust derived from thermal processes, such as municipal solid waste incineration and metallurgy. A new method is tested for sampling and analysing dioxin surrogates and precursors in the TGA effluent, which are collected on sampling tubes; the adsorbed compounds are eventually desorbed and quantified by TD-GC-MS. The major sources of error and losses are considered, including potential sorbent artefacts, possible breakthrough of volatiles through sampling tubes, or eventual losses of semi-volatiles due to their incomplete desorption or re-condensation inside the TG Analyser. The method is optimised and validated for di- to hexa-chlorinated benzenes in a range of 10-1000 ppb with average recovery exceeding 85%. The results are compared with data obtained in similar studies, performed by other research groups. As a result, the method provides the means for simulating de novo synthesis of dioxins in fly-ash and facilitates reliable and easy estimation of de novo activity, comparable with results of other studies, in combination with wide flexibility of testing conditions.

  1. Sorption, Desorption and Diffusion of Tc Under Anaerobic Conditions

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The sorption and diffusion of Tc on granite under anaerobic conditions were investigated. Influencesof pH values, ferrous minerals(reduced iron powder or magnetite), bentonite, concentration of cations andanion (Fe3+, Fe2+ and CO32-) on the distribution coefficient, Kd, were studied. The sorption mechanism of99Tc on granite was analyzed by the desorption method of adding H2O2 into desorption solvent. Based on

  2. Sorption and desorption of 1,4-dichlorobenzene on peat

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Sorption and desorption of 1,4-dichlorobenzene (DCB) on peat (>92% organic matter)display large-scale hysteresis and nonlinearity. The magnitude of desorption hysteresis decreases in the order: untreated Pahokee peat (P)>acid treated peat (FP)>humin (TP). The desorption percentages are lower than 28% of the sorbed 1, 4-DCB after desorbing for 6 days. The sorption and desorption isotherms are well fitted to Freundlich equation, whose parameter 1/n ranges from 0.055 to 0.527. Moreover, the parameter 1/n of the desorption isotherm is significantly lower than that of the sorption isotherm, but the parameter IogK increases on contrary to 1/n. The desorption isotherms are very well fitted to Langmuir equation, whose Qm decreases in the order: TP>FP>P.The apparent partition coefficients (Kp) increase with increasing sorption time or decreasing aqueous equilibrium concentration of DCB. And Kp of P is significantly higher than that of FP or TP.

  3. Calcium lignosulfonate adsorption and desorption on Berea sandstone.

    Science.gov (United States)

    Grigg, Reid B; Bai, Baojun

    2004-11-01

    This paper describes adsorption and desorption studies carried out with calcium lignosulfonate (CLS) on Berea sandstone. Circulation experiments were performed to determine CLS adsorption isotherms and the effects of CLS concentration, temperature, salinity, brine hardness, and injection rate on adsorption density. Flow-through experiments were performed to assess the reversibility of CLS adsorption and the influence of postflush rate, brine concentration, brine hardness, brine pH, and temperature on the desorption process. Results indicate that CLS adsorption isotherms on Berea sandstone follow the Freundlich isotherm law. The results presented in this paper on the effects of CLS adsorption and desorption on Berea sandstone show that: (1) increasing CLS concentration and salinity increases CLS adsorption density; (2) increasing temperature will decrease adsorption density; (3) increasing injection rate of CLS solution will slightly decrease CLS adsorption density; (4) postflush rate and salinity of brine have a large impact on the CLS desorption process; (5) the adsorption and desorption process are not completely reversible; and (5) temperature and pH of the postflush brine have little effect on desorption.

  4. Adsorption and desorption dynamics of citric acid anions in soil

    KAUST Repository

    Oburger, E.

    2011-07-26

    The functional role of organic acid anions in soil has been intensively investigated, with special focus on (i) microbial respiration and soil carbon dynamics, (ii) nutrient solubilization or (iii) metal detoxification and reduction of plant metal uptake. Little is known about the interaction dynamics of organic acid anions with the soil matrix and the potential impact of adsorption and desorption processes on the functional significance of these effects. The aim of this study was to characterize experimentally the adsorption and desorption dynamics of organic acid anions in five agricultural soils differing in iron and aluminium oxide contents and using citrate as a model carboxylate. Results showed that both adsorption and desorption processes were fast in all soils, reaching a steady state within approximately 1 hour. However, for a given total soil citrate concentration (ct) the steady state was critically dependent on the starting conditions of the experiment, whether most of the citrate was initially present in solution (cl) or held on the solid phase (cs). Specifically, desorption-led processes resulted in significantly smaller steady-state solution concentrations than adsorption-led processes, indicating that hysteresis occurred. As it is not possible to distinguish between different adsorption and desorption pools in soil experimentally, a new dynamic hysteresis model that relies only on measured soil solution concentrations was developed. The model satisfactorily explained experimental data and was able to predict dynamic adsorption and desorption behaviour. To demonstrate its use, we applied the model to two relevant situations involving exudation and microbial degradation. The study highlighted the complex nature of citrate adsorption and desorption dynamics in soil. We conclude that existing models need to incorporate both temporal and hysteresis components to describe realistically the role and fate of organic acids in soil processes. © 2011 The

  5. The laser desorption/laser ionization mass spectra of some methylated xanthines and the laser desorption of caffeine and theophylline from thin layer chromatography plates

    Science.gov (United States)

    Rogers, Kevin; Milnes, John; Gormally, John

    1993-02-01

    Laser desorption/laser ionization time-of-flight mass spectra of caffeine, theophylline, theobromine and xanthine are reported. These mass spectra are compared with published spectra obtained using electron impact ionization. Mass spectra of caffeine and theophylline obtained by IR laser desorption from thin layer chromatography plates are also described. The laser desorption of materials from thin layer chromatography plates is discussed.

  6. Effects of BaRuO{sub 3} addition on hydrogen desorption in MgH{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Baricco, M., E-mail: marcello.baricco@unito.it [Dipartimento di Chimica IFM and NIS, Universita di Torino, Via P. Giuria 9, 10125 Torino (Italy); Rahman, M.W.; Livraghi, S.; Castellero, A. [Dipartimento di Chimica IFM and NIS, Universita di Torino, Via P. Giuria 9, 10125 Torino (Italy); Enzo, S. [Dipartimento di Chimica, Universita di Sassari, Via Vienna, 2, 07100 Sassari (Italy); Giamello, E. [Dipartimento di Chimica IFM and NIS, Universita di Torino, Via P. Giuria 9, 10125 Torino (Italy)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer Interaction of BaRuO{sub 3} with hydrogen studied. Black-Right-Pointing-Pointer BaRuO{sub 3} is able to release hydrogen after absorption. Black-Right-Pointing-Pointer A distorted rhomohedral phase is formed in BaRuO{sub 3} after hydrogen absorption. Black-Right-Pointing-Pointer A mixture of BaRuO{sub 3} with MgH{sub 2} is able to desorb hydrogen much faster than the parent materials. The interaction of hydrogen with the oxide additive is a crucial aspect for improving the hydrogen desorption rate. - Abstract: Hydrogen storage in MgH{sub 2} is strongly limited by kinetic constraints, so that several additives have been considered in order to improve the rate of hydrogen desorption. The present work is devoted to investigate the effect of BaRuO{sub 3} addition on hydrogen absorption and desorption properties of MgH{sub 2}. BaRuO{sub 3} was prepared by solid-state synthesis of BaO and Ru in oxidizing environment. The interaction of as-prepared BaRuO{sub 3} with hydrogen at room temperature was examined by thermal desorption and X-ray diffraction experiments, showing that BaRuO{sub 3} has the ability to uptake hydrogen in the bulk. The hydrogen interaction is discussed with respect to octahedral ruthenium local environment present in the oxide structure. Addition of 1 mol.% BaRuO{sub 3} to MgH{sub 2} was performed by ball milling. Hydrogen desorption properties were investigated by Sievert and DSC, connected with a H{sub 2} detector. The H{sub 2} desorbed from of the nano-structured materials is lower than the theoretical content in MgH{sub 2}, due to the presence of a non-reactive MgO layer. A remarkable increase of the H{sub 2} desorption kinetics in nano-structured MgH{sub 2} was observed with respect to bare MgH{sub 2}. The activation energy for hydrogen desorption from MgH{sub 2}/BaRuO{sub 3} mixture was estimated by Arrhenius and Kissinger methods and a value around 130 kJ mol{sup -1} and 90 kJ mol{sup -1} was obtained

  7. Sorption-desorption behavior of polybrominated diphenyl ethers in soils

    Energy Technology Data Exchange (ETDEWEB)

    Olshansky, Yaniv; Polubesova, Tamara [Department of Soil and Water Sciences, Robert H. Smith Faculty of Agriculture, Food and Environment, Hebrew University of Jerusalem, P.O. Box 12, Rehovot 76100 (Israel); Vetter, Walter [Institute of Food Chemistry (170b), University of Hohenheim, Garbenstr. 28, D-70599 Stuttgart (Germany); Chefetz, Benny, E-mail: chefetz@agri.huji.ac.il [Department of Soil and Water Sciences, Robert H. Smith Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 76100 (Israel)

    2011-10-15

    Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4'-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K{sub OC}) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration. - Highlights: > BDE-15 exhibited pronounced desorption hysteresis. > BDE-15 sowed higher sorption affinity to humin as compared to the bulk soils. > Sequestration of PBDEs depends on soil organic matter constitutes other than humin. - Pronounced desorption hysteresis was observed for BDE-15 in natural soils.

  8. Solid solution barium–strontium chlorides with tunable ammonia desorption properties and superior storage capacity

    Energy Technology Data Exchange (ETDEWEB)

    Bialy, Agata [Amminex Emissions Technology A/S, Gladsaxevej 363, 2860 Soeborg (Denmark); Jensen, Peter B. [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, Fysikvej 311, DK-2800 Kgs. Lyngby (Denmark); Blanchard, Didier [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Vegge, Tejs, E-mail: teve@dtu.dk [Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Quaade, Ulrich J., E-mail: ujq@amminex.com [Amminex Emissions Technology A/S, Gladsaxevej 363, 2860 Soeborg (Denmark)

    2015-01-15

    Metal halide ammines are very attractive materials for ammonia absorption and storage—applications where the practically accessible or usable gravimetric and volumetric storage densities are of critical importance. Here we present, that by combining advanced computational materials prediction with spray drying and in situ thermogravimetric and structural characterization, we synthesize a range of new, stable barium-strontium chloride solid solutions with superior ammonia storage densities. By tuning the barium/strontium ratio, different crystallographic phases and compositions can be obtained with different ammonia ab- and desorption properties. In particular it is shown, that in the molar range of 35–50% barium and 65–50% strontium, stable materials can be produced with a practically usable ammonia density (both volumetric and gravimetric) that is higher than any of the pure metal halides, and with a practically accessible volumetric ammonia densities in excess of 99% of liquid ammonia. - Graphical abstract: Thermal desorption curves of ammonia from Ba{sub x}Sr{sub (1−x)}Cl{sub 2} mixtures with x equal to 0.125, 0.25 and 0.5 and atomic structure of Sr(NH{sub 3}){sub 8}Cl{sub 2}. - Highlights: • Solid solutions of strontium and barium chloride were synthesized by spray drying. • Adjusting molar ratios led to different crystallographic phases and compositions. • Different molar ratios led to different ammonia ab-/desorption properties. • 35–50 mol% BaCl{sub 2} in SrCl{sub 2} yields higher ammonia density than any other metal halide. • DFT calculations can be used to predict properties of the mixtures.

  9. Laboratory H2O:CO2 ice desorption data: entrapment dependencies and its parameterization with an extended three-phase model

    CERN Document Server

    Fayolle, Edith C; Cuppen, Herma M; Visser, Ruud; Linnartz, Harold; 10.1051/0004-6361/201016121

    2011-01-01

    Ice desorption affects the evolution of the gas-phase chemistry during the protostellar stage, and also determines the chemical composition of comets forming in circumstellar disks. From observations, most volatile species are found in H2O-dominated ices. The aim of this study is first to experimentally determine how entrapment of volatiles in H2O ice depends on ice thickness, mixture ratio and heating rate, and second, to introduce an extended three-phase model (gas, ice surface and ice mantle) to describe ice mixture desorption with a minimum number of free parameters. Thermal H2O:CO2 ice desorption is investigated in temperature programmed desorption experiments of thin (10 - 40 ML) ice mixtures under ultra-high vacuum conditions. Desorption is simultaneously monitored by mass spectrometry and reflection-absorption infrared spectroscopy. The H2O:CO2 experiments are complemented with selected H2O:CO, and H2O:CO2:CO experiments. The results are modeled with rate equations that connect the gas, ice surface an...

  10. Femtosecond laser pulse induced desorption: A molecular dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Lončarić, Ivor, E-mail: ivor.loncaric@gmail.com [Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Alducin, Maite [Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Saalfrank, Peter [Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, D-14476 Potsdam (Germany); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain); Juaristi, J. Iñaki [Departamento de Física de Materiales, Facultad de Químicas, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080 San Sebastián (Spain); Centro de Física de Materiales CFM/MPC (CSIC-UPV/EHU), P. Manuel de Lardizabal 5, 20018 San Sebastián (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastián (Spain)

    2016-09-01

    In recent simulations of femtosecond laser induced desorption of molecular oxygen from the Ag(110) surface, it has been shown that depending on the properties (depth and electronic environment) of the well in which O{sub 2} is adsorbed, the desorption can be either induced dominantly by hot electrons or via excitations of phonons. In this work we explore whether the ratios between the desorption yields from different adsorption wells can be tuned by changing initial surface temperature and laser pulse properties. We show that the initial surface temperature is an important parameter, and that by using low initial surface temperatures the electronically mediated process can be favored. In contrast, laser properties seem to have only a modest influence on the results.

  11. A study of the process of desorption of hexavalent chromium

    Directory of Open Access Journals (Sweden)

    W.B. Amorim

    2003-09-01

    Full Text Available In this work the process of desorption of hexavalent chromium, a toxic metal ion, from the marine algae Sargassum sp, following biosorption experiments 2³ factorial design was studied. A technique was applied to three eluents: HCl, H2SO4 and EDTA. Three factors of importance were evaluated: concentration of eluent, the ratio between mass of biosorbent and volume of eluent (S/L and process time. A statistical analysis of the experimental results showed that the three variables evaluated are significant for all three eluents. The models for chromium desorption were validated, as the results agreed well with the observed values. Through use of the response surface methodology, a factorial design based optimization technique; it was possible to identify the most suitable eluent and the interval of values for the process variables that resulted in the most significant desorption of chromium, which is relevant information for work aiming at process optimization.

  12. Direct scattering, trapping, and desorption in atom-surface collisions.

    Science.gov (United States)

    Fan, Guoqing; Manson, J R

    2008-08-08

    Maxwell is credited as the first to invoke the assumption that an impinging gas beam scatters from a surface with a direct contribution exhibiting little change in state and a trapping-desorption fraction that desorbs in equilibrium [J. C. Maxwell, Phil. Trans. R. Soc. London 170, 231 (1879)]. Here a classical mechanical scattering theory is developed to describe direct scattering, trapping, and subsequent desorption of the incident beam. This theory allows a rigorous test of the Maxwell assumption and determines the conditions under which it is valid. The theory also gives quantitative explanations of important new experimental measurements [K. D. Gibson, N. Isa, and S. J. Sibener, J. Chem. Phys. 119, 13 083 (2003)] for direct and trapping-desorption scattering of Ar atoms by a self-assembled layer of 1-decanethiol on Au(111).

  13. Desorption Dynamics, Internal Energies and Imaging of Organic Molecules from Surfaces with Laser Desorption and Vacuum Ultraviolet (VUV) Photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Takahashi, Lynelle K.; Ahmed, Musahid

    2011-04-05

    There is enormous interest in visualizing the chemical composition of organic material that comprises our world. A convenient method to obtain molecular information with high spatial resolution is imaging mass spectrometry. However, the internal energy deposited within molecules upon transfer to the gas phase from a surface can lead to increased fragmentation and to complications in analysis of mass spectra. Here it is shown that in laser desorption with postionization by tunable vacuum ultraviolet (VUV) radiation, the internal energy gained during laser desorption leads to minimal fragmentation of DNA bases. The internal temperature of laser-desorbed triacontane molecules approaches 670 K, whereas the internal temperature of thymine is 800 K. A synchrotron-based VUV postionization technique for determining translational temperatures reveals that biomolecules have translational temperatures in the range of 216-346 K. The observed low translational temperatures, as well as their decrease with increased desorption laser power is explained by collisional cooling. An example of imaging mass spectrometry on an organic polymer, using laser desorption VUV postionization shows 5 mu m feature details while using a 30 mu m laser spot size and 7 ns duration. Applications of laser desorption postionization to the analysis of cellulose, lignin and humic acids are briefly discussed.

  14. Leaf water absorption and desorption functions for three turfgrasses

    Science.gov (United States)

    Liang, Xi; Su, Derong; Yin, Shuxia; Wang, Zhi

    2009-09-01

    SummaryPlant leaf can absorb water when the leaf is in contact with water. This happens when the rainfall is intercepted by plant leaves, where the intercepted part of rain remains on the leaf surface. When the intercepted water is either absorbed or subsequently evaporated into the atmosphere, the plant leaves can dissipate water through the desorption process until the plant is dry or rewatered. In this paper, two symptomatic models in the form of exponential functions for leaf water absorption and leaf water desorption were derived and validated by experimental data using leaves of three turfgrasses (Tall fescue, Perennial ryegrass and Kentucky bluegrass). Both the models and measured data showed that the rate of leaf water absorption was high at the low initial leaf water content and then gradually leveled off toward the saturated leaf water content. The rate of leaf water desorption was high at the high initial leaf water content then decreased drastically over time toward zero. The different plant leaves showed different exponents and other parameters of the functions which indicate the difference of plant species. Both the absorption and desorption rates were relatively higher for the Kentucky bluegrass and lower for the Tall fescue and Perennial ryegrass. The concept of specific leaf area ( SLA) was used to understand the saturated leaf water content ( C s) of the three turfgrasses. Linear relationships were found between C s and SLA. The leaf water absorption and desorption functions are useful for deriving physiological parameters of the plant such as permanent wilting leaf water content, naturally irreducible leaf water content, exponential leaf water absorption coefficient, and exponential leaf desorption coefficient, as well as for evaluating the effects of rainfall interception on plant growth and water use efficiency.

  15. Coverage-dependent adsorption and desorption of oxygen on Pd(100).

    Science.gov (United States)

    den Dunnen, Angela; Jacobse, Leon; Wiegman, Sandra; Berg, Otto T; Juurlink, Ludo B F

    2016-06-28

    We have studied the adsorption and desorption of O2 on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O2 initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O2 overlayer. Dissociation of molecularly bound O2 during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediate temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O2 dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.

  16. Coverage-dependent adsorption and desorption of oxygen on Pd(100)

    Science.gov (United States)

    den Dunnen, Angela; Jacobse, Leon; Wiegman, Sandra; Berg, Otto T.; Juurlink, Ludo B. F.

    2016-06-01

    We have studied the adsorption and desorption of O2 on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O2 initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O2 overlayer. Dissociation of molecularly bound O2 during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediate temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O2 dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.

  17. Heavy-Ion-Induced Electronic Desorption of Gas from Metals

    CERN Document Server

    Molvik, A W; Mahner, E; Kireeff Covo, M; Bellachioma, M C; Bender, M; Bieniosek, F M; Hedlund, E; Krämer, A; Kwan, J; Malyshev, O B; Prost, L; Seidl, P A; Westenskow, G; Westerberg, L

    2007-01-01

    During heavy-ion operation in several particle accelerators worldwide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion-induced gas desorption scales with the electronic energy loss (dEe/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  18. Desorption of toluene from modified clays using supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    Carneiro D. G. P.

    2004-01-01

    Full Text Available The main objective of this work is to study the regeneration capacity of modified clays using supercritical fluid. These modified clays are used as organic compound adsorvents. The experimental step was done using a packed column with the clay contaminated by toluene. The results obtained showed the influence of the density of the supercritical CO2 and of the organic modifier in the desorption process. These data were modeled with first- and second-order models. Better results were obtained using the second-order model. This study makes possible the scale-up of the desorption process for regeneration of solid matrices using supercritical fluids.

  19. Heavy-ion induced electronic desorption of gas from metals

    Energy Technology Data Exchange (ETDEWEB)

    Molvik, A W; Kollmus, H; Mahner, E; Covo, M K; Bellachioma, M C; Bender, M; Bieniosek, F M; Hedlund, E; Kramer, A; Kwan, J; Malyshev, O B; Prost, L; Seidl, P A; Westenskow, G; Westerberg, L

    2006-12-19

    During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/d/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  20. PAH desorption from river floodplain soils using supercritical fluid extraction.

    Science.gov (United States)

    Yang, Yi; Cajthaml, Tomás; Hofmann, Thilo

    2008-12-01

    Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (rhoextractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.

  1. Nonthermal current-stimulated desorption of gases from carbon nanotubes.

    Science.gov (United States)

    Salehi-Khojin, Amin; Lin, Kevin Y; Field, Christopher R; Masel, Richard I

    2010-09-10

    The desorption of gases from carbon nanotubes is usually a slow process that limits the nanotubes' utility as sensors or as memristors. Here, we demonstrate that flow in the nanotube above the Poole-Frenkel conduction threshold can stimulate adsorbates to desorb without heating the sensor substantially. The method is general: alcohols, aromatics, amines, and phosphonates were all found to desorb. We postulate that the process is analogous to electron-stimulated desorption, but with an internally conducted rather than externally applied source of electrons.

  2. The use of coarse, separable, condensed-phase organic carbon particles to characterize desorption resistance of polycyclic aromatic hydrocarbons in contaminated sediments

    Energy Technology Data Exchange (ETDEWEB)

    Chai, Y.Z.; Kochetkov, A.; Reible, D.D. [University of Texas, Austin, TX (United States)

    2007-07-15

    Physical separations were employed to characterize the source of desorption-resistant behavior for polycyclic aromatic hydrocarbons (PAHs) in laboratory- and field-contaminated sediments. Size and density separation of laboratory-contaminated sediments did not effectively separate the amorphous-phase (volatile) and condensed-phase (nonvolatile) organic carbon as measured by thermal oxidation at 375 {sup o}C. These separations also did not result in sediment fractions with significantly different desorption characteristics as measured by apparent partition coefficients. Coarse particles from a field-contaminated sediment from Utica Harbor (UH; Utica, NY, USA), however, could be directly separated into sandy fractions and organic fractions that were composed of woody organic matter, charcoal or charred vegetative matter, and coal-like and coal-cinder particles. Chemical analysis showed that coal-like (glassy, nonporous) and coal-cinder (porous, sintered) particles exhibited very high PAH concentrations and high apparent partition coefficients. These particles also exhibited significantly higher condensed-phase (nonvolatile) organic carbon contents as defined by thermal oxidation at 375{sup o}C. The apparent partition coefficients of PAHs in the coal-cinder particles were a good indication of the apparent partition coefficients in the desorption-resistant fraction of UH sediment, indicating that the coarse particles provided a reasonable characterization of the desorption-resistance phenomena in these sediments even though the coarse fractions represented less than 25% of the organic carbon in the whole sediment.

  3. The use of coarse, separable, condensed-phase organic carbon particles to characterize desorption resistance of polycyclic aromatic hydrocarbons in contaminated sediments.

    Science.gov (United States)

    Chai, Yunzhou; Kochetkov, Alexander; Reible, Danny D

    2007-07-01

    Physical separations were employed to characterize the source of desorption-resistant behavior for polycyclic aromatic hydrocarbons (PAHs) in laboratory- and field-contaminated sediments. Size and density separation of laboratory-contaminated sediments did not effectively separate the amorphous-phase (volatile) and condensed-phase (nonvolatile) organic carbon as measured by thermal oxidation at 375 degrees C. These separations also did not result in sediment fractions with significantly different desorption characteristics as measured by apparent partition coefficients. Coarse particles from a field-contaminated sediment from Utica Harbor (UH; Utica, NY, USA), however, could be directly separated into sandy fractions and organic fractions that were composed of woody organic matter, charcoal or charred vegetative matter, and coal-like and coal-cinder particles. Chemical analysis showed that coal-like (glassy, nonporous) and coal-cinder (porous, sintered) particles exhibited very high PAH concentrations and high apparent partition coefficients. These particles also exhibited significantly higher condensed-phase (nonvolatile) organic carbon contents as defined by thermal oxidation at 375 degrees C. The apparent partition coefficients of PAHs in the coal-cinder particles were a good indication of the apparent partition coefficients in the desorption-resistant fraction of UH sediment, indicating that the coarse particles provided a reasonable characterization of the desorption-resistance phenomena in these sediments even though the coarse fractions represented less than 25% of the organic carbon in the whole sediment.

  4. Terahertz Desorption Emission Spectroscopy (THz DES) - ‘ALMA in the Lab’

    Science.gov (United States)

    Emile Auriacombe, Olivier Bruno Jacques; Fraser, Helen; Ellison, Brian; Ioppolo, Sergio; Rea, Simon

    2016-06-01

    ALMA is revolutionising our scope to identify and locate molecules that have been desorbed from ices, particularly complex organic molecules (COMS), which provide a vital link between interstellar and prebiotic chemistry. Explaining the existence of these molecules in star-forming regions relies on an empirical understanding of the chemistry that underpins their formation:- do COMS form predominantly in the solid-phase and then desorb to the gas phase, or do only “smaller” species, radials or ions desorb and then undergo gas-phase chemical reactions to generate larger COMS?-are the rotational state populations in COMS only attributable to equilibrium chemistry, or could their formation mechanisms and desorption processes affect the rotational state occupancy of these molecules, thereby directly tying certain species to solid-state origins?We have developed a novel laboratory method - THz Desorption Emission Spectroscopy (THz-DES) that combines “traditional” laboratory astrophysics high-vacuum ice experiments with a sensitive high-spectral-resolution terahertz total-power heterodyne radiometer 1,2, partially mirroring the spectral range of ALMA band 7 (275- 373 GHz). Ices are grown in situ on a cold-plate, situated in a vacuum cell, then (thermally) desorbed. The sub-mm emission spectra of the resultant gas-phase molecules are detected as a function of time, temperature, or distance from the surface. Our first THz DES results will be shown for pure and binary ice systems including H2O, N2O and CH3OH. They show good correlation with established methods e.g. TPD, with the advantage of exploiting the molecular spectroscopy to unravel surface dynamics, state-occupancy, and unequivocal molecular identification, as well as concurrently measuring desorption barriers and molecular yields. We will extend our technique to a broader frequency range, enabling us to detect radical and ion desorption, to differentiate between A and E populations of CH3OH or ortho

  5. Applications of electrospray laser desorption ionization mass spectrometry for document examination.

    Science.gov (United States)

    Cheng, Sy-Chyi; Lin, Yu-Shan; Huang, Ming-Zong; Shiea, Jentaie

    2010-01-01

    We have employed electrospray laser desorption ionization mass spectrometry (ELDI-MS) to rapidly characterize certain classes of compounds--the inks within the characters made by inks and inkjet printer on regular paper and the chemical compounds within thermal papers. This ELDI-MS approach allowed the ink and paper samples to be distinguished in terms of their chemical compositions. Sample pretreatment was unnecessary and the documents were practically undamaged after examination. The ink chemicals on the documents were desorbed through laser irradiation (sampling spot area: <100 microm(2)); the desorbed molecules then entered an electrospray plume--prepared from an acidic methanol/water solution (50%)--where they became ionized through fusion or ion-molecule reactions with the charged solvent species and droplets in the plume.

  6. Adsorption kinetics, thermodynamics and desorption of natural dissolved organic matter by multiwalled carbon nanotubes.

    Science.gov (United States)

    Su, Fengsheng; Lu, Chungsying

    2007-09-01

    Multiwalled carbon nanotubes (CNTs) were thermally treated and were employed as adsorbents to study their adsorption kinetics and thermodynamics of natural dissolved organic matter (NDOM) from aqueous solutions. The adsorption kinetics follows the first-order rate law while the adsorption thermodynamics indicates the exothermic and spontaneous nature. A comparative study on the adsorption/desorption properties of NDOM between CNTs and granular activated carbon (GAC) was also conducted and revealed that the CNTs possess more NDOM adsorption capacities and show less weight loss through 10 cycles of water treatment and reactivation than the GAC. This suggests that the CNTs are promising NDOM adsorbents for preventing the microbiological degradation of drinking water quality as well as the formation of disinfection by products in water treatment.

  7. Electron Stimulated Desorption of Condensed Gases on Cryogenic Surfaces

    CERN Document Server

    Tratnik, H; Hilleret, Noël

    2005-01-01

    In ultra-high vacuum systems outgassing from vacuum chamber walls and desorption from surface adsorbates are usually the factors which in°uence pressure and residual gas composition. In particular in beam vacuum systems of accelerators like the LHC, where surfaces are exposed to intense synchro- tron radiation and bombardment by energetic ions and electrons, properties like the molecular desorption yield or secondary electron yield can strongly in°uence the performance of the accelerator. In high-energy particle accelerators operating at liquid helium temperature, cold surfaces are exposed to the bombardment of energetic photons, electrons and ions. The gases released by the subsequent desorption are re-condensed on the cold surfaces and can be re-desorbed by the impinging electrons and ions. The equilibrium coverage reached on the surfaces exposed to the impact of energetic particles depends on the desorption yield of the condensed gases and can a®ect the operation of the accelerator by modifying th...

  8. Gold ion beams induced desorption studies for Booster Nuclotron

    Science.gov (United States)

    Kuznetsov, A. B.; Tuzikov, A. V.; Philippov, A. V.

    2016-12-01

    Heavy ions induced pressure rise is one of the machine limits. The calculation results of the gold ion beam 197Au31+ losses due to residual gas interaction in view of desorption of adsorbed particles on the Booster Nuclotron vacuum chamber surface are discussed.

  9. Organic contaminants in soil, desorption kinetics and microbial degradation

    NARCIS (Netherlands)

    Schlebaum, W.

    1999-01-01

    The availability of organic contaminants in soils or sediments for microbial degradation or removal by physical means (e.g.) soil washing or soil venting) depends on the desorption kinetics of these contaminants from the soil matrix. When the organic contaminants desorb very slow from the soil matri

  10. Linking desorption kinetics to phenanthrene biodegradation in soil

    Energy Technology Data Exchange (ETDEWEB)

    Rhodes, Angela H.; McAllister, Laura E. [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Semple, Kirk T., E-mail: k.semple@lancaster.ac.u [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom)

    2010-05-15

    The desorption of polycyclic aromatic hydrocarbons (PAHs) often exhibits a biphasic profile similar to that observed for biodegradation whereby an initial rapid phase of degradation or desorption is followed by a phase of much slower transformation or release. Most investigations to-date have utilised a polymeric sorbent, such as Tenax, to characterise desorption, which is methodologically unsuitable for the analysis of soil. In this study, desorption kinetics of {sup 14}C-phenanthrene were measured by consecutive extraction using aqueous solutions of hydroxypropyl-beta-cyclodextrin (HPCD). The data indicate that the fraction extracted after 24 h generally approximated the linearly sorbed, rapidly desorbing fraction (F{sub rap}), calculated using a three-compartment model. A good linear correlation between phenanthrene mineralised and F{sub rap} was observed (r{sup 2} = 0.89; gradient = 0.85; intercept = 8.20). Hence HPCD extraction (24 h) and first-order three-compartment modelling appear to provide an operationally straightforward tool for estimating mass-transfer limited biodegradation in soil. - Aqueous hydroxypropyl-beta-cyclodextrin (HPCD) solutions can predict the rapidly desorbing and microbially degradable fractions of phenanthrene in soils.

  11. Development of the positron-induced ion-desorption apparatus

    CERN Document Server

    Kanazawa, I

    2002-01-01

    The principle of the positron-induced ion-desorption, which is developed recently, and experimental apparatus are explained and study of desorption of positron-induced hydrogen ion from surface of Ni is reported as an example. The slow positron beam system in the positron-induced ion-desorption spectroscopy is consisted of two stages, moderator and transformation from magnetic transport type to electrostatic transport type. Positron is antiparticle of electron and localized both outside and monolayer of surface, which is special futures and used to analyze the surface. The number of emission positive charge particles from the clean Ni surface was changed by coil current at 1.9 keV and 2.9 keV incident positron energy. The number of re-emission positron at 1.9 keV was larger than at 2.9 keV. The number of emission positive charge particles from the clean Ni surface adsorbed monolayer hydrogen atom were decreased with coil current at 1.9 keV and 2.9 keV. The number of desorption hydrogen particle at 1.9 keV was...

  12. Permeability changes in coal resulting from gas desorption

    Energy Technology Data Exchange (ETDEWEB)

    Levine, J.R.; Johnson, P.M.

    1992-01-01

    Research continued on the study of coal permeability and gas desorption. This quarter, most of the effort involved identifying problems with the microbalance and then getting it repaired. Measurement of the amount of gas adsorbed with the microbalance involved corrections for the buoyancy change with pressure and several experiments with helium were made to determine this correction.

  13. Sorption and desorption of arsenate and arsenite on calcite

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Diederik Jan; Jakobsen, Rasmus

    2008-01-01

    The adsorption and desorption of arsenate (As(V)) and arsenite (As(111)) oil calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic...

  14. Analytical theory of finite-size effects in mechanical desorption

    NARCIS (Netherlands)

    Skvortsov, A.M.; Klushin, L.I.; Fleer, G.J.; Leermakers, F.A.M.

    2010-01-01

    We discuss a unique system that allows exact analytical investigation of first- and second-order transitions with finite-size effects: mechanical desorption of an ideal lattice polymer chain grafted with one end to a solid substrate with a pulling force applied to the other end. We exploit the analo

  15. Influence of surface coverage on the chemical desorption process

    CERN Document Server

    Marco, Minissale

    2014-01-01

    In cold astrophysical environments, some molecules are observed in the gas phase whereas they should have been depleted, frozen on dust grains. In order to solve this problem, astrochemists have proposed that a fraction of molecules synthesized on the surface of dust grains could desorb just after their formation. Recently the chemical desorption process has been demonstrated experimentally, but the key parameters at play have not yet been fully understood. In this article we propose a new procedure to analyze the ratio of di-oxygen and ozone synthesized after O atoms adsorption on oxidized graphite. We demonstrate that the chemical desorption efficiency of the two reaction paths (O+O and O+O$_2$) is different by one order of magnitude. We show the importance of the surface coverage: for the O+O reaction, the chemical desorption efficiency is close to 80 $\\%$ at zero coverage and tends to zero at one monolayer coverage. The coverage dependence of O+O chemical desorption is proved by varying the amount of pre-...

  16. Measurement of hydrogen solubility and desorption rate in V-4Cr-4Ti and liquid lithium-calcium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Park, J.H.; Erck, R.; Park, E.T. [Argonne National Lab., IL (United States)] [and others

    1997-04-01

    Hydrogen solubility in V-4Cr-4Ti and liquid lithium-calcium was measured at a hydrogen pressure of 9.09 x 10{sup {minus}4} torr at temperatures between 250 and 700{degrees}C. Hydrogen solubility in V-4Cr-4Ti and liquid lithium decreased with temperature. The measured desorption rate of hydrogen in V-4Cr-4Ti is a thermally activated process; the activation energy is 0.067 eV. Oxygen-charged V-4Cr-4Ti specimens were also investigated to determine the effect of oxygen impurity on hydrogen solubility and desorption in the alloy. Oxygen in V-4Cr-4Ti increases hydrogen solubility and desorption kinetics. To determine the effect of a calcium oxide insulator coating on V-4Cr-4Ti, hydrogen solubility in lithium-calcium alloys that contained 0-8.0 percent calcium was also measured. The distribution ratio R of hydrogen between liquid lithium or lithium-calcium and V-4Cr-4Ti increased as temperature decreased (R {approx} 10 and 100 at 700 and 250{degrees}C, respectively). However at <267{degrees}C, solubility data could not be obtained by this method because of the slow kinetics of hydrogen permeation through the vanadium alloy.

  17. Desorption of plutonium from montmorillonite: An experimental and modeling study

    Science.gov (United States)

    Begg, James D.; Zavarin, Mavrik; Kersting, Annie B.

    2017-01-01

    Desorption of plutonium (Pu) will likely control the extent to which it is transported by mineral colloids. We evaluated the adsorption/desorption behavior of Pu on SWy-1 montmorillonite colloids at pH 4, pH 6, and pH 8 using batch adsorption and flow cell desorption experiments. After 21 days adsorption, Pu(IV) affinity for montmorillonite displayed a pH dependency, with Kd values highest at pH 4 and lowest at pH 8. The pH 8 experiment was further allowed to equilibrate for 6 months and showed an increase in Kd, indicating that true sorption equilibrium was not achieved within the first 21 days. For the desorption experiments, aliquots of the sorption suspensions were placed in a flow cell, and Pu-free solutions were then pumped through the cell for a period of 12 days. Changes in influent solution flow rate were used to investigate the kinetics of Pu desorption and demonstrated that it was rate-limited over the experimental timescales. At the end of the 12-day flow cell experiments, the extent of desorption was again pH dependent, with pH 8 > pH 6 > pH 4. Further, at pH 8, less Pu was desorbed after an adsorption contact time of 6 months than after a contact time of 21 days, consistent with an aging of Pu on the clay surface. A conceptual model for Pu adsorption/desorption that incorporated known surface-mediated Pu redox reactions was used to fit the experimental data. The resulting rate constants indicated processes occurring on timescales of months and even years which may, in part, explain observations of clay colloid-facilitated Pu transport on decadal timescales. Importantly, however, our results also imply that migration of Pu adsorbed to montmorillonite colloids at long (50-100 year) timescales under oxic conditions may not be possible without considering additional phenomena, such as co-precipitation.

  18. Investigations into ultraviolet matrix-assisted laser desorption

    Energy Technology Data Exchange (ETDEWEB)

    Heise, Theodore W. [Iowa State Univ., Ames, IA (United States)

    1993-07-01

    Matrix-assisted laser desorption (MALD) is a technique for converting large biomolecules into gas phase ions. Some characteristics of the commonly used uv matrices are determined. Solubilities in methanol range from 0.1 to 0.5 M. Solid phase absorption spectra are found to be similar to solution, but slightly red-shifted. Acoustic and quartz crystal microbalance signals are investigated as possible means of uv-MALD quantitation. Evidence for the existence of desorption thresholds is presented. Threshold values are determined to be in the range of 2 to 3 MW/cm2. A transient imaging technique based on laser-excited fluorescence for monitoring MALD plumes is described. Sensitivity is well within the levels required for studying matrix-assisted laser desorption, where analyte concentrations are significantly lower than those in conventional laser desorption. Results showing the effect of film morphology, particularly film thickness, on plume dynamics are presented. In particular, MALD plumes from thicker films tend to exhibit higher axial velocities. Fluorescent labeling of protein and of DNA is used to allow imaging of their uv-MALD generated plumes. Integrated concentrations are available with respect to time, making it possible to assess the rate of fragmentation. The spatial and temporal distributions are important for the design of secondary ionization schemes to enhance ion yields and for the optimization of ion collection in time-of-flight MS instruments to maximize resolution. Such information could also provide insight into whether ionization is closely associated with the desorption step or whether it is a result of subsequent collisions with the matrix gas (e.g., proton transfer). Although the present study involves plumes in a normal atmosphere, adaptation to measurements in vacuum (e.g., inside a mass spectrometer) should be straightforward.

  19. Sorption and desorption of carbamazepine from water by smectite clays.

    Science.gov (United States)

    Zhang, Weihao; Ding, Yunjie; Boyd, Stephen A; Teppen, Brian J; Li, Hui

    2010-11-01

    Carbamazepine is a prescription anticonvulsant and mood stabilizing pharmaceutical administered to humans. Carbamazepine is persistent in the environment and frequently detected in water systems. In this study, sorption and desorption of carbamazepine from water was measured for smectite clays with the surface negative charges compensated with K+, Ca2+, NH4+, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA) cations. The magnitude of sorption followed the order: TMPA-smectite≥HDTMA-smectite>NH4-smectite>K-smectite>Ca-smectite⩾TMA-smectite. The greatest sorption of carbamazepine by TMPA-smectite is attributed to the interaction of conjugate aromatic moiety in carbamazepine with the phenyl ring in TMPA through π-π interaction. Partitioning process is the primary mechanism for carbamazepine uptake by HDTMA-smectite. For NH4-smectite the urea moiety in carbamazepine interacts with exchanged cation NH4+ by H-bonding hence demonstrating relatively higher adsorption. Sorption by K-, Ca- and TMA-smectites from water occurs on aluminosilicate mineral surfaces. These results implicate that carbamazepine sorption by soils occurs primarily in soil organic matter, and soil mineral fractions play a secondary role. Desorption of carbamazepine from the sorbents manifested an apparent hysteresis. Increasing irreversibility of desorption vs. sorption was observed for K-, Ca-, TMA-, TMPA- and HDTMA-clays as aqueous carbamazepine concentrations increased. Desorption hysteresis of carbamazepine from K-, Ca-, NH4-smectites was greater than that from TMPA- and HDTMA-clays, suggesting that the sequestrated carbamazepine molecules in smectite interlayers are more resistant to desorption compared to those sorbed by organic phases in smectite clays.

  20. Adsorption/desorption of phenanthrene on contaminated soils

    Energy Technology Data Exchange (ETDEWEB)

    Saada, A.; Gaboriau, H.; Amalric, L.; Crouzet, C. [BRGM, Orleans (France)

    2003-07-01

    Polycyclic Aromatic Hydrocarbons (PAH) are persistent environmental contaminants whose behaviour has been thoroughly studies because of their genotoxicity. One of the main processes governing PAH evolution is adsorption onto soil matrices due to the marked hydrophobic properties of this group of pollutants. In this study, pehnanthrene adsorption and desorption were measured for: - an untreated polluted soil (S) from a former coking plant - the same soil washed with toluene in a soxhlet extractor (S{sub w}), which enables the pollutants (PAH and tar) to be extracted from the soil - the fine fraction (<50 {mu}m) of the washed soil (S{sub f}), - a mineral (kaolinite) representative of the polluted soil (K), - the mineral coated with the tar extracted from the polluted soil (K-T). Isotherms of phenanthrene adsorption/desorption on K, K-T and S shows that the hysteresis between the adsorption and desorption isotherms increases 1) with the organic matter content, and 2) for the untreated soil S containing endogenic bacteria, in addition to organic matter. This indicates that tar-type organic matter is capable of reducing the release of phenanthrene by forming bonded residue. For the untreated soil S, endogenic bacteria consume phenanthrene as it is desorbed. Consequently, the desorption isotherm for S is almost horizontal, as if no desorption had taken place. This study has demonstrated the effect that the type of organic matter has on PAH fate, and thus the need to take this into account, particularly where tar is concerned, when assessing the adsorption capacity of soils. (orig.)

  1. Rapid on-site detection of explosives on surfaces by ambient pressure laser desorption and direct inlet single photon ionization or chemical ionization mass spectrometry.

    Science.gov (United States)

    Ehlert, S; Hölzer, J; Rittgen, J; Pütz, M; Schulte-Ladbeck, R; Zimmermann, R

    2013-09-01

    Considering current security issues, powerful tools for detection of security-relevant substances such as traces of explosives and drugs/drug precursors related to clandestine laboratories are required. Especially in the field of detection of explosives and improvised explosive devices, several relevant compounds exhibit a very low vapor pressure. Ambient pressure laser desorption is proposed to make these substances available in the gas phase for the detection by adapted mass spectrometers or in the future with ion-mobility spectrometry as well. In contrast to the state-of-the-art thermal desorption approach, by which the sample surface is probed for explosive traces by a wipe pad being transferred to a thermal desorber unit, by the ambient pressure laser desorption approach presented here, the sample is directly shockwave ablated from the surface. The laser-dispersed molecules are sampled by a heated sniffing capillary located in the vicinity of the ablation spot into the mass analyzer. This approach has the advantage that the target molecules are dispersed more gently than in a thermal desorber unit where the analyte molecules may be decomposed by the thermal intake. In the technical realization, the sampling capillary as well as the laser desorption optics are integrated in the tip of an endoscopic probe or a handheld sampling module. Laboratory as well as field test scenarios were performed, partially in cooperation with the Federal Criminal Police Office (Bundeskriminalamt, BKA, Wiesbaden, Germany), in order to demonstrate the applicability for various explosives, drugs, and drug precursors. In this work, we concentrate on the detection of explosives. A wide range of samples and matrices have been investigated successfully.

  2. Photon- and electron-stimulated desorption from laboratory models of interstellar ice grains

    Energy Technology Data Exchange (ETDEWEB)

    Thrower, J. D.; Abdulgalil, A. G. M.; Collings, M. P.; McCoustra, M. R. S.; Burke, D. J.; Brown, W. A.; Dawes, A.; Holtom, P. J.; Kendall, P.; Mason, N. J.; Jamme, F.; Fraser, H. J.; Rutten, F. J. M. [School of Engineering and Physical Sciences, Heriot-Watt University, Riccarton, Edinburgh EH 14 4AS (United Kingdom); Department of Chemistry, University College London, 20 Gordon Street, London W1CH 0AJ (United Kingdom); Department of Physics and Astronomy, Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom); SOLEIL Synchrotron, BP 48, L' Orme des Merisiers, F-91192 Gif surf Yvette Cedex (France); Department of Physics, Scottish Universities Physics Alliance (SUPA), University of Strathclyde, John Anderson Building, 107 Rottenrow East, Glasgow G4 0NG (United Kingdom); School of Pharmacy and iEPSAM, Keele University, Keele ST5 5BG (United Kingdom)

    2010-07-15

    The nonthermal desorption of water from ice films induced by photon and low energy electron irradiation has been studied under conditions mimicking those found in dense interstellar clouds. Water desorption following photon irradiation at 250 nm relies on the presence of an absorbing species within the H{sub 2}O ice, in this case benzene. Desorption cross sections are obtained and used to derive first order rate coefficients for the desorption processes. Kinetic modeling has been used to compare the efficiencies of these desorption mechanisms with others known to be in operation in dense clouds.

  3. Dust as interstellar catalyst I. Quantifying the chemical desorption process

    CERN Document Server

    Minissale, M; Cazaux, S; Hocuk, S

    2015-01-01

    Context. The presence of dust in the interstellar medium has profound consequences on the chemical composition of regions where stars are forming. Recent observations show that many species formed onto dust are populating the gas phase, especially in cold environments where UV and CR induced photons do not account for such processes. Aims. The aim of this paper is to understand and quantify the process that releases solid species into the gas phase, the so-called chemical desorption process, so that an explicit formula can be derived that can be included into astrochemical models. Methods. We present a collection of experimental results of more than 10 reactive systems. For each reaction, different substrates such as oxidized graphite and compact amorphous water ice are used. We derive a formula to reproduce the efficiencies of the chemical desorption process, which considers the equipartition of the energy of newly formed products, followed by classical bounce on the surface. In part II we extend these resul...

  4. Unconventional resource's production under desorption-induced effects

    Directory of Open Access Journals (Sweden)

    S. Sina Hosseini Boosari

    2016-06-01

    We have developed a numerical model to study the effect of changes in porosity, permeability and compaction on four major U.S. shale formations considering their Langmuir isotherm desorption behavior. These resources include; Marcellus, New Albany, Barnett and Haynesville Shales. First, we introduced a model that is a physical transport of single-phase gas flow in shale porous rock. Later, the governing equations are implemented into a one-dimensional numerical model and solved using a fully implicit solution method. It is found that the natural gas production is substantially affected by desorption-induced porosity/permeability changes and geomechancis. This paper provides valuable insights into accurate modeling of unconventional reservoirs that is more significant when an even small correction to the future production prediction can enormously contribute to the U.S. economy.

  5. Experimental study on desorption of soluble matter as influenced by cations in static water

    Institute of Scientific and Technical Information of China (English)

    Wen-sheng XU; Li CHEN; Xiao-xia TONG; Xiao-ping CHEN; Ping-cang ZHANG

    2014-01-01

    With variation of drainage basin environments, desorption of soluble matter has become one of the significant erosion processes in rivers. It has a considerable impact on flow and sediment transport, as well as processes of river bed deformation and landform evolution throughout a watershed. In this study, considering influences on sediment movement, especially on cohesive sediment transport, Ca2+ and H+ were chosen as characteristic ions of soluble matter, and the total desorption quantity of Ca2+ and pH value when the desorption equilibrium is reached were employed as two indexes representing the desorption of soluble matter. By means of an indoor experiment, desorption of soluble matter as influenced by cations in static water was investigated. The results show that the total desorption quantity of soluble matter increases with the initial cation concentration until a maximum desorption quantity value is obtained and maintained. The total desorption quantity of soluble matter depends on properties of the specific cations in static water, and the stronger the affinity is between the cation and sediment surface, the higher the total desorption quantity will be. Finally, a strong approximate linear relationship between desorption quantities for different kinds of soluble matters was obtained, which means that variation of pH values can accurately reflect the desorption results of soluble matter.

  6. Atmospheric pressure laser-induced acoustic desorption chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for the analysis of complex mixtures.

    Science.gov (United States)

    Nyadong, Leonard; McKenna, Amy M; Hendrickson, Christopher L; Rodgers, Ryan P; Marshall, Alan G

    2011-03-01

    We present a novel nonresonant laser-based matrix-free atmospheric pressure ionization technique, atmospheric pressure laser-induced acoustic desorption chemical ionization (AP/LIAD-CI). The technique decouples analyte desorption from subsequent ionization by reagent ions generated from a corona discharge initiated in ambient air or in the presence of vaporized toluene as a CI dopant at room temperature. Analyte desorption is initiated by a shock wave induced in a titanium foil coated with electrosprayed sample, irradiated from the rear side by high-energy laser pulses. The technique enables facile and independent optimization of the analyte desorption, ionization, and sampling events, for coupling to any mass analyzer with an AP interface. Moreover, the generated analyte ions are efficiently thermalized by collisions with atmospheric gases, thereby reducing fragmentation. We have coupled AP/LIAD-CI to ultrahigh-resolution FT-ICR MS to generate predominantly [M + H](+) or M(+•) ions to resolve and identify thousands of elemental compositions from organic mixtures as complex as petroleum crude oil distillates. Finally, we have optimized the AP/LIAD CI process and investigated ionization mechanisms by systematic variation of placement of the sample, placement of the corona discharge needle, discharge current, gas flow rate, and inclusion of toluene as a dopant.

  7. Sorption/desorption reversibility of polycyclic aromatic hydrocarbons (PAHs) in soils and carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guohui

    2008-07-01

    Understanding sorption/desorption is an important prerequisite for the prediction of fate and transport of pollutants in the environment. During the last two decades, numerous studies have reported hysteresis phenomenon for the interaction of hydrophobic organic contaminants (HOCs) with natural organic matter (NOM). It manifests as nonsingular sorption/desorption isotherms or different rates for sorption and desorption, where during desorption a higher affinity of a compound on a given sorbent and a longer time scale for release than for sorption is observed. Other studies showed that some of the reported sorption/desorption hysteresis phenomena are due to experimental artifacts, mainly resulting from non-attainment of sorption equilibrium before desorption experiments, which result in 'pseudo-hysteresis'. Except for the hypothesis of sorbent reconfiguration, clear experimental evidence for the physical or chemical mechanisms proposed to lead to hysteresis is still lacking. In this study, sorption/desorption equilibrium and kinetics of phenanthrene sorption/desorption from two soils and three carbonaceous samples were investigated using both batch and column techniques. The main objective of this work was to monitor hysteresis phenomenon by carefully recovering the solute mass in the system and to compare sorption/desorption equilibria and kinetics thermodynamically. Nonsingular isotherms and higher desorption enthalpies as well as increased activation energies with proceeding desorption are expected if significant hysteresis exists. Sorption-desorption cycles were carried out to compare equilibrium isotherms and associated sorption/desorption enthalpies (AeH, isosteric heats). Instead of the traditional decant-and-refill batch method, the experiments were conducted using a newly designed batch protocol, which enables the determination of sorption/desorption isotherms at different temperatures using a closed batch system. This method additionally allows

  8. [Sorption-desorption of phosphate in wastewater by hydrous iron oxide].

    Science.gov (United States)

    Xiang, Xue-Min; Liu, Ying; Zhou, Ji-Ti; Wang, Ren

    2008-11-01

    FeCl3 was used t o prepare hydrous iron oxide (HIO) as a n absorbent for phosphate (P) sorption and desorption study. The results showed that as pH decreased, the sorption capacity of HIO increased, and the sorption kinetics followed the second-order model, and the sorption isotherm could be fitted by the Langmuir equation. A 50 g/L NaOH solution was used for desorption of P from HIO, and the desorption rate could be reached over 98% . No relation was found between desorption rate and adsorption capacity. Based on above results, HIO was applied to adsorption of P from supernatant of sludge thickener, and after desorption, more than 90% of P was recovered. According to the results obtained, an effective system for P removal and recovery from municipal wastewater was suggested, which includes the following processes: adsorption, desorption, regeneration of HIO, and of recovery of P from P-rich desorption solution.

  9. Residence time dependent desorption of Staphylococcus epidermidis from hydrophobic and hydrophilic substrata.

    Science.gov (United States)

    Boks, Niels P; Kaper, Hans J; Norde, Willem; Busscher, Henk J; van der Mei, Henny C

    2008-12-01

    Adhesion and desorption are simultaneous events during bacterial adhesion to surfaces, although desorption is far less studied than adhesion. Here, desorption of Staphylococcus epidermidis from substratum surfaces is demonstrated to be residence time dependent. Initial desorption rate coefficients were similar for hydrophilic and hydrophobic dimethyldichlorosilane (DDS)-coated glass, likely because initial desorption is controlled by attractive Lifshitz-Van der Waals interactions, which are comparable on both substratum surfaces. However, significantly slower decay times of the desorption rate coefficients are found for hydrophilic glass than for hydrophobic DDS-coated glass. This difference is suggested to be due to the acid-base interactions between staphylococci and these surfaces, which are repulsive on hydrophilic glass and attractive on hydrophobic DDS-coated glass. Final desorption rate coefficients are higher on hydrophilic glass than on hydrophobic DDS-coated glass, due to the so called hydrophobic effect, facilitating a closer contact on hydrophobic DDS-coated glass.

  10. Laser Desorption Mass Spectrometry. II. Applications to Structural Analysis.

    Science.gov (United States)

    1982-02-02

    was unexpected, was the quaternary amine Safranin -O. Ions corresponding to (M-HC)- at m/z 313 dominate the negative ion mass spectrum. Two classes of...and cluster species were observed. The positive ion LD mass spectrum of safranin -O, shown in Figure 6, is tvnical of LD results for salts. The...Figure 6. Laser Desorption Positive-ion Spectrum of Safranin 0. Figure 7. Laser Desorntion Mass Spectra of Doubly Charged Organic Salts Top - N,N

  11. Thermodynamic properties of water desorption of forage turnip seeds

    OpenAIRE

    Kelly Aparecida Sousa; Osvaldo Resende; André Luis Duarte Goneli; Thaís Adriana de Souza Smaniotto; Daniel Emanuel Cabral de Oliveira

    2014-01-01

    The purpose of this study was to determine the thermodynamic properties of the process of water sorption in forage turnip  seeds. The equilibrium moisture content of forage turnip  seeds was determined by the gravimetric-dynamic method for different values of temperature and water activity. According to the results, increasing the moisture content increases the energy required for the evaporation of water in forage turnip seeds, and the values of integral isosteric heat of desorption, within ...

  12. Thermodynamic properties of water desorption of forage turnip seeds

    OpenAIRE

    Sousa,Kelly Aparecida de; Resende,Osvaldo; Goneli, André Luis Duarte; Smaniotto,Thaís Adriana de Souza; Oliveira,Daniel Emanuel Cabral de

    2015-01-01

    The purpose of this study was to determine the thermodynamic properties of the process of water sorption in forage turnip seeds. The equilibrium moisture content of forage turnip seeds was determined by the gravimetric-dynamic method for different values of temperature and water activity. According to the results, increasing the moisture content increases the energy required for the evaporation of water in forage turnip seeds, and the values of integral isosteric heat of desorption, within th...

  13. Ammonia nitrogen desorption from sanitary landfill leachate in filling towers

    OpenAIRE

    Leite,Valderi D.; Barros,Aldre J. M.; Lopes,Wilton S.; Sousa,José T. de

    2014-01-01

    Sanitary landfill leachates present high concentrations of carbonaceous and nitrogenous materials. The crucial point is that carbonaceous materials are of difficult biodegradation, what compromises the performance of biological treatment processes, while nitrogenous materials, such as ammonia nitrogen, probably preclude the use of biological treatments. Therefore, the aim of this work was to study the desorption process of ammonia nitrogen from sanitary landfill leachate in filling towers. De...

  14. Study on adsorption and desorption of ammonia on graphene

    Science.gov (United States)

    Zhang, Zhengwei; Zhang, Xinfang; Luo, Wei; Yang, Hang; He, Yanlan; Liu, Yixing; Zhang, Xueao; Peng, Gang

    2015-09-01

    The gas sensor based on pristine graphene with conductance type was studied theoretically and experimentally. The time response of conductance measurements showed a quickly and largely increased conductivity when the sensor was exposed to ammonia gas produced by a bubble system of ammonia water. However, the desorption process in vacuum took more than 1 h which indicated that there was a larger number of transferred carriers and a strong adsorption force between ammonia and graphene. The desorption time could be greatly shortened down to about 2 min by adding the flow of water-vapor-enriched air at the beginning of the recovery stage which had been confirmed as a rapid and high-efficiency desorption process. Moreover, the optimum geometries, adsorption energies, and the charge transfer number of the composite systems were studied with first-principle calculations. However, the theoretical results showed that the adsorption energy between NH3 and graphene was too small to fit for the experimental phenomenon, and there were few charges transferred between graphene and NH3 molecules, which was completely different from the experiment measurement. The adsorption energy between NH4 and graphene increased stage by stage which showed NH4 was a strong donor. The calculation suggested that H2O molecule could help a quick desorption of NH4 from graphene by converting NH4 to NH3 or (NH3)n(H2O)m groups, which was consistent with the experimental results. This study demonstrates that the ammonia gas produced by a bubble system of ammonia water is mainly ammonium groups of NH3 and NH4, and the NH4 moleculars are ideal candidates for the molecular doping of graphene while the interaction between graphene and the NH3 moleculars is weak.

  15. Temperature Effect on Boron Adsorption—Desorption Kinetics in Soils

    Institute of Scientific and Technical Information of China (English)

    ZHUDUANWEI; SHILEI; 等

    1999-01-01

    The effect of temperature on the properties of boron adsorption-desorption in brown-red soil,yellowbrown soil and calcareous alluvial soil of Hubei Province was investigated with the mobile displacement technique.The experimental data of B adsorption-desorption amounts and reaction time at 25 and 40℃ were fitted by the zero-order,first-order and parabolic diffusion kinetic equations.The adsorption process was in conformity with the parabolic diffusion law at both the temperatures,and the values of rate constant of the parabolic diffusion equation in B adsorption were 0.138,0.124 and 0.105 mg kg-1 min-1/2 at 25℃,and 0.147,0.146and 0.135mg kg-1 min1/2 at 40℃ for the brown-red soil,yellow-brown soil,and calcareous alluvial soil,respectively,The relationship between amount of B desorption and reaction time could be well described by the first-order kinetic equation,and the corresponding values of rate constant were 0.0422,0.0563 and 0.0384min-1 at 25℃,and 0.0408,0.0423 and 0.0401min-1 at 40℃ for the brown-red soil,the yellow-brown soil and the calcareous alluvial soil,respectively.Therefore,the desorption process of B might be related to the amount of B adsorbed in soil,The higher th temperature,the lower the amount of B adsorption of the same soil in the same reaction time,The values of the apparent activation energy of B adsorption in the three soils calculated with the rate constants of parabolic diffusion equation were 3.27,8.44 and 12.99 kJ mol-1,respectively,based on the experimental data of B adsorption amounts and reaction time at and 40℃.

  16. Study on adsorption and desorption of ammonia on graphene.

    Science.gov (United States)

    Zhang, Zhengwei; Zhang, Xinfang; Luo, Wei; Yang, Hang; He, Yanlan; Liu, Yixing; Zhang, Xueao; Peng, Gang

    2015-12-01

    The gas sensor based on pristine graphene with conductance type was studied theoretically and experimentally. The time response of conductance measurements showed a quickly and largely increased conductivity when the sensor was exposed to ammonia gas produced by a bubble system of ammonia water. However, the desorption process in vacuum took more than 1 h which indicated that there was a larger number of transferred carriers and a strong adsorption force between ammonia and graphene. The desorption time could be greatly shortened down to about 2 min by adding the flow of water-vapor-enriched air at the beginning of the recovery stage which had been confirmed as a rapid and high-efficiency desorption process. Moreover, the optimum geometries, adsorption energies, and the charge transfer number of the composite systems were studied with first-principle calculations. However, the theoretical results showed that the adsorption energy between NH3 and graphene was too small to fit for the experimental phenomenon, and there were few charges transferred between graphene and NH3 molecules, which was completely different from the experiment measurement. The adsorption energy between NH4 and graphene increased stage by stage which showed NH4 was a strong donor. The calculation suggested that H2O molecule could help a quick desorption of NH4 from graphene by converting NH4 to NH3 or (NH3)n(H2O)m groups, which was consistent with the experimental results. This study demonstrates that the ammonia gas produced by a bubble system of ammonia water is mainly ammonium groups of NH3 and NH4, and the NH4 moleculars are ideal candidates for the molecular doping of graphene while the interaction between graphene and the NH3 moleculars is weak.

  17. Laser Desorption Postionization for Imaging MS of Biological Material

    OpenAIRE

    Akhmetov, Artem; Moore, Jerry F.; Gasper, Gerald L.; Koin, Peter J.; Hanley, Luke

    2010-01-01

    Vacuum ultraviolet single photon ionization (VUV SPI) is a soft ionization technique that has the potential to address many of the limitations of MALDI for imaging MS. Laser desorption postionization (LDPI) employs VUV SPI for postionization and is experimentally analogous to a MALDI instrument with the addition of a pulsed VUV light source. This review discusses progress in LDPI-MS over the last decade, with an emphasis on imaging MS of bacterial biofilms, analytes whose high salt environmen...

  18. Dicyandiamide Sorption-Desorption Behavior on Soils and Peat Humus

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hai-Jun; WU Zhi-Jie; ZHOU Qi-Xing

    2004-01-01

    The sorption-desorption behavior of dicyandiamide (DCD) is an important chemical process that affects DCD fate and mobility in soils. Therefore, this study quantified DCD sorption-desorption on a phaeozem (Mollisol), a burozem (Alfisol), a soil with organic matter-removed and peat humus using the batch-equilibration procedure, and identified soil properties that influenced DCD sorption. The sorption on peat humus was higher than that on the phaeozem and the burozem, with much lower sorption observed on the soil with organic matter-removed, indicating that soil organic matter was the main carrier of DCD sorption. Due to its amphipathic property the DCD molecule sorption on the phaeozem and the burozem decreased as pH increased from about 2 to 5, but a further increase in pH led to a rise in DCD sorption.The DCD desorption hysteretic effect for peat humus was greater than that for the phaeozem and the burozem using 0.01 mol L-1 CaC12 as the background electrolyte, suggesting that the hydrophobic domains of organic matter may play an important role in DCD sorption.

  19. Thermodynamic properties of water desorption of forage turnip seeds

    Directory of Open Access Journals (Sweden)

    Kelly Aparecida Sousa

    2014-11-01

    Full Text Available The purpose of this study was to determine the thermodynamic properties of the process of water sorption in forage turnip  seeds. The equilibrium moisture content of forage turnip  seeds was determined by the gravimetric-dynamic method for different values of temperature and water activity. According to the results, increasing the moisture content increases the energy required for the evaporation of water in forage turnip seeds, and the values of integral isosteric heat of desorption, within the moisture content range of 3.33 to 11.30 (% d.b., varies from 4,222.70 to 2,870.34 kJ kg-1. With the elevation in the equilibrium moisture content, there is an increase in differential entropy and Gibbs free energy, which has positive values, demonstrating non-spontaneity in the process of desorption in the seeds. The theory of enthalpy-entropy compensation can be satisfactorily applied to the sorption phenomenon, and the process of water desorption of forage turnip seeds is controlled by enthalpy.

  20. Hydrogen absorption and desorption in rapidly solidified Mg- Al alloys

    Science.gov (United States)

    Urgnani, J.; Di Chio, M.; Palumbo, M.; Feuerbacher, M.; Fernandez, J. F.; Leardini, F.; Baricco, M.

    2009-01-01

    The addition of Al to Mg has been indicated as a suitable way to destabilise the hydride phase, in order to bring the absorption and desorption reactions close to reasonable temperatures and pressure values for hydrogen storage. Rapid solidification is known to refine the microstructure of Mg-Al alloys and it might improve the H2 absorption/desorption kinetics. In this paper, the interaction of H2 with rapidly solidified Mg-Al alloys have been studied for three different composition: Mg38.5Al61.5, Mg69Al31 and Mg72Al28. For Mg72Al28, no significant changes in the microstructure have been obtained by rapid solidification. In Mg69Al31, a significant grain refinement has been observed, whereas, for Mg38.5Al61.5, the formation of a metastable hexagonal phase has been found. In all cases, a disproportionation reaction has been observed after H2 absorption, leading to MgH2. After heating up to 430 °C the hydrogenated samples, a main desorption reaction from MgH2 has been observed, which brings again to the starting phases. Experimental results have been discussed on the basis of a thermodynamic assessment of the Mg-Al-H system.

  1. Adsorption and desorption of bivalent metals to hematite nanoparticles.

    Science.gov (United States)

    Grover, Valerie A; Hu, Jinxuan; Engates, Karen E; Shipley, Heather J

    2012-01-01

    The use of commercially prepared hematite nanoparticles (37.0 nm) was studied as an adsorbent in the removal of Cd(II), Cu(II), Pb(II), and Zn(II) from aqueous solutions. Single-metal adsorption was studied as a function of metal and adsorbent concentrations, whereas binary metal competition was found to be dependent on the molar ratio between the competing metals. Competitive effects indicated that Pb had strong homogenous affinity to the nanohematite surface, and decreased adsorption of Cd, Cu, and Zn occurred when Pb was present in a binary system. Metal adsorption strength to nanohematite at pH 6.0 increased with metal electronegativity: Pb > Cu > Zn ∼ Cd. Equilibrium modeling revealed that the Langmuir-Freundlich composite isotherm adequately described the adsorption and competitive effects of metals to nanohematite, whereas desorption was best described by the Langmuir isotherm. The desorption of metals from nanohematite was found to be pH dependent, with pH 4.0 > pH 6.0 > pH 8.0, and results showed that greater than 65% desorption was achieved at pH 4.0 within three 24-h cycles for all metals.

  2. Laser desorption lamp ionization source for ion trap mass spectrometry.

    Science.gov (United States)

    Wu, Qinghao; Zare, Richard N

    2015-01-01

    A two-step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI-ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm) is directed to a target inside a chamber evacuated to ~15 Pa causing desorption of molecules from the target's surface. The desorbed molecules are ionized by a vacuum ultraviolet (VUV) lamp (filled with xenon, major wavelength at 148 nm). The resulting ions are stored and detected in a three-dimensional quadrupole ion trap modified from a Finnigan Mat LCQ mass spectrometer operated at a pressure of ≥ 0.004 Pa. The limit of detection for desorbed coronene molecules is 1.5 pmol, which is about two orders of magnitude more sensitive than laser desorption laser ionization mass spectrometry using a fluorine excimer laser (157 nm) as the ionization source. The mass spectrum of four standard aromatic compounds (pyrene, coronene, rubrene and 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (OPC)) shows that parent ions dominate. By increasing the infrared laser power, this instrument is capable of detecting inorganic compounds.

  3. New perspectives in vacuum high voltage insulation. II. Gas desorption

    CERN Document Server

    Diamond, W T

    1998-01-01

    An examination has been made of gas desorption from unbaked electrodes of copper, niobium, aluminum, and titanium subjected to high voltage in vacuum. It has been shown that the gas is composed of water vapor, carbon monoxide, and carbon dioxide, the usual components of vacuum outgassing, plus an increased yield of hydrogen and light hydrocarbons. The gas desorption was driven by anode conditioning as the voltage was increased between the electrodes. The gas is often desorbed as microdischarges-pulses of a few to hundreds of microseconds-and less frequently in a more continuous manner without the obvious pulsed structure characteristic of microdischarge activity. The quantity of gas released was equivalent to many monolayers and consisted mostly of neutral molecules with an ionic component of a few percent. A very significant observation was that the gas desorption was more dependent on the total voltage between the electrodes than on the electric field. It was not triggered by field-emitted electrons but oft...

  4. Rapid decompression and desorption induced energetic failure in coal

    Directory of Open Access Journals (Sweden)

    Shugang Wang

    2015-06-01

    Full Text Available In this study, laboratory experiments are conducted to investigate the rapid decompression and desorption induced energetic failure in coal using a shock tube apparatus. Coal specimens are recovered from Colorado at a depth of 610 m. The coal specimens are saturated with the strong sorbing gas CO2 for a certain period and then the rupture disc is suddenly broken on top of the shock tube to generate a shock wave propagating upwards and a rarefaction wave propagating downwards through the specimen. This rapid decompression and desorption has the potential to cause energetic fragmentation in coal. Three types of behaviors in coal after rapid decompression are found, i.e. degassing without fragmentation, horizontal fragmentation, and vertical fragmentation. We speculate that the characteristics of fracture network (e.g. aperture, spacing, orientation and stiffness and gas desorption play a role in this dynamic event as coal can be considered as a dual porosity, dual permeability, dual stiffness sorbing medium. This study has important implications in understanding energetic failure process in underground coal mines such as coal gas outbursts.

  5. Sorption and desorption of silver ions by bentonite clays.

    Science.gov (United States)

    Constantino, Leonel Vinicius; Quirino, Juliana Nunes; Monteiro, Alessandra Maffei; Abrão, Taufik; Parreira, Paulo Sérgio; Urbano, Alexandre; Santos, Maria Josefa

    2017-04-01

    Anthropogenic activities have increased the concentration of metal species in the environment. The toxicity of silver ions to aquatic and terrestrial organisms has required monitoring by analytical methods, besides actions to promote its control as pollutant. Sorption and desorption processes are directly related to the mobility and availability of metal ions in the environment. In this context, clay minerals can be used for pre-concentration, removal and recovery of silver ions from aqueous solution. Herein, two bentonite clays (BaVC-1 and SWy-2) were characterised and applied to investigate the sorption and desorption of silver ions. Isotherms were fitted to the dual-mode Langmuir-Freundlich model to qualify and quantify sorption sites and evaluate the mobilisation process. The maximum sorption capacity was 743 and 849 meq kg(-1) for BaVC-1 and SWy-2, respectively. Hysteresis index (HI) and mobilisation factor (MF) suggest that the desorption of silver ions in BaVC-1 is about four times more conducive compared to that in SWy-2, although both materials have demonstrated a great potential for Ag(+) pre-concentration from aqueous solutions.

  6. Hydrogen absorption and desorption in rapidly solidified Mg- Al alloys

    Energy Technology Data Exchange (ETDEWEB)

    Urgnani, J; Di Chio, M; Palumbo, M; Baricco, M [Dipartimento di Chimica I.F.M. and NIS, Universita di Torino, via P. Giuria, 10125, Torino (Italy); Feuerbacher, M [Institut fuer Mikrostrukturforschung, Forschungszentrum Juelich GmbH, Leo-Brand- Strasse, 52428 Juelich (Germany); Fernandez, J F; Leardini, F, E-mail: jacopo.urgnani@unito.i [Departamento de Fisica de Materiales, Universidad Autonoma de Madrid, Cantoblanco, 28049, Madrid (Spain)

    2009-01-01

    The addition of Al to Mg has been indicated as a suitable way to destabilise the hydride phase, in order to bring the absorption and desorption reactions close to reasonable temperatures and pressure values for hydrogen storage. Rapid solidification is known to refine the microstructure of Mg-Al alloys and it might improve the H{sub 2} absorption/desorption kinetics. In this paper, the interaction of H{sub 2} with rapidly solidified Mg-Al alloys have been studied for three different composition: Mg{sub 38.5}Al{sub 61.5}, Mg{sub 69}Al{sub 31} and Mg{sub 72}Al{sub 28}. For Mg{sub 72}Al{sub 28}, no significant changes in the microstructure have been obtained by rapid solidification. In Mg{sub 69}Al{sub 31}, a significant grain refinement has been observed, whereas, for Mg{sub 38.5}Al{sub 61.5}, the formation of a metastable hexagonal phase has been found. In all cases, a disproportionation reaction has been observed after H{sub 2} absorption, leading to MgH{sub 2}. After heating up to 430 deg. C the hydrogenated samples, a main desorption reaction from MgH{sub 2} has been observed, which brings again to the starting phases. Experimental results have been discussed on the basis of a thermodynamic assessment of the Mg-Al-H system.

  7. Trapping, migration and desorption of helium in tungsten: influence of the implantation conditions

    Energy Technology Data Exchange (ETDEWEB)

    Debelle, A.; Barthe, M.F.; Sauvage, T.; Desgardin, P. [CERI, Centre d' Etudes et de Recherches par Irradiation, CNRS, 45 - Orleans (France); Peaucelle, C. [Lyon-1 Univ. Claude Bernard, CNRS/IN2P3/IPNL, 69 - Villeurbanne (France)

    2007-07-01

    Full text of publication follows: In the future International Thermonuclear Experimental Reactor (ITER), tungsten, due to its physical intrinsic properties, is a potential divertor candidate. The divertor, as a plasma-facing component, will be subjected to intense irradiations at high temperature. In the specific case of fusion reactor, high 14 MeV neutrons flux will cause the continuous production of both H and He by (n,p) and (n,{alpha}) nuclear reactions, and of irradiation-induced defects by recoils. Thus, it appears of crucial interest to study the He behaviour in tungsten introduced in such conditions, that means implanted at high energy and low fluences, and its evolution in temperature. To address this issue, polycrystalline and single crystal tungsten samples were {sup 3}He implanted, at room temperature, at different energies and fluences, ranging from 60 to 500 keV and 2x10{sup 13} to 10{sup 16} cm{sup -2} respectively. Then, thermal annealings upon different conditions (up to 1870 K) were carried out. Lateral distributions, depth profiling and desorption curves measurements of the implanted helium were performed using the {sup 3}He(d,{alpha}){sup 1}H nuclear reaction technique. Results show that, whatever the implantation conditions, helium is trapped during implantation, presumably at vacancy-type defects. However, the nature and consequently the stability of the helium-vacancy-like complexes differ. At high energy, the complexes are highly stable, and no desorption is observed after annealing up to 1773 K. A helium migration over a weak length is nonetheless noticed, as deduced from the comparison of the depth profiles, and attributed to the migration of the complexes. At low energy, a helium desorption is detected for annealing temperatures higher than 1470 K. It is very likely that under these conditions, simple HeV complexes are formed during implantation. Results obtained from a positron annihilation spectroscopy study on the implantation

  8. {sup 252}Cf plasma desorption and laser desorption mass spectrometry for the determination of molecular weight distribution of coal derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, B.R.; Bartle, K.D.; Ross, A.B.; Herod, A.A.; Kandiyoti, R.; Larsen, J.W. [University of Leeds, Leeds (United Kingdom). School of Chemistry

    1999-11-01

    A detailed knowledge of the molecular mass (MM) distribution in coal and its derived products is essential for a fundamental understanding of coal structure, and of the processes occurring during coal conversion. Fractionation using size exclusion chromatography (s.e.c.) using N-methyl-2-pyrrolidinone as the mobile phase has been applied to such materials and has provided improved MM distributions. Absolute calibration has been provided using matrix assisted laser desorption ionisation mass spectrometry (MAl.d.I.-m.s.). An alternative method of volatilising and ionising large molecules for mass spectrometry (m.s.) is {sup 252}Cf plasma desorption ({sup 252}Cf p.d.-m.s.). This involves the use of energetic fission fragments from the decay of {sup 252}Cf and produces mass spectra consisting predominantly of molecular ions from a range of polymers and biomolecules. This has been used by other workers to determine the molecular weight distribution of heavy distillation residues obtained from coal liquefaction processes either unfractionated or fractionated into broad fractions. Generally, a good agreement was obtained between values of MM determined by {sup 252}Cf p.d.-m.s. and s.e.c. A comparison is reported of MM distribution determined by {sup 252}Cf p.d.-m.s. and laser desorption mass spectrometry (l.d.-m.s.) for narrower fractions separated by s.e.c. from a coal tar pitch. 19 refs., 4 figs., 1 tab.

  9. Sorption/desorption reversibility of polycyclic aromatic hydrocarbons (PAHs) in soils and carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guohui

    2008-07-01

    Understanding sorption/desorption is an important prerequisite for the prediction of fate and transport of pollutants in the environment. During the last two decades, numerous studies have reported hysteresis phenomenon for the interaction of hydrophobic organic contaminants (HOCs) with natural organic matter (NOM). It manifests as nonsingular sorption/desorption isotherms or different rates for sorption and desorption, where during desorption a higher affinity of a compound on a given sorbent and a longer time scale for release than for sorption is observed. Other studies showed that some of the reported sorption/desorption hysteresis phenomena are due to experimental artifacts, mainly resulting from non-attainment of sorption equilibrium before desorption experiments, which result in 'pseudo-hysteresis'. Except for the hypothesis of sorbent reconfiguration, clear experimental evidence for the physical or chemical mechanisms proposed to lead to hysteresis is still lacking. In this study, sorption/desorption equilibrium and kinetics of phenanthrene sorption/desorption from two soils and three carbonaceous samples were investigated using both batch and column techniques. The main objective of this work was to monitor hysteresis phenomenon by carefully recovering the solute mass in the system and to compare sorption/desorption equilibria and kinetics thermodynamically. Nonsingular isotherms and higher desorption enthalpies as well as increased activation energies with proceeding desorption are expected if significant hysteresis exists. Sorption-desorption cycles were carried out to compare equilibrium isotherms and associated sorption/desorption enthalpies (AeH, isosteric heats). Instead of the traditional decant-and-refill batch method, the experiments were conducted using a newly designed batch protocol, which enables the determination of sorption/desorption isotherms at different temperatures using a closed batch system. This method additionally allows

  10. Formation of nanocarbon spheres by thermal treatment of woody char from fast pyrolysis process

    Science.gov (United States)

    Qiangu Yan; Hossein Toghiani; Zhiyong Cai; Jilei Zhang

    2014-01-01

    Influences of thermal treatment conditions of temperature, reaction cycle and time, and purge gas type on nanocarbon formation over bio-chars from fast pyrolysis and effects of thermal reaction cycle and purge gas type on bio-char surface functional groups were investigated by temperature-programmed desorption (TPD) and temperature programmed reduction methods....

  11. Desorption Kinetics and Mechanisms of CO2 on Amine-Based Mesoporous Silica Materials

    Directory of Open Access Journals (Sweden)

    Yang Teng

    2017-01-01

    Full Text Available Tetraethylenepentamine (TEPA-based mesoporous MCM-41 is used as the adsorbent to determine the CO2 desorption kinetics of amine-modified materials after adsorption. The experimental data of CO2 desorption as a function of time are derived by zero-length column at different temperatures (35, 50, and 70 °C and analyzed by Avrami’s fractional-order kinetic model. A new method is used to distinguish the physical desorption and chemical desorption performance of surface-modified mesoporous MCM-41. The activation energy Ea of CO2 physical desorption and chemical desorption calculated from Arrhenius equation are 15.86 kJ/mol and 57.15 kJ/mol, respectively. Furthermore, intraparticle diffusion and Boyd’s film models are selected to investigate the mechanism of CO2 desorption from MCM-41 and surface-modified MCM-41. For MCM-41, there are three rate-limiting steps during the desorption process. Film diffusion is more prominent for the CO2 desorption rates at low temperatures, and pore diffusion mainly governs the rate-limiting process under higher temperatures. Besides the surface reaction, the desorption process contains four rate-limiting steps on surface-modified MCM-41.

  12. Glyphosate sorption and desorption in soils with distinct phosphorus levels

    Energy Technology Data Exchange (ETDEWEB)

    Prata, Fabio [BIOAGRI Labs., Piracicaba, SP (Brazil). Div. de Quimica. Lab. de Radioquimica; Cardinali, Vanessa Camponez do Brasil; Tornisielo, Valdemar Luiz; Regitano, Jussara Borges [Sao Paulo Univ., Piracicaba, SP (Brazil). Escola Superior de Agricultura Luiz de Queiroz. Dept. de Ciencias Exatas; Lavorenti, Arquimedes [Centro de Energia Nuclear na Agricultura (CENA), Piracicaba, SP (Brazil). Secao de Toxicologia

    2003-03-01

    The sorption of glyphosate by soils occurs due to the inner sphere complex formation with metals of soil oxides, which are related to the soil phosphate adsorption capacity. The aim of this study was to evaluate the effects of increasing rates of phosphorus on sorption and desorption of glyphosate in three soils with different mineralogical attributes. Soils were a Rhodic Kandiudalf, an Anionic Acrudox and a Typic Humaquept. Soil samples were amended with Kh{sub 2}PO{sub 4} at equivalent rates of 0; 1,000; 5,000; 20,000 and 50,000 kg ha{sup -1} of P{sub 2}O{sub 5}, which are high from the agricultural point of view, but necessary in order to perform sorption and desorption studies. The experimental design consisted of a completely randomized factorial: 2 soils x 5 phosphorus rates and 3 replicates. For the sorption experiments, five glyphosate solutions were employed (0.42; 0.84; 1.68; 3.36 and 6.72 mg L{sup -1}), with a {sup 14}C radioactivity of 0.233 kBq mL{sup -1}. Four steps of the desorption procedures withCaCl{sub 2} 0.01 mol L{sup -1} and one extraction with Mehlich 3 were performed only at one concentration (0.84 mol L{sup -1}). Soil samples were afterwards biologically oxidized to establish the radioactive balance. Glyphosate competes with phosphorus for specific sorption sites, but this competition becomes important when phosphorus is present at rates higher than 1,000 mg dm{sup -3}. Moreover, a small amount of applied glyphosate was extracted (<10%), and the extraction increased with increasing soil phosphorus content. (author)

  13. Glyphosate sorption and desorption in soils with distinct phosphorus levels

    Directory of Open Access Journals (Sweden)

    Prata Fábio

    2003-01-01

    Full Text Available The sorption of glyphosate by soils occurs due to the inner sphere complex formation with metals of soil oxides, which are related to the soil phosphate adsorption capacity. The aim of this study was to evaluate the effects of increasing rates of phosphorus on sorption and desorption of glyphosate in three soils with different mineralogical attributes. Soils were a Rhodic Kandiudalf, an Anionic Acrudox and a Typic Humaquept. Soil samples were amended with KH2PO4 at equivalent rates of 0; 1,000; 5,000; 20,000 and 50,000 kg ha-1 of P2O5, which are high from the agricultural point of view, but necessary in order to perform sorption and desorption studies. The experimental design consisted of a completely randomized factorial: 2 soils x 5 phosphorus rates and 3 replicates. For the sorption experiments, five glyphosate solutions were employed (0.42; 0.84; 1.68; 3.36 and 6.72 mg L-1, with a 14C radioactivity of 0.233 kBq mL-1. Four steps of the desorption procedure with CaCl2 0.01 mol L-1 and one extraction with Mehlich 3 were performed only at one concentration (0.84 mol L-1. Soil samples were afterwards biologically oxidized to establish the radioactive balance. Glyphosate competes with phosphorus for specific sorption sites, but this competition becomes important when phosphorus is present at rates higher than 1,000 mg dm-3. Moreover, a small amount of applied glyphosate was extracted (<10%, and the extraction increased with increasing soil phosphorus content.

  14. Determination of Surface Exciton Energies by Velocity Resolved Atomic Desorption

    Energy Technology Data Exchange (ETDEWEB)

    Hess, Wayne P.; Joly, Alan G.; Beck, Kenneth M.; Sushko, Petr V.; Shluger, Alexander L.

    2004-08-20

    We have developed a new method for determining surface exciton band energies in alkali halides based on velocity-resolved atomic desorption (VRAD). Using this new method, we predict the surface exciton energies for K1, KBr, KC1, and NaC1 within +0.15 eV. Our data, combined with the available EELS data for alkali fluorides, demonstrate a universal linear correlation with the inverse inter-atomic distance in these materials. The results suggest that surface excitons exist in all alkali halides and their excitation energies can be predicted from the known bulk exciton energies and the obtained correlation plot.

  15. Temperature-programmed desorption for membrane inlet mass spectrometry

    DEFF Research Database (Denmark)

    Ketola, R.A.; Grøn, C.; Lauritsen, F.R.

    1998-01-01

    We present a novel technique for analyzing volatile organic compounds in air samples using a solid adsorbent together with temperature-programmed desorption and subsequent detection by membrane inlet mass spectrometry (TPD-MIMS). The new system has the advantage of a fast separation of compounds...... prior to the detection by MIMS. The gaseous sample is simply adsorbed on the adsorbent, which is then rapidly heated from 30 degrees C to 250 degrees C at a rate of 50 degrees C/min, Trapped organic compounds are released from the adsorbent into a helium stream at different temperatures depending...

  16. Desorption Techniques for Determination of Metals Mobility in Soils

    Directory of Open Access Journals (Sweden)

    P. Bartoš

    2002-01-01

    Full Text Available Three leaching techniques for assessment of fixed and mobile metal or radionuclides in soils are demonstrated on radiocaesium speciation. A new leaching technique based on the variation of the leaching solution volume to solid phase amount is proposed. It enables parallel treatment of large numbers of samples and, therefore, is suitable for a routine analysis of contaminant mobility in soils. As a leaching solution, 1 M ammonium acetate is proposed for caesium, but any other desorption solution harmonised with existing speciation schemes can be used.

  17. SVSCf plasma desorption mass spectrometry: recent advances and applications

    Energy Technology Data Exchange (ETDEWEB)

    Kamensky, I.; Craig, A.G.

    1987-01-01

    SVSCf plasma desorption mass spectrometry (PDMS) as utilized in the BIO-ION instruments is described. The sensitivity of the technique is investigated for varying amounts of bovine insulin. The results show accurate mass assignment for pmole amounts of sample. Several methods, currently used for sample preparation in PDMS, are described. Spectra of the antibiotic nisin using two different sample preparation techniques show significant variation. The fragmentation pattern of reduced acetylated maltoheptaose is also presented. The initial results obtained using a new PDMS instrument equipped with variable flight path are shown. The increased resolution is illustrated using the extended flight path to measure the molecular ion region of the maltoheptaose.

  18. DESORPTION OF VOCs FROM POLYMERIC ADSORBENTS UNDER MICROWAVE FIELD

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Desorption of volatile organic compounds (VOCs)from polymeric adsorbents by microwave was investigated experimentally. Two kinds of organic compounds, benzene and toluene,were separately used as adsorbates in this work. Results showed that the application of microwave to regenerate the polymeric adsorbents not only can get higher regeneration efficiency in comparison with the use of heat regeneration, but also make the temperatures of the fixed beds much lower than that when using the heat regeneratton The weaker the polarity of a polymeric adsorbent, the easier its regeneration was.

  19. DESORPTION OF VOCs FROM POLYMERIC ADSORBENTS UNDER MICROWAVE FIELD

    Institute of Scientific and Technical Information of China (English)

    LIXiang; LIZhong; 等

    2001-01-01

    Desorption of volatile organic compounds(VOCs) from polymeric adsorbents by microwave was investigated experimentally.Two kinds of organic compounds.benzene and toluene.were separately used as adsorbates in this work Results showed that the application of microwave to regenerate the polymeric adsorbents not only can get higher regeneration efficiency in comparison with the use of heat regeneration,but also make the temperatures of the fixed beds much lower than that when using the heat regeneration the weaker the polarity of a polymericadsorbent,the easier its regeneration was.

  20. Site Specificity in Femtosecond Laser Desorption of Neutral H Atoms from Graphite(0001)

    DEFF Research Database (Denmark)

    Frigge, R.; Hoger, T.; Siemer, B.;

    2010-01-01

    Femtosecond laser excitation and density functional theory reveal site and vibrational state specificity in neutral atomic hydrogen desorption from graphite induced by multiple electronic transitions. Multimodal velocity distributions witness the participation of ortho and para pair states...... of chemisorbed hydrogen in the desorption process. Very slow velocities of 700 and 400  ms-1 for H and D atoms are associated with the desorption out of the highest vibrational state of a barrierless potential....

  1. Desorption of metals from Cetraria islandica (L. Ach. Lichen using solutions simulating acid rain

    Directory of Open Access Journals (Sweden)

    Čučulović Ana A.

    2014-01-01

    Full Text Available Desorption of metals K, Al, Ca, Mg, Fe, Ba, Zn, Mn, Cu and Sr from Cetraria islandica (L. with solutions whose composition was similar to that of acid rain, was investigated. Desorption of metals from the lichen was performed by five successive desorption processes. Solution mixtures containing H2SO4, HNO3 and H2SO4-HNO3 were used for desorption. Each solution had three different pH values: 4.61, 5.15 and 5.75, so that the desorptions were performed with nine different solutions successively five times, always using the same solution volume. The investigated metals can be divided into two groups. One group was comprised of K, Ca and Mg, which were desorbed in each of the five desorption processes at all pH values used. The second group included Al, Fe, Zn, Ba, Mn and Sr; these were not desorbed in each individual desorption and not at all pH values, whereas Cu was not desorbed at all under any circumstances. Using the logarithmic dependence of the metal content as a function of the desorption number, it was found that potassium builds two types of links and is connected with weaker links in lichen. Potassium is completely desorbed, 80% in the first desorption, and then gradually in the following desorptions. Other metals are linked with one weaker link (desorption 1-38% and with one very strong link (desorption below the metal detection limit. [Projekat Ministarstva nauke Republike Srbije, br. III43009 i br. ON 172019

  2. Complex surface analytical investigations on hydrogen absorption and desorption processes of a TiMn2-based alloy.

    Science.gov (United States)

    Schülke, Mark; Kiss, Gábor; Paulus, Hubert; Lammers, Martin; Ramachandran, Vaidyanath; Sankaran, Kannan; Müller, Karl-Heinz

    2009-04-01

    Metal hydrides are one of the most promising technologies in the field of hydrogen storage due to their high volumetric storage density. Important reaction steps take place at the very surface of the solid during hydrogen absorption. Since these reaction steps are drastically influenced by the properties and potential contamination of the solid, it is very important to understand the characteristics of the surface, and a variety of analytical methods are required to achieve this. In this work, a TiMn(2)-type metal hydride alloy is investigated by means of high-pressure activation measurements, X-ray photoelectron spectroscopy (XPS), secondary neutral mass spectrometry (SNMS) and thermal desorption mass spectrometry (TDMS). In particular, TDMS is an analytical tool that, in contrast to SIMS or SNMS, allows the hydrogen content in a metal to be quantified. Furthermore, it allows the activation energy for desorption to be determined from TDMS profiles; the method used to achieve this is presented here in detail. In the results section, it is shown that the oxide layer formed during manufacture and long-term storage prevents any hydrogen from being absorbed, and so an activation process is required. XPS measurements show the oxide states of the main alloy elements, and a layer 18 nm thick is determined via SNMS. Furthermore, defined oxide layers are produced and characterized in UHV using XPS. The influence of these thin oxide layers on the hydrogen sorption process is examined using TDMS. Finally, the activation energy of desorption is determined for the investigated alloy using the method presented here, and values of 46 kJ/mol for hydrogen sorbed in UHV and 103 kJ/mol for hydrogen originating from the manufacturing process are obtained.

  3. 2nd International Workshop on Desorption Induced by Electronic Transitions

    CERN Document Server

    Menzel, Dietrich

    1985-01-01

    The second workshop on Desorption Induced by Electronic Transitions (DIET II) took place October 15-17, 1984, in SchloB Elmau, Bavaria. DIET II, fol­ lowing the great success of DIET I (edited by N. H. Tolk, M. M. Traum, J. C. Tully, T. E. Madey and published in Springer Ser. Chem. Phys. , Vol. 24), again brought together over 60 workers in this exciting field. The "hard co­ re of experts" was essentially the same as in DIET I but the general overlap of participants between the two meetings was small. While DIET I had the function of an exposition of the status of the field DIET II focussed more on new developments. The main emphasis was again on the microscopic under­ standing of DIET but a number of side aspects and the application of DIET ideas to other fields such as sputtering, laser-induced desorption, fractu­ re, erosion, etc. were considered, too. New mechanisms and new refined expe­ rimental techniques were proposed and discussed at the meeting critically but with great enthusiasm. In addition t...

  4. 3rd International Workshop on Desorption Induced by Electronic Transitions

    CERN Document Server

    Knotek, Michael

    1988-01-01

    These proceedings are the result of the third international workshop on Desorption Induced by Electronic Transitions, DIET III, which took place on Shelter Island, NY, May. 20-22, 1987. The work contained in this volume is an excellent summary of the current status of the field and should be a valuable reference text for both "seasoned" researchers and newcomers in the field of DIET. Based on the success of the meeting it seems clear that interest and enthusiasm in the field is strong. It is also apparent, from the many lively discussions during the meeting, that many unanswered questions (and controversies) remain to be solved. It was particularly pleasing to see many new participants from new and rapidly advancing fields, ranging from gas phase dynamics to semiconductor processing. The resulting cross-fertilization from these separate but related fields is playing an important role in helping us understand desorption processes at solid surfaces. In general, the topics covered during the course of the worksh...

  5. Hydrocarbon analysis using desorption atmospheric pressure chemical ionization

    KAUST Repository

    Jjunju, Fred Paul Mark

    2013-07-01

    Characterization of the various petroleum constituents (hydronaphthalenes, thiophenes, alkyl substituted benzenes, pyridines, fluorenes, and polycyclic aromatic hydrocarbons) was achieved under ambient conditions without sample preparation by desorption atmospheric pressure chemical ionization (DAPCI). Conditions were chosen for the DAPCI experiments to control whether ionization was by proton or electron transfer. The protonated molecule [M+H]+ and the hydride abstracted [MH]+ form were observed when using an inert gas, typically nitrogen, to direct a lightly ionized plasma generated by corona discharge onto the sample surface in air. The abundant water cluster ions generated in this experiment react with condensed-phase functionalized hydrocarbon model compounds and their mixtures at or near the sample surface. On the other hand, when naphthalene was doped into the DAPCI gas stream, its radical cation served as a charge exchange reagent, yielding molecular radical cations (M+) of the hydrocarbons. This mode of sample ionization provided mass spectra with better signal/noise ratios and without unwanted side-products. It also extended the applicability of DAPCI to petroleum constituents which could not be analyzed through proton transfer (e.g., higher molecular PAHs such as chrysene). The thermochemistry governing the individual ionization processes is discussed and a desorption/ionization mechanism is inferred. © 2012 Elsevier B.V.

  6. The cooling effect by adsorption-desorption cycles

    Directory of Open Access Journals (Sweden)

    Wolak Eliza

    2017-01-01

    Full Text Available Adsorption appliances may turn out to be an alternative to compression-type refrigerators. The adsorption refrigeration machine may be driven by a low-grade heat source, especially solar energy. Solar adsorption cooling systems are environment-friendly and have zero ozone depletion potential. Therefore, the adsorption refrigeration is one kind of energy saving refrigeration methods. The merits of the adsorption refrigeration systems will be more significant especially when it is used in vehicles (automobiles, ships and locomotives, to preserve food and medicines and in air-conditioning. The paper presents the advantages and disadvantages as well as the evolution of the technology of adsorptive refrigeration systems. The methods of improving of adsorption refrigeration systems through improvements in adsorbents properties, use of advanced cycles and hybrid systems is also presented. Possible applications and perspectives for development of adsorption cooling systems are also analyzed. The paper describes a test stand of the adsorption-desorption refrigeration. The present investigations have been carried out utilizing the activated carbon granules as an adsorbent and methanol as an adsorbate. The paper demonstrates the measurement of temperature changes in the adsorbent bed and condenser during adsorption-desorption cycles.

  7. Laser desorption postionization for imaging MS of biological material.

    Science.gov (United States)

    Akhmetov, Artem; Moore, Jerry F; Gasper, Gerald L; Koin, Peter J; Hanley, Luke

    2010-02-01

    Vacuum ultraviolet single photon ionization (VUV SPI) is a soft ionization technique that has the potential to address many of the limitations of matrix-assisted laser desorption/ionization (MALDI) for imaging MS. Laser desorption postionization (LDPI) uses VUV SPI for postionization and is experimentally analogous to a MALDI instrument with the addition of a pulsed VUV light source. This review discusses progress in LDPI-MS over the last decade, with an emphasis on imaging MS of bacterial biofilms, analytes whose high salt environment make them particularly resistant to imaging by MALDI-MS. This review first considers fundamental aspects of VUV SPI including ionization mechanisms, cross sections, quantum yields of ionization, dissociation and potential mass limits. The most common sources of pulsed VUV radiation are then described along with a newly constructed LDPI-MS instrument with imaging capabilities. Next, the detection and imaging of small molecules within intact biofilms is demonstrated by LDPI-MS using 7.87 eV (157.6 nm) VUV photons from a molecular fluorine excimer laser, followed by the use of aromatic tags for detection of selected species within the biofilm. The final section considers the future prospects for imaging intact biological samples by LDPI-MS. Copyright 2010 John Wiley & Sons, Ltd.

  8. Laser desorption VUV postionization MS imaging of a cocultured biofilm.

    Science.gov (United States)

    Bhardwaj, Chhavi; Moore, Jerry F; Cui, Yang; Gasper, Gerald L; Bernstein, Hans C; Carlson, Ross P; Hanley, Luke

    2013-09-01

    Laser desorption postionization mass spectrometry (LDPI-MS) imaging is demonstrated with a 10.5 eV photon energy source for analysis and imaging of small endogenous molecules within intact biofilms. Biofilm consortia comprised of a synthetic Escherichia coli K12 coculture engineered for syntrophic metabolite exchange are grown on membranes and then used to test LDPI-MS analysis and imaging. Both E. coli strains displayed many similar peaks in LDPI-MS up to m/z 650, although some observed differences in peak intensities were consistent with the appearance of byproducts preferentially expressed by one strain. The relatively low mass resolution and accuracy of this specific LDPI-MS instrument prevented definitive assignment of species to peaks, but strategies are discussed to overcome this shortcoming. The results are also discussed in terms of desorption and ionization issues related to the use of 10.5 eV single-photon ionization, with control experiments providing additional mechanistic information. Finally, 10.5 eV LDPI-MS was able to collect ion images from intact, electrically insulating biofilms at ~100 μm spatial resolution. Spatial resolution of ~20 μm was possible, although a relatively long acquisition time resulted from the 10 Hz repetition rate of the single-photon ionization source.

  9. Desorption of alkali atoms from 4He nanodroplets.

    Science.gov (United States)

    Hernando, Alberto; Barranco, Manuel; Pi, Martí; Loginov, Evgeniy; Langlet, Marina; Drabbels, Marcel

    2012-03-21

    The dynamics following the photoexcitation of Na and Li atoms located on the surface of helium nanodroplets has been investigated in a joint experimental and theoretical study. Photoelectron spectroscopy has revealed that excitation of the alkali atoms via the (n + 1)s ←ns transition leads to the desorption of these atoms. The mean kinetic energy of the desorbed atoms, as determined by ion imaging, shows a linear dependence on excitation frequency. These experimental findings are analyzed within a three-dimensional, time-dependent density functional approach for the helium droplet combined with a Bohmian dynamics description of the desorbing atom. This hybrid method reproduces well the key experimental observables. The dependence of the observables on the impurity mass is discussed by comparing the results obtained for the (6)Li and (7)Li isotopes. The calculations show that the desorption of the excited alkali atom is accompanied by the creation of highly non-linear density waves in the helium droplet that propagate at supersonic velocities.

  10. Sorption and desorption of dyes by sulfonated coal

    Energy Technology Data Exchange (ETDEWEB)

    Mittal, A.K. (Motilal Nehru Regional Coll. of Engineering, Allahabad (India)); Venkobachar, C. (Indian Inst. of Tech., Kanpur (India))

    Wastewaters from dye-manufacturing factories and textile, paper, and pulp industries are highly colored. Their discharge into river waters make the water inhibitory to aquatic life, aside from causing, visible pollution. Dyes have a tendency to sequester metals, thus causing microtoxicity to fish and other aquatic organisms. A wide variety of low-cost materials such as flyash, clay minerals, coal, tire chippings, coconut shell powder and biosorbents are being tried as viable substitutes for activated carbon to remove different pollutants such as pesticides, heavy metals, and dyes. The removal of dyes depends upon their physical and chemical characteristics, as well as the properties of the selected sorbents. To understand the nature of the chemical bonding between dyes and sorbents during the sorption process, it is essential to conduct desorption studies. The reversibility of adsorption of dyes can also be determined by a simple mathematical equation. These studies provide information on whether or not the sorbent material can be regenerated after exhaustion. The present study focuses on sorption-desorption of dyes by sulfonated coal, whose dye sorption potential was established by Mittal and Venkobachar (1990).

  11. Adsorption and desorption on coals for CO2 sequestration

    Institute of Scientific and Technical Information of China (English)

    WANG Zuo-tang; FU Zhen-kun; ZHANG Ban-gan; WANG Guo-xiong; RUDOLPH Victor; HUO Li-wen

    2009-01-01

    Adsorption and desorption of carbon dioxide, methane and other gases on coals has been investigated experimentally using representative Zhongliangshan coals. Gas adsorption is one of the major concerns for both CO2 sequestration and methane recovery processes. The experiments were carried out using both single and multi-component mixtures at 25 ℃ and 30 ℃ with the highest pressure of 12 MPa. The coal was under moisture equilibrated conditions. This provides experimental data from which a predictive assessment of CO2 sequestration and/or methane recovery can be conducted. The results show that for pure gasses the CH4 adsorption capacity is higher than the N2 adsorption capacity but lower than the CO2 adsorption capacity. Injection of CO2 or other gases into the coal significantly affects CH4 desorption. This allows the enhancement of CH4 recovery from the coals, thus supplying more clean energy while sequestering significant amounts of CO2 thereby reducing the greenhouse effect from human beings.

  12. IMPULSIVE SPOT HEATING AND THERMAL EXPLOSION OF INTERSTELLAR GRAINS REVISITED

    Energy Technology Data Exchange (ETDEWEB)

    Ivlev, A. V.; Röcker, T. B.; Vasyunin, A.; Caselli, P., E-mail: ivlev@mpe.mpg.de [Max-Planck-Institut für Extraterrestrische Physik, D-85741 Garching (Germany)

    2015-05-20

    The problem of the impulsive heating of dust grains in cold, dense interstellar clouds is revisited theoretically with the aim of better understanding the leading mechanisms of the explosive desorption of icy mantles. We rigorously show that if the heating of a reactive medium occurs within a sufficiently localized spot (e.g., the heating of mantles by cosmic rays (CRs)), then the subsequent thermal evolution is characterized by a single dimensionless number λ. This number identifies a bifurcation between two distinct regimes: when λ exceeds a critical value (threshold), the heat equation exhibits the explosive solution, i.e., the thermal (chemical) explosion is triggered. Otherwise, thermal diffusion causes the deposited heat to spread over the entire grain—this regime is commonly known as whole-grain heating. The theory allows us to find a critical combination of physical parameters that govern the explosion of icy mantles due to impulsive spot heating. In particular, our calculations suggest that heavy CR species (e.g., iron ions) colliding with dust are able to trigger the explosion. Based on recently calculated local CR spectra, we estimate the expected rate of explosive desorption. The efficiency of the desorption, which in principle affects all solid species independent of their binding energy, is shown to be comparable to other CR desorption mechanisms typically considered in the literature. Also, the theory allows us to estimate the maximum abundances of reactive species that may be stored in the mantles, which provides important constraints on the available astrochemical models.

  13. Effects of A Top SiO2 Surface Layer on Cavity Formation and Helium Desorption in Silicon

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Cz n-type Si (100) samples with and without a top SiO2 layer were implanted with 40 keV helium ions at the same dose of 5×1016 cm-2. Cross-sectional transmission electron microscopy (XTEM) and thermal desorption spectroscopy (THDS) were used to study the thermal evolution of cavities upon and helium thermal release, respectively. XTEM results show that the presence of the top SiO2 layer could suppress the thermal growth of cavities mainly formed in the region close to the SiO2/Si interface, which leads to the reduction in both the cavity band and cavity density. THDS results reveal that the top oxide layer could act as an effective barrier for the migration of helium atoms to the surface, and it thus gives rise to the formation of more overpresurrized bubbles and to the occurrence of a third release peak located at about 1100 K. The results were qualitively discussed by considering the role of the oxide surface layer in defect migration and evolution upon annealing.

  14. Development of a Thermal Desorption Gas Chromatography-Mass Spectrometry Analysis Method for Airborne Dichlorodiphenyltrichloroethane

    Science.gov (United States)

    2013-05-28

    capable of taking a blood meal, require protein from blood for egg laying. The selection of where to lay eggs is highly variable, but Anopheles and Aedes...chemist Paul Hermann Müeller discovered DDT’s insecticidal activity, a finding that earned him the 1948 Nobel Prize for Medicine and Physiology “for his...Ecological Connections:65-9 23. Frierson JG. 2010. The yellow fever vaccine: a history . Yale J Biol Med 83:77-85 24. Galadi A, Bitar H, Chanon M

  15. Analysis of Thermal Desorption System for the Chemical Treatment of Old Storages of Oil Based Mud

    Directory of Open Access Journals (Sweden)

    Tanweer Hussain

    2013-04-01

    Full Text Available This paper presents an analysis for the chemical treatment of OBM (Oil Based Mud used in the drilling process in the oil and gas industry. The analysis is based on OBM stored at ENI (Italian National Energy gas fields at Bhit mount district Jamshoro since the last ten years that has been chemically and physically deteriorated. Characterization of various OBM samples was performed and these samples were processed in order to evaluate the best characteristics of the OBM for optimum treatment results. The OBM treatment process involves the separation of hazardous fluid (such as diesel or mineral oil from solids Due to the lean quality of the OBM, the dust separation process in the cyclone caused blockage in the cyclone. This paper suggests a remedial way by means of installation of a hammer stick in the cyclone dust collector to overcome cyclone blockage. The analysis is performed to compare the pressure drop and the dust collection efficiency in the cyclone with and without the hammer stick. The post-installation experimental results showed that hammer stick can improve the cyclone dust collection efficiency without blockage of the cyclone.

  16. Analysis of Thermal Desorption System for the Chemical Treatment of Old Storages of Oil Based Mud

    OpenAIRE

    Tanweer Hussain; Abdul Rehman Memon; Javed Larik

    2013-01-01

    This paper presents an analysis for the chemical treatment of OBM (Oil Based Mud) used in the drilling process in the oil and gas industry. The analysis is based on OBM stored at ENI (Italian National Energy) gas fields at Bhit mount district Jamshoro since the last ten years that has been chemically and physically deteriorated. Characterization of various OBM samples was performed and these samples were processed in order to evaluate the best characteristics of the OBM for optimum treatment ...

  17. Spatial distributions and transient effects in molecular fluxes for the calibration of thermal desorption spectrometers

    Science.gov (United States)

    Jackson, Robert Howard

    The measurement of molecular fluxes with a differentially pumped mass spectrometer requires a method by which the mass spectrometer signal can be calibrated against a known molecular flux. This work presents a methodology for producing known molecular fluxes using a flow calibrated effusion source in conjunction with a glass capillary array molecular doser. The effusion source is comprised of a calibrated volume, a spinning rotor pressure gauge, and a positive shutoff capillary leak valve. The efficiency of calculating the spatial flux distribution from the doser was improved by reparameterization of the formalism of Winkler and Yates. This formalism was extended to arbitrarily shaped planar targets using Fourier convolution techniques. The flux distribution from the doser was measured close to the array at 0.635mm and at 1 cm distance. Using the effective diameter of the array as the only fitting parameter for the close data, the model correctly predicts the flux distribution at 1 cm. The loss of molecular flow due to sticking in the doser affects the calibration and, therefore was estimated from the transient response through the doser using a 1-dimensional diffusion model of the transient flow from the capillary valve through the doser. Three cases are considered: a long narrow tube without sticking, with sticking, and with a restricted exit. In each case, the partial differential equation for 1-D diffusion was solved for a step change in the inlet flow with a well-pumped exit. The transient exit flow measured for argon gas fits the non-sticking model accurately. The oxygen response included a non-sticking transient, consistent with the mass adjusted argon transient, and a slowly saturating exponential function. This slow function is not consistent with sticking in the doser tube but may be due to changes in the mass spectrometer multiplier or some other adsorption loss. Finally, the above methodology was used to calibrate the mass spectrometer for oxygen and the c(2 x 4) oxygen coverage on Pd(110) was measured to be 0.44MIL, consistent with measurements by nuclear reaction analysis. A modified King-Wells method for adsorption is also presented but shows an adsorbed coverage 30% lower than that previously measured.

  18. Auger decay mechanism in photon-stimulated desorption of ions from surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Parks, C.C.

    1983-11-01

    Photon-stimulated desorption (PSD) of positive ions was studied with synchrotron radiation using an angle-integrating time-of-flight mass spectrometer. Ion yields as functions of photon energy near core levels were measured from condensed gases, alkali fluorides, and other alkali and alkaline earth halides. These results are compared to bulk photoabsorption measurements with emphasis on understanding fundamental desorption mechanisms. The applicability of the Auger decay mechanism, in which ion desorption is strictly proportional to surface absorption, is discussed in detail. The Auger decay model is developed in detail to describe Na/sup +/ and F/sup +/ desorption from NaF following Na(1s) excitation. The major decay pathways of the Na(1s) hole leading to desorption are described and equations for the energetics of ion desorption are developed. Ion desorption spectra of H/sup +/, Li/sup +/, and F/sup +/ are compared to bulk photoabsorption near the F(2s) and Li(1s) edges of LiF. A strong photon beam exposure dependence of ion yields from alkali fluorides is revealed, which may indicate the predominance of metal ion desorption from defect sites. The large role of indirect mechanisms in ion desorption condensed N/sub 2/-O/sub 2/ multilayers is demonstrated and discussed. Ion desorption spectra from several alkali halides and alkaline earth halides are compared to bulk photoabsorption spectra. Relative ion yields from BaF/sub 2/ and a series of alkali halides are discussed in terms of desorption mechanisms.

  19. A Combined Desorption Ionization by Charge Exchange (DICE) and Desorption Electrospray Ionization (DESI) Source for Mass Spectrometry

    Science.gov (United States)

    Chan, Chang-Ching; Bolgar, Mark S.; Miller, Scott A.; Attygalle, Athula B.

    2011-01-01

    A source that couples the desorption ionization by charge exchange (DICE) and desorption electrospray ionization (DESI) techniques together was demonstrated to broaden the range of compounds that can be analyzed in a single mass spectrometric experiment under ambient conditions. A tee union was used to mix the spray reagents into a partially immiscible blend before this mixture was passed through a conventional electrospray (ES) probe capillary. Using this technique, compounds that are ionized more efficiently by the DICE method and those that are ionized better with the DESI procedure could be analyzed simultaneously. For example, hydroquinone, which is not detected when subjected to DESI-MS in the positive-ion generation mode, or the sodium adduct of guaifenesin, which is not detected when examined by DICE-MS, could both be detected in one experiment when the two techniques were combined. The combined technique was able to generate the molecular ion, proton and metal adduct from the same compound. When coupled to a tandem mass spectrometer, the combined source enabled the generation of product ion spectra from the molecular ion and the [M + H]+ or [M + metal]+ ions of the same compound without the need to physically change the source from DICE to DESI. The ability to record CID spectra of both the molecular ion and adduct ions in a single mass spectrometric experiment adds a new dimension to the array of mass spectrometric methods available for structural studies.

  20. Feasibility of desorption atmospheric pressure photoionization and desorption electrospray ionization mass spectrometry to monitor urinary steroid metabolites during pregnancy.

    Science.gov (United States)

    Vaikkinen, Anu; Rejšek, Jan; Vrkoslav, Vladimír; Kauppila, Tiina J; Cvačka, Josef; Kostiainen, Risto

    2015-06-23

    Steroids have important roles in the progress of pregnancy, and their study in maternal urine is a non-invasive method to monitor the steroid metabolome and its possible abnormalities. However, the current screening techniques of choice, namely immunoassays and gas and liquid chromatography-mass spectrometry, do not offer means for the rapid and non-targeted multi-analyte studies of large sample sets. In this study, we explore the feasibility of two ambient mass spectrometry methods in steroid fingerprinting. Urine samples from pregnant women were screened by desorption electrospray ionization (DESI) and desorption atmospheric pressure photoionization (DAPPI) Orbitrap high resolution mass spectrometry (HRMS). The urine samples were processed by solid phase extraction for the DESI measurements and by enzymatic hydrolysis and liquid-liquid-extraction for DAPPI. Consequently, steroid glucuronides and sulfates were detected by negative ion mode DESI-HRMS, and free steroids by positive ion mode DAPPI-HRMS. In DESI, signals of eleven steroid metabolite ions were found to increase as the pregnancy proceeded, and in DAPPI ten steroid ions showed at least an order of magnitude increase during pregnancy. In DESI, the increase was seen for ions corresponding to C18 and C21 steroid glucuronides, while DAPPI detected increased excretion of C19 and C21 steroids. Thus both techniques show promise for the steroid marker screening in pregnancy.

  1. Effect of cold rolling on the hydrogen absorption and desorption kinetics of Zircaloy-4

    Energy Technology Data Exchange (ETDEWEB)

    Dupim, I.S.; Moreira, J.M.L. [CESC, Universidade Federal do ABC, Av. dos Estados 5001, CEP: 09210-580 Santo André, SP (Brazil); Huot, J. [IRH, Université du Québec à Trois Rivières, 3351 boul. des Forges, CP 500, G9Y5H7 Trois Rivières, QC (Canada); Santos, S.F., E-mail: sydney.ferreira@ufabc.edu.br [CESC, Universidade Federal do ABC, Av. dos Estados 5001, CEP: 09210-580 Santo André, SP (Brazil)

    2015-04-01

    Metal matrix composites have been considered promising candidates as nuclear fuels for pressurized water reactors and also for nuclear waste management. Among others, Zircaloy is considered an excellent alternative for metallic matrix in such composites due to its excellent mechanical properties, high thermal conductivity and high corrosion resistance at operating temperatures. For manufacturing these fuels, a necessary step is the production of Zircaloy powder to be used as raw material. A feasible route to produce powders of refractory metals and alloys like Zircaloy is the hydriding and dehydriding process. For this type of processing route, hydrogen absorption and desorption should be performed at the lowest temperature and pressure possible in order to reduce the processing costs. In this paper, we investigated the hydrogen sorption kinetics of Zircaloy and the effect of cold rolling on the reaction rate. It was found that cold rolling greatly increases the hydrogenation kinetics and drastically reduces the dehydrogenation temperature. - Highlights: • The effects of temperature and pressure on the hydrogen reaction kinetics in Zircaloy-4 are analyzed. • The incubation time during absorption measurements increased for higher H2 pressures. • Changes in hydriding reaction kinetics at 1500 kPa of H{sub 2} and 1.25 wt.% of absorption. • Cold rolling increased the hydrogen absorption kinetics and decreased the hydride decomposition temperature.

  2. The contribution to Mercury’s exosphere by sputtering, micrometeorite impact and photon-stimulated desorption

    Science.gov (United States)

    Wurz, P.; Whitby, J.; Martin-Fernandez, J.; Rohner, U.; Lammer, H.; Kolb, C.

    2009-12-01

    We have extended our Monte-Carlo model of exospheres [Wurz and Lammer, Icarus 164, 2003, 1-13] by treating the ion-induced sputtering process, photon-stimulated desorption, and micro-meteorite impact vaporisation in a self-consistent way. Based on available literature data we established a global model for the surface mineralogy of Mercury and from that derived the average elemental composition of the surface. Our total calculated exospheric density at the hermean surface of about 4e7 m^-3 as a result of solar wind sputtering is much less than the experimental total exospheric density of about 1e12 m^-3. The total calculated exospheric density from micro-meteorite impact vaporisation is about 1.58e8 m^-3. We conclude that sputtering and micro-meteorite impact vaporisation contribute only a small fraction of Mercury’s exosphere, at least close to the surface. Because of the considerably larger scale height of atoms released via sputtering into the exosphere, sputtered atoms start to dominate the exosphere at altitudes exceeding around 1000 km, with the exception of some light and abundant species released thermally, e.g. H2 and He. Because of Mercury’s strong gravitational field not all particles released by sputtering and micro-meteorite impact escape. Over extended time scales this will lead to an alteration of the surface composition.

  3. A study on metal organic framework (MOF-177) synthesis, characterization and hydrogen adsorption -desorption cycles

    Energy Technology Data Exchange (ETDEWEB)

    Viditha, V.; Venkateswer Rao, M.; Srilatha, K.; Himabindu, V. [Centre for Environment, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad-500 085, A.P. (India); Yerramilli, Anjaneyulu [Director, TLGVRC, JSU Box 18739, JSU, Jackson, MS 32917-0939 (United States)

    2013-07-01

    Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs) are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  4. A study on metal organic framework (MOF-177 synthesis, characterization and hydrogen adsorption -desorption cycles

    Directory of Open Access Journals (Sweden)

    V.Viditha, M.Venkateswer Rao, K.Srilatha11, V.Himabindu, Anjaneyulu Yerramilli

    2013-01-01

    Full Text Available Hydrogen has long been considered to be an ideal alternative to fossil-fuel systems and much work has now been done on its storage. There are four main methods of hydrogen storage: as a liquid; as compressed hydrogen; in the form of metal hydrides; and by physisorption. Among all the materials metal organic frameworks (MOFs are considered to have desirable properties like high porosity, pore volume and high thermal stability. MOF-177 is considered to be an ideal storage material. In this paper we study about its synthesis and hydrogen storage capacities of MOF-177 at different pressures ranging from 25, 50, 75 and 100 bar respectively. The obtained samples are characterized by XRD, BET and SEM. The recorded results show that the obtained hydrogen capacity is 1.1, 2.20, 2.4 and 2.80 wt%. The desorption capacity is 0.9, 2.1, 2.37 and 2.7 wt% at certain temperatures like 373 K.

  5. Formation of Metal-Related Ions in Matrix-Assisted Laser Desorption Ionization

    Science.gov (United States)

    Lee, Chuping; Lu, I.-Chung; Hsu, Hsu Chen; Lin, Hou-Yu; Liang, Sheng-Ping; Lee, Yuan-Tseh; Ni, Chi-Kung

    2016-09-01

    In a study of the metal-related ion generation mechanism in matrix-assisted laser desorption ionization (MALDI), crystals of matrix used in MALDI were grown from matrix- and salt-containing solutions. The intensities of metal ion and metal adducts of the matrix ion obtained from unwashed crystals were higher than those from crystals washed with deionized water, indicating that metal ions and metal adducts of the matrix ions are mainly generated from the surface of crystals. The contributions of preformed metal ions and metal adducts of the matrix ions inside the matrix crystals were minor. Metal adducts of the matrix and analyte ion intensities generated from a mixture of dried matrix, salt, and analyte powders were similar to or higher than those generated from the powder of dried droplet crystals, indicating that the contributions of the preformed metal adducts of the matrix and analyte ions were insignificant. Correlation between metal-related ion intensity fluctuation and protonated ion intensity fluctuation was observed, indicating that the generation mechanism of the metal-related ions is similar to that of the protonated ions. Because the thermally induced proton transfer model effectively describes the generation of the protonated ions, we suggest that metal-related ions are mainly generated from the salt dissolution in the matrix melted by the laser.

  6. Electronically driven adsorbate excitation mechanism in femtosecond-pulse laser desorption

    DEFF Research Database (Denmark)

    Brandbyge, Mads; Hedegård, Per; Heinz, T. F.

    1995-01-01

    Femtosecond-pulse laser desorption is a process in which desorption is driven by a subpicosecond temperature pulse of order 5000 K in the substrate-adsorbate electron system, whose energy is transferred into the adsorbate center-of-mass degrees of freedom by a direct coupling mechanism. We presen...

  7. Desorption of two organophosphorous pesticides from soil with wastewater and surfactant solutions.

    Science.gov (United States)

    Hernández-Soriano, M C; Mingorance, M D; Peña, A

    2012-03-01

    A batch test was used to evaluate the extent of desorption of diazinon and dimethoate, preadsorbed on a calcareous agricultural soil, representative of the Mediterranean area. Urban wastewater from a secondary treatment and seven surfactant solutions, at concentrations ranging from 0.75 mg L(-1) to 10 gL(-1), were used. The surfactants assayed were cationic (hexadecyl trimethyl ammonium bromide (HD)), anionic (sodium dodecyl sulfate (SDS), Aerosol 22 (A22) and Biopower (BP)), and nonionic (Tween 80 (TW), Triton X 100 (TX) and Glucopon 600 (G600)). Desorption of dimethoate was either not affected or only slightly by the nonionic and anionic surfactants tested, while desorption of diazinon from the soil was only enhanced by A22, BP and TW. This desorption increase correlated significantly with the surfactant concentration of the solution used for desorption and with the concurrent increase in the supernatant of the dissolved organic carbon, in particular that originating from the surfactant. This parameter did not vary with the use of SDS, G600 and TX. The cationic surfactant HD was retained on the soil surface, as confirmed by an increase in soil organic carbon, resulting in a fall in desorption rate for both pesticides. Comparing treatment by wastewater with control water, there was no difference in desorption rate for either pesticide. Mixed TW/anionic surfactant solutions either did not modify or slightly increased desorption of both pesticides in comparison with individual surfactant solutions.

  8. [Effects of soil compositions on sorption and desorption behavior of tetrachloroethylene in soil].

    Science.gov (United States)

    Hu, Lin; Qiu, Zhao-Fu; He, Long; Dou, Ying; Lü, Shu-Guang; Sui, Qian; Lin, Kuang-Fei

    2013-12-01

    Sorption and desorption play an important role in the transport and the fate of tetrachloroethylene (PCE) in soil. In order to examine influences of different soil compositions on PCE sorption-desorption, equilibrium batch experiments were carried out using four sorbents (natural soil with 2.23% total organic carbon (TOC), H2O2-treated soil, 375 degrees C-treated soil and 600 degrees C-treated soil) with different initial PCE liquid concentrations (c0). The effects of main parameters (TOC, soft carbon, hard carbon, minerals, c0) on PCE sorption-desorption were investigated. At 16 degrees C, when c0 was increased from 5 to 80 mg x L(-1), the results showed that sorption and desorption isotherms of PCE on four sorbents can be best described by the Freundlich model (r2 > 0.96). The sorption contribution rate of SOM was higher than 60% in natural soil, and hard carbon was the main influencing factor,while the desorption contribution rate of SOM was close to that of minerals in natural soil, and soft carbon accounted for more than 80% in the total desorption contribution rate of SOM. In addition, the higher the c0, the higher the sorption contribution rate of PCE in hard carbon and desorption contribution rate of PCE in soft carbon and minerals were. Moreover, desorption of PCE from four sorbents exhibited hysteresis, and hard carbon played a remarkable role in the hysteresis of natural soil.

  9. Kinetic characteristics of coal gas desorption based on the pulsating injection

    Institute of Scientific and Technical Information of China (English)

    Ni Guanhua; Lin Baiquan; Zhai Cheng; Li Quangui; Peng Shen; Li Xianzhong

    2014-01-01

    In order to understand the kinetic characteristics of coal gas desorption based on the pulsating injection (PI), the research experimentally studied the kinetic process of methane desorption in terms of the PI and hydrostatic injection (HI). The results show that the kinetic curves of methane desorption based on PI and HI are consistent with each other, and the diffusion model can best describe the characteristics of meth-ane desorption. Initial velocity, diffusion capacity and ultimate desorption amount of methane desorption after PI are greater than those after HI, and the ultimate desorption amount increases by 16.7-39.7%. Methane decay rate over the time is less than that of the HI. The PI influences the diffusion model param-eters, and it makes the mass transfer Biot number B0i decrease and the mass transfer Fourier series F00 increase. As a result, PI makes the methane diffusion resistance in the coal smaller, methane diffusion rate greater, mass transfer velocity faster and the disturbance range of methane concentration wider than HI. Therefore, the effect of methane desorption based on PI is better than that of HI.

  10. Hypotonic elution, a new desorption principle in immunoadsorbent chromatography

    DEFF Research Database (Denmark)

    Danielsen, Erik Michael; Sjöström, H; Norén, O

    1982-01-01

    of finding an efficient means of elution which is not denaturing to neither the purified enzyme nor the immunoadsorbent column. Common properties of the microvillar enzymes with regard to amphiphilicity, glycosylation or subunit composition could hypothetically account for the similar elution properties......A largely unrecognized immunoadsorbent desorption technique, hypotonic elution, has been successfully used in the immunoadsorbent purification of the microvillar enzymes aminopeptidase N (EC 3.4.11.2), dipeptidyl peptidase IV (EC 3.4.14.5), sucrase-isomaltase (EC 3.2.1.48-10), lactase......-phlorizin hydrolase (EC 3.2.1.23-62) and maltase-glucoamylase (EC 3.2.1.20). This elution method proved capable of achieving an acceptable yield (30-70%) while at the same time preserving the purified enzymes in an enzymically active state. It hereby offers a solution to the problem in immunoadsorbent chromatography...

  11. Solvent desorption dynamic headspace sampling of fermented dairy product volatiles.

    Science.gov (United States)

    Rankin, S A

    2001-01-01

    A method was developed based on solvent desorption dynamic headspace analysis for the identification and relative quantification of volatiles significant to the study of fermented dairy product aroma. Descriptions of applications of this method are presented including the measurement of diacetyl and acetoin in fermented milk, the evaluation of volatile-hydrocolloid interactions in dairy-based matrices, and the identification of volatiles in cheeses for canonical discriminative analysis. Advantages of this method include rapid analysis, minimal equipment investment, and the ability to analyze samples with traditional GC split/splitless inlet systems. Limitations of this method are that the sample must be in the liquid state and the inherent analytical limitation to those compounds that do not coelute with the solvent or solvent impurity peaks.

  12. Desorption of radioactive cesium by seawater from the suspended particles in river water.

    Science.gov (United States)

    Onodera, Masaki; Kirishima, Akira; Nagao, Seiya; Takamiya, Kouichi; Ohtsuki, Tsutomu; Akiyama, Daisuke; Sato, Nobuaki

    2017-10-01

    In 2011, the accident at the Fukushima-Daiichi nuclear power plant dispersed radioactive cesium throughout the environment, contaminating the land, rivers, and sea. Suspended particles containing clay minerals are the transportation medium for radioactive cesium from rivers to the ocean because cesium is strongly adsorbed between the layers of clay minerals, forming inner sphere complexes. In this study, the adsorption and desorption behaviors of radioactive cesium from suspended clay particles in river water have been investigated. The radioactive cesium adsorption and desorption experiments were performed with two kinds of suspended particulate using a batch method with (137)Cs tracers. In the cesium adsorption treatment performed before the desorption experiments, simulated river water having a total cesium concentration ([(133+137)Cs(+)]total) of 1.3 nM (10(-9) mol/L) was used. The desorption experiments were mainly conducted at a solid-to-liquid ratio of 0.17 g/L. The desorption agents were natural seawater collected at 10 km north of the Fukushima-Daiichi nuclear power plant, artificial seawater, solutions of NaCl, KCl, NH4Cl, and (133)CsCl, and ultrapure water. The desorption behavior, which depends on the preloaded cesium concentration in the suspended particles, was also investigated. Based on the cesium desorption experiments using suspended particles, which contained about 1000 ng/g loaded cesium, the order of cesium desorption ratios for each desorption agent was determined as 1 M NaCl (80%) > 470 mM NaCl (65%) > 1 M KCl (30%) ≈ seawater (natural seawater and Daigo artificial seawater) > 1 M NH4Cl (20%) > 1 M (133)CsCl (15%) ≫ ultrapure water (2%). Moreover, an interesting result was obtained: The desorption ratio in the 470 mM NaCl solution was much higher than that in seawater, even though the Na(+) concentrations were identical. These results indicate that the cesium desorption mechanism is not a simple ion exchange reaction

  13. On plate graphite supported sample processing for simultaneous lipid and protein identification by matrix assisted laser desorption ionization mass spectrometry.

    Science.gov (United States)

    Calvano, Cosima Damiana; van der Werf, Inez Dorothé; Sabbatini, Luigia; Palmisano, Francesco

    2015-05-01

    The simultaneous identification of lipids and proteins by matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) after direct on-plate processing of micro-samples supported on colloidal graphite is demonstrated. Taking advantages of large surface area and thermal conductivity, graphite provided an ideal substrate for on-plate proteolysis and lipid extraction. Indeed proteins could be efficiently digested on-plate within 15 min, providing sequence coverages comparable to those obtained by conventional in-solution overnight digestion. Interestingly, detection of hydrophilic phosphorylated peptides could be easily achieved without any further enrichment step. Furthermore, lipids could be simultaneously extracted/identified without any additional treatment/processing step as demonstrated for model complex samples such as milk and egg. The present approach is simple, efficient, of large applicability and offers great promise for protein and lipid identification in very small samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Industrial surfaces behaviour related to the adsorption and desorption of hydrogen at cryogenic temperature [in LHC vacuum system

    CERN Document Server

    Moulard, G; Saitô, Y

    2001-01-01

    The determination of the hydrogen adsorption capacity on different industrial surfaces has been carried out by measuring isothermal adsorption. First results show that the adsorption capacity is mainly determined by surface porosity. Therefore, the samples may be classified into two categories: smooth and porous surfaces. Thermal desorption spectra reveal two adsorption energy levels for hydrogen physisorbed on porous materials, but only a single one on smooth samples. The value of the lowest energy level seems to be independent of the substrate nature. The physisorption process studied at low coverage, well below a monolayer, shows that these two levels are not well defined but an energy distribution exists for each of them. The influences of the isotherm temperature and an annealing at 7 K of an adsorbed monolayer on hydrogen adsorption capacity have been studied. (16 refs).

  15. Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

    Energy Technology Data Exchange (ETDEWEB)

    Matsuyama, M.; Kondo, M.; Noda, N. [Hydrogen Isotope Research Center, University of Toyama, Gofuku, Toyama (Japan); Tanaka, M.; Nishimura, K. [National Institute for Fusion Science, Toki-shi, Gifu (Japan)

    2015-03-15

    In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel is limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)

  16. Experimental study of water effects on gas desorption during high-pressure water injection

    Institute of Scientific and Technical Information of China (English)

    ZHANG Guo-hua; LIU Xian-xin; BI Ye-wu; PU Wen-long

    2011-01-01

    For the question of applying high-pressure water injection to increase gas extraction efficiency by increasing the permeability of water to drive gas action,an independently designed gas desorption experimental measuring device was used under the condition of external solution invasion.The law of water effect on gas desorption was obtained after water invasion through experiment for the first time.The results show that water's later invasion not only can make the quantity of gas desorption greatly reduced,but also can make gas desorption end early.Therefore,when evaluating the applications of high-pressure water injection to increase gas extraction efficiency,we should take water damaging effects on gas desorption into account.

  17. Desorption behavior of zinc atoms from zinc-sulfate solution irradiated with pulsed DC plasma

    Science.gov (United States)

    Takaba, Takafumi; Suzuki, Haruka; Toyoda, Hirotaka

    2016-07-01

    A DC pulsed plasma ignited between a metal needle and zinc sulfate (ZnSO4) solution electrode was used to investigate Zn metal desorption from an electrolyte solution. Using an ICCD camera and optical band-pass filter, 2D atomic absorption spectroscopy was carried out during irradiation of pulsed plasma to the surface of the solution. The time-resolved measurement of Zn atoms released to the gas phase revealed that the Zn desorption rate monotonically increased with increasing number of discharge repetitions. The surface temperature of the electrolyte solution was observed with a thermographic camera, and correlations between the H2O and Zn desorption rate were inspected. The correlation between the H2O and Zn desorption rate suggested that Zn desorption is assisted not only by the electric field of the discharge but also by H2O evaporating from the solution.

  18. Atoms and Nanoparticles of Transition Metals as Catalysts for Hydrogen Desorption from Magnesium Hydride

    Directory of Open Access Journals (Sweden)

    N. Bazzanella

    2011-01-01

    Full Text Available The hydrogen desorption kinetics of composite materials made of magnesium hydride with transition metal additives (TM: Nb, Fe, and Zr was studied by several experimental techniques showing that (i a few TM at.% concentrations catalyse the H2 desorption process, (ii the H2 desorption kinetics results stabilized after a few H2 sorption cycles when TM atoms aggregate by forming nanoclusters; (iii the catalytic process occurs also at TM concentration as low as 0.06 at.% when TM atoms clustering is negligible, and (iv mixed Fe and Zr additives produce faster H2 desorption kinetics than single additive. The improved H2 desorption kinetics of the composite materials can be explained by assuming that the interfaces between the MgH2 matrix and the TM nanoclusters act as heterogeneous sites for the nucleation of the Mg phase in the MgH2 matrix and promote the formation of fast diffusion channels for H migrating atoms.

  19. Sorption, desorption, and surface oxidative fate of nicotine.

    Science.gov (United States)

    Petrick, Lauren; Destaillats, Hugo; Zouev, Irena; Sabach, Sara; Dubowski, Yael

    2010-09-21

    Nicotine dynamics in an indoor environment can be greatly affected by building parameters (e.g. relative humidity (RH), air exchange rate (AER), and presence of ozone), as well as surface parameters (e.g. surface area (SA) and polarity). To better understand the indoor fate of nicotine, these parameter effects on its sorption, desorption, and oxidation rates were investigated on model indoor surfaces that included fabrics, wallboard paper, and wood materials. Nicotine sorption under dry conditions was enhanced by higher SA and higher polarity of the substrate. Interestingly, nicotine sorption to cotton and nylon was facilitated by increased RH, while sorption to polyester was hindered by it. Desorption was affected by RH, AER, and surface type. Heterogeneous nicotine-ozone reaction was investigated by Fourier transform infrared spectrometry with attenuated total reflection (FTIR-ATR), and revealed a pseudo first-order surface reaction rate of 0.035 +/- 0.015 min(-1) (at [O(3)] = 6 +/- 0.3 x 10(15) molecules cm(-3)) that was partially inhibited at high RH. Extrapolation to a lower ozone level ([O(3)] = 42 ppb) showed oxidation on the order of 10(-5) min(-1) corresponding to a half-life of 1 week. In addition, similar surface products were identified in dry and high RH using gas chromatography-mass spectrometry (GC-MS). However, FTIR analysis revealed different product spectra for these conditions, suggesting additional unidentified products and association with surface water. Knowing the indoor fate of condensed and gas phase nicotine and its oxidation products will provide a better understanding of nicotine's impact on personal exposures as well as overall indoor air quality.

  20. Enhancing magnetic properties of anisotropic NdDyFeCoNbCuB powder by applying magnetic field at high temperature during hydrogen desorption

    Institute of Scientific and Technical Information of China (English)

    LUO Jianjun; P.De Rango; D.Fruchart; MEI Jinna; HU Rui; LI Jinshan; ZHOU Lian

    2010-01-01

    Anisotropic powder was prepared with precursor (NdDy)-(FeCoNbCu)-B sintered magnets by hydrogen decrepitation,desorption,and subsequent annealing treatment.The hydrogen desorption was performed in magnetic fields of 0,1,3,and 5 T.The orientation of tetragonal phase grains of the powder was evaluated from the hysteresis loops measured by extraction magnetometer.Residual hydrogen content of the powder was evaluated by thermal-magnetic analysis.The powder with Hcj,Br,and (BH)max of 1138 kA.m-1,1.029 T,and 172.5 kJ.m-3,respectively,was achieved under the condition of the magnetic field of 3 T.Magnetic properties of the powder,especially,the remanence of the powder,are enhanced upon magnetic fields,which is due to better orientation of powder particles and less residual hydrogen in the powder resulted from the magnetic field during the hydrogen desorption process.

  1. Photoabsorption and desorption studies on thiophene-based polymers following sulphur K-shell excitation

    Energy Technology Data Exchange (ETDEWEB)

    Santa Rita, J.R.; Arantes, C.; Araujo, G. [Departamento de Fisico-Quimica, Universidade Federal do Rio de Janeiro, 21941-909 Rio de Janeiro, RJ (Brazil); Roman, L.S. [Departamento de Fisica, Universidade Federal do Parana, 81531-990 Curitiba, PR (Brazil); Micaroni, L. [Departamento de Quimica, Universidade Federal do Parana, 81531-990 Curitiba, PR (Brazil); Rocco, M.L.M., E-mail: luiza@iq.ufrj.br [Departamento de Fisico-Quimica, Universidade Federal do Rio de Janeiro, 21941-909 Rio de Janeiro, RJ (Brazil)

    2011-04-15

    Research highlights: {yields} Photon stimulated ion desorption (PSID) measurements at the S K-shell excitation energies were performed on three thiophene-based polymer films, following their NEXAFS spectra. {yields} For poly(thiophene) (PT) and poly(3-methylthiophene) (P3MT) it was found that the S 1s {yields} {pi}*, {sigma}* (S-C) excitation produces S{sup +} desorption efficiently, showing the importance of the resonant Auger process for breaking the C-S bond. {yields} In the case of poly(3-hexylthiophene) (P3HT) S{sup +} desorption seems to be suppressed due to the orientation of 3-hexyl side-chains on the surface. {yields} Desorption ion yield curves for molecular fragments reproduce the photoabsorption spectrum, indicating that the indirect process is here predominant. - Abstract: Photon stimulated ion desorption (PSID) and NEXAFS studies have been performed on thiophene-based polymers at the Brazilian Synchrotron Light Source following sulphur K-shell photoexcitation. For poly(thiophene) (PT) and poly(3-methylthiophene) (P3MT) it was found that the S 1s {yields} {pi}*, {sigma}{sup *} (S-C) excitation produces S{sup +} desorption efficiently. On the other hand, S{sup 2+} desorption is enhanced at higher energy excitations. These results are interpreted in terms of the Auger-stimulated ion desorption mechanism. For poly(3-hexylthiophene) (P3HT) S{sup +} desorption seems to be suppressed, which may be due to the hexyl side-chains. Desorption ion yield curves for molecular fragments reproduce the photoabsorption spectrum, being dominated by the indirect process.

  2. Phosphorus sorption, desorption and resorption by soils of the Brazilian Cerrado supporting eucalypt

    Energy Technology Data Exchange (ETDEWEB)

    Barros, Nairam F. Filho [Universidade Federal de Santa Maria, Dept. de Ciencia Florestal, Porto Alegre, RS (Brazil); Comerford, N.B. [Florida Univ., Soil and Water Science Dept., Gainesville, FL (United States); Barros, Nairam F. [Universidade Federal de Vicosa, Dept. do Solos, Vicosa, MG (Brazil)

    2005-02-01

    Oxisols of the Brazilian Cerrado are highly weathered phosphorus deficient soils, on which eucalypt is increasingly being grown as a source of carbon and energy for steel manufacturing. Phosphorus (P) fertilization is a necessary practice to assure adequate eucalypt production; therefore, an understanding of cycling by inorganic soil P should lead to efficient P management and more accurate modeling of P bioavailability. Since sorption and desorption reactions control inorganic P bioavailability, the purpose of this study was to contrast P sorption, desorption and subsequent resorption for a range of Cerrado soils. Its specific objectives were to determine (i) if desorption and resorption show the same hysteresis shown by sorption and desorption, (ii) if K{sub d} values of resorption and desorption for Cerrado soils are dependent on the soil's clay content and (iii) if resorption and desorption K{sub d} values are a function of the amount of labile P on the soil surface. Three levels of P were sorbed onto four Cerrado soils with clay contents between 13% and 81%. Phosphorus desorption was measured using anion-exchange membranes. Sorption was a function of soil clay content, and a pedotransfer function for the soil partition coefficient was calculated with an r{sup 2} = 0.99. Desorption and resorption were dependent on both the clay content of the soil (r{sup 2} = 0.59-0.99) and the amount of sorbed labile P. Pedotransfer functions for each of these processes depend on accurate measurement of the inorganic P that responds to disequilibria exchange. Desorption and resorption were not hysteretic; yet desorption was hysteretic with the original sorption isotherm. This suggests the question: how useful are commonly produced sorption isotherms? (Author)

  3. Hydrogen Desorption Properties of Nanocrystalline MgH2-10 wt.% ZrB2 Composite Prepared by Mechanical Alloying

    OpenAIRE

    Mona Maddah; Mohammad Rajabi; Seyed Mahmood Rabiee

    2014-01-01

    Storage of hydrogen is one of the key challenges in developing hydrogen economy. Magnesium hydride (MgH2) is an attractive candidate for solid-state hydrogen storage for on-board applications. In this study, 10 wt.% ZrB2 was co-milled with magnesium hydride at different milling times to produce nanocrystalline composite powder. The effect of milling time and additive on the hydrogen desorption properties of obtained powder was evaluated by thermal analyzer method and compared with pure MgH2....

  4. Thermal comfort

    CSIR Research Space (South Africa)

    Osburn, L

    2010-01-01

    Full Text Available Thermal comfort is influenced by environmental parameters as well as other influences including asymmetric heating and cooling conditions. Additionally, some aspects of thermal comfort may be exploited so as to enable a building to operate within a...

  5. Lowering the desorption temperature of Mg(BH4)2 through doping

    Science.gov (United States)

    Harrison, D.; Thonhauser, T.

    2014-03-01

    Magnesium borohydride Mg(BH4)2 is a very promising hydrogen storage material due to its high gravimetric (14.9 mass%) and volumetric density. However, it is limited for practical storage applications by its high hydrogen desorption temperature of 270°C. Arguments have been made for both high thermodynamic stability and slow kinetics to be responsible for this high desorption temperature. In our study we show that doping of Mg(BH4)2 can address the thermodynamic stability issue and predictably lower its desorption enthalpy. We use ab initio calculations at the DFT level (utilizing vdW-DF) and calculate the change in desorption enthalpy from ground state energy and phonon contributions for several possible hydrogen release reactions. Note that van der Waals interactions are crucial to correctly describe the ground state of this complex hydride. We find that, depending on the reaction, the undoped phase has a desorption enthalpy of 50-75 kJ/mol H2 and doping can lower this number by approximately 5 kJ/mol per 10% doping at 300 K, making the desired range of 40 kJ/mol easily accessible. We argue that this lowering of desorption enthalpy will correspond to a lowering of the desorption temperature. Supported by NSF DMR-1145968.

  6. Plutonium desorption from mineral surfaces at environmental concentrations of hydrogen peroxide.

    Science.gov (United States)

    Begg, James D; Zavarin, Mavrik; Kersting, Annie B

    2014-06-01

    Knowledge of Pu adsorption and desorption behavior on mineral surfaces is crucial for understanding its environmental mobility. Here we demonstrate that environmental concentrations of H2O2 can affect the stability of Pu adsorbed to goethite, montmorillonite, and quartz across a wide range of pH values. In batch experiments where Pu(IV) was adsorbed to goethite for 21 days at pH 4, 6, and 8, the addition of 5-500 μM H2O2 resulted in significant Pu desorption. At pH 6 and 8 this desorption was transient with readsorption of the Pu to goethite within 30 days. At pH 4, no Pu readsorption was observed. Experiments with both quartz and montmorillonite at 5 μM H2O2 desorbed far less Pu than in the goethite experiments highlighting the contribution of Fe redox couples in controlling Pu desorption at low H2O2 concentrations. Plutonium(IV) adsorbed to quartz and subsequently spiked with 500 μM H2O2 resulted in significant desorption of Pu, demonstrating the complexity of the desorption process. Our results provide the first evidence of H2O2-driven desorption of Pu(IV) from mineral surfaces. We suggest that this reaction pathway coupled with environmental levels of hydrogen peroxide may contribute to Pu mobility in the environment.

  7. Effects of methamidophos and glyphosate on copper sorption-desorption behavior in soils

    Institute of Scientific and Technical Information of China (English)

    YU Ying; ZHOU Qixing; HE Zhenli

    2005-01-01

    A batch-equilibration technique was employed to study the impact of two organophosphorus pesticides methamidophos (MDP) and glyphosate (GPS) on copper (Cu2+) sorptiondesorption for phaeozem and burozem collected from Northeastern China. The addition of the two pesticides decreased Cu2+ sorption, increased Cu2+ desorption and prolonged the equilibrium time of Cu2+ sorption-desorption. But GPS appeared to exert a stronger influence on Cu2+ sorption-desorption due to its stronger complexion with Cu2+. When MDP was added, Cu2+ sorption-desorption was linearly correlated with MDP treatment concentrations. But in the presence of GPS, Cu2+ sorption first underwent a rapid decrease period, and then slowly tended towards a steady period. The reverse pattern could be found for Cu2+ desorption in the presence of GPS.Without pesticides and with the existence of MDP, Cu2+ sorption-desorption kinetics was well conformed to two-constant equation and Elovich equation. But that was not the case for Cu2+ desorption kinetics in the presence of GPS although its sorption could be also described by these two equations.

  8. Dynamical Model in Low-Frequency-Pulsed Electron-Stimulated Desorption

    Institute of Scientific and Technical Information of China (English)

    张彤; 吴小山; 胡安; 毛福明; 杨学谦; 崔一平

    2003-01-01

    A dynamical model of low-frequency=pulsed electron=stimulated desorption is developed. The characteristic of desorbed gas flow is taken as an exponential function, and can be degenerated to a triangular and square wave.The transient pressure is given according to the gas flow of desorbing gas and vacuum system parameters,including the pumping speed and the system volume. Although the mathematical model is deduced from the electron-stimulated desorption, it can be applied to other similar processes of intermittent desorption.

  9. A kinetic Monte Carlo study of desorption of H2 from graphite (0001)

    CERN Document Server

    Gavardi, E; Hornekaer, L; 10.1016/j.cplett.2009.07.003

    2009-01-01

    The formation of H2 in the interstellar medium proceeds on the surfaces of silicate or carbonaceous particles. To get a deeper insight of its formation on the latter substrate, this letter focuses on H2 desorption from graphite (0001) in Temperature-Programmed-Desorption Monte-Carlo simulations. The results are compared to experimental results which show two main peaks and an intermediate shoulder for high initial coverage. The simulation program includes barriers obtained by ab-initio methods and is further optimised to match two independent experimental observations. The simulations reproduce the two experimental observed desorption peaks. Additionally, a possible origin of the intermediate peak is given.

  10. Tunable Adsorption and Desorption of Hydrogen Atoms on Single-Walled Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    赵明文; 夏日源; 马玉臣; 英敏菊; 刘向东; 梅良模

    2002-01-01

    Chemical adsorption and desorption of hydrogen atoms on single-walled carbon nanotubes (SWNTs) are investi-gated by using molecular dynamics simulations. It is found that the adsorption and desorption energy of hydrogenatoms depend on the hydrogen coverage and the diameter of the SWNTs. Hydrogen-adsorption geometry at thecoverage of 1.0 is more energetically stable. The adsorption energy decreases with the increasing diameter ofthe armchair tubes. The adsorption and desorption energy of hydrogen atoms can be modified reversibly byexternally radial deformation. The averaged C-H bond energy on the high curvature sites of the deformed tubeincreases with increasing radial deformation, while that on the low curvature sites decreases.

  11. Desorption of H atoms from graphite (0001) using XUV free electron laser pulses

    DEFF Research Database (Denmark)

    Siemer, B.; Olsen, Thomas; Hoger, T.;

    2010-01-01

    , and identifies the highest vibrational state in the adsorbate potential as a major source for the slow atoms. It is evident that multiple electron scattering processes are required for this desorption. A direct electronic excitation of a repulsive hydrogen-carbon bond seems not to be important.......The desorption of neutral H atoms from graphite with femtosecond XUV pulses is reported. The velocity distribution of the atoms peaks at extremely low kinetic energies. A DFT-based electron scattering calculation traces this distribution to desorption out of specific adsorption sites on graphite...

  12. A statistical study on in vivo sorption and desorption of water in ichthyosis vulgaris.

    Science.gov (United States)

    Mukherjee, S; Gupta, A B

    1994-02-01

    Experiments on the variation of electrical conductance on sorption and desorption of water were performed on the skin of 34 subjects: 17 ichthyosis vulgaris patients and 17 normal subjects, matched for age and gender, under different ambient conditions. An exponential model of the form ft = theta oe theta t, where ft denotes fractional conductance at time t, describes the process of desorption with high accuracy. The parameter theta, identifiable as the rate of desorption, is significantly different between the ichthyotic and normal populations. The study discusses the impaired barrier function of the ichthyotic skin.

  13. First-principles calculations of helium and neon desorption from cavities in silicon.

    Science.gov (United States)

    Eddin, A Charaf; Pizzagalli, L

    2012-05-02

    Combining density functional theory, the nudged elastic band technique, and the ultradense fluid model, we investigated the desorption process of He and Ne in silicon. Our results show that the internal surfaces of gas-filled bubbles are not a limiting factor during desorption experiments, since the surface reconstruction opens diffusion paths easier than in the bulk. We show that the vibrational contribution to the energy of helium in the bulk has to be considered in order to determine realistic pressures in the bubbles, when comparing experiments and simulations. At the maximum of desorption, an average pressure of 1-2 GPa is computed.

  14. Equilibrium moisture content (EMC) in Norway spruce during the first and second desorptions

    DEFF Research Database (Denmark)

    Hoffmeyer, Preben; Engelund, Emil Tang; Thygesen, Lisbeth G.

    2011-01-01

    how drying and saturation procedures influence the differences between the 1st and the 2nd desorption curves for Norway spruce (Picea abies (L.) Karst.) sapwood. The study establishes 1st and 2nd desorption isotherms for a variety of initial conditions and it covers the RH range from 60.1% to 99.......9%. The state of the water is not affected by oven-drying and rewetting as demonstrated by time domain low field NMR relaxometry. The results challenge the conclusions of earlier studies and indicate that in these studies the 2nd desorption was initiated at much too low EMC and therefore fails to describe...

  15. Simultaneous effect of dissolved organic carbon, surfactant, and organic acid on the desorption of pesticides investigated by response surface methodology

    DEFF Research Database (Denmark)

    Trinh, Ha Thu; Duong, Hanh Thi; Ta, Thao Thi

    2017-01-01

    Desorption of pesticides (fenobucarb, endosulfan, and dichlorodiphenyltrichloroethane (DDT)) from soil to aqueous solution with the simultaneous presence of dissolved organic carbon (DOC), sodium dodecyl sulfate (SDS), and sodium oxalate (Oxa) was investigated in batch test by applying a full fac...... characteristics of flooding and irrigation water in rice fields, and surfactants from pollution increase the problem with desorption of legacy pesticides in the rice fields....... caused the minimum desorption. This point at conditions of concern for flooding water is high content of organic compounds causing potentially high contamination by desorption, and the remarkably lower desorption at organic matter-free conditions. The suspended organic matter is one of the common...

  16. Thermal coupling potential of Solid Oxide Fuel Cells with metal hydride tanks: Thermodynamic and design considerations towards integrated systems

    Science.gov (United States)

    Yiotis, Andreas G.; Kainourgiakis, Michael E.; Kosmidis, Lefteris I.; Charalambopoulou, Georgia C.; Stubos, Athanassios K.

    2014-12-01

    We study the thermal coupling potential between a high temperature metal hydride (MH) tank and a Solid Oxide Fuel Cell (SOFC) aiming towards the design of an efficient integrated system, where the thermal power produced during normal SOFC operation is redirected towards the MH tank in order to maintain H2 desorption without the use of external heating sources. Based on principles of thermodynamics, we calculate the energy balance in the SOFC/MH system and derive analytical expressions for both the thermal power produced during SOFC operation and the corresponding thermal power required for H2 desorption, as a function of the operating temperature, efficiency and fuel utilization ratio in the SOFC, and the MH enthalpy of desorption in the tank. Based on these calculations, we propose an integrated SOFC/MH design where heat is transferred primarily by radiation to the tank in order to maintain steady-state desorption conditions. We develop a mathematical model for this particular design that accounts for heat/mass transfer and desorption kinetics in the tank, and solve for the dynamics of the system assuming MgH2 as a storage material. Our results focus primarily on tank operating conditions, such as pressure, temperature and H2 saturation profiles vs operation time.

  17. Kinetics of Surfactant Desorption at an Air–Solution Interface

    KAUST Repository

    Morgan, C. E.

    2012-12-18

    The kinetics of re-equilibration of the anionic surfactant sodium dodecylbenzene sulfonate at the air-solution interface have been studied using neutron reflectivity. The experimental arrangement incorporates a novel flow cell in which the subphase can be exchanged (diluted) using a laminar flow while the surface region remains unaltered. The rate of the re-equilibration is relatively slow and occurs over many tens of minutes, which is comparable with the dilution time scale of approximately 10-30 min. A detailed mathematical model, in which the rate of the desorption is determined by transport through a near-surface diffusion layer into a diluted bulk solution below, is developed and provides a good description of the time-dependent adsorption data. A key parameter of the model is the ratio of the depth of the diffusion layer, H c, to the depth of the fluid, Hf, and we find that this is related to the reduced Péclet number, Pe*, for the system, via Hc/Hf = C/Pe*1/2. Although from a highly idealized experimental arrangement, the results provide an important insight into the "rinse mechanism", which is applicable to a wide variety of domestic and industrial circumstances. © 2012 American Chemical Society.

  18. Quantitative analysis of biopolymers by matrix-assisted laser desorption

    Energy Technology Data Exchange (ETDEWEB)

    Tang, K.; Allman, S.L.; Jones, R.B.; Chen, C.H. (Oak Ridge National Lab., TN (United States))

    1993-08-01

    During the past few years, major efforts have been made to use mass spectrometry to measure biopolymers because of the great potential benefit to biological and medical research. Although the theoretical details of laser desorption and ionization mechanisms of MALDI are not yet fully understood, several models have been presented to explain the production of large biopolymer ions. In brief, it is very difficult to obtain reliable measurements of the absolute quantity of analytes by MALDI. If MALDI is going to become a routine analytical tool, it is obvious that quantitative measurement capability must be pursued. Oligonucleotides and protein samples used in this work were purchased from commercial sources. Nicotinic acid was used as matrix for both types of biopolymers. From this experiment, it is seen that it is difficult to obtain absolute quantitative measurements of biopolymers using MALDI. However, internal calibration with molecules having similar chemical properties can be used to resolve these difficulties. Chemical reactions between biopolymers must be avoided to prevent the destruction of the analyte materials. 10 refs., 8 figs.

  19. Pulsed light desorption of molecular nitrogen from a glass surface

    Science.gov (United States)

    Atutov, S. N.; Danilina, N. A.; Mikerin, S. L.; Plekhanov, A. I.

    2014-03-01

    Experimental results on the pulsed light desorption (PLD) of molecular Nitrogen from the surface of C-52 and Pyrex glasses are presented. The aim of the study was to determine the experimental conditions to obtain the maximum manifestation of the PLD effect of molecular gases. These studies were conducted in vacuum glass cells of different sizes and shapes filled by Nitrogen, whose inner surface was illuminated by the light of a powerful flash lamp. The variation in the density of the desorbed gas in the cell caused by PLD was studied using both a mass spectrometer and a vacuum gauge attached to the illuminated cells. The experimental results are in qualitative agreement with the theoretical model developed. We demonstrates that PLD can drastically increase a peak density of desorbed Nitrogen in a cell and the maximal Nitrogen density can be achieved in a small diameter long cell of cylindrical form. We believe that the results of this experiment can be applied to the loading of some gases inside a hollow-core, photonic band-gap fiber to generate a large optical depth for an experiment in low-light-level nonlinear optics.

  20. Prompt Gas Desorption Due to Ion Impact on Accelerator Structures

    Science.gov (United States)

    Vijay, Sagar; Seidl, Peter A.; Faltens, Andy; Lidia, Steven M.

    2011-10-01

    The repetition rate and peak current of high intensity ion accelerators for inertial fusion or other applications may be limited under certain conditions by the desorption of gas molecules and atoms due to stray ions striking the accelerator structure. We have measured the prompt yield of atoms in close proximity to the point of impact of the ions on a surface. Using the 300-keV, K+ ion beam of the Neutralized Drift Compression Experiment (NDCX-I), ions strike a metal target in a 5-10 microsecond bunch. The collector of a Bayert-Alpert style ionization gauge is used to detect the local pressure burst several centimeters away. Pressure transients are observed on a micro-second time scale due to the initial burst of desorbed gas, and on a much longer (~1 second) timescale, corresponding to the equilibration of the pressure after many ``bounces'' of atoms in the vacuum chamber. We report on these time dependent pressure measurements, modeling of the pressure transient, and implications for high-intensity ion accelerators. Work performed under auspices of U.S. DOE by LBNL under Contract DE-AC02-05CH1123.

  1. A combined whelk watch suggests repeated TBT desorption pulses.

    Science.gov (United States)

    Ruiz, J M; Albaina, N; Carro, B; Barreiro, R

    2015-01-01

    Environmental quality in coastal Europe has improved since the complete 2003 ban on the use of tributyltin (TBT) in antifouling paints. However, there is evidence that TBT is entering the water column, presumably from illegal practices. We determined the concentration of butyltins (BTs: TBT and derivatives) in populations of two gastropods, the rock snail Nucella lapillus (n=17) and the mud snail Nassarius reticulatus (n=18) at regular intervals from pre-ban times until 2009 and 2011, respectively, in NW Spain. Although a substantial decline in TBT occurred shortly after the ban, no significant changes were observed in either species over the last 3-year period of study. In addition, the proportion of TBT relative to the sum of BTs (a marker of recent pollution) in the most recent rock snail samples unexpectedly increased; this proportion therefore showed a generally decreasing but oscillatory trend over time. The results are consistent with the theoretical expectation of BT desorption from sediments; however, this natural phenomenon is now interpreted as a recurrent episode rather than a unique, transient event. Evidence of this subtle input improves our understanding of TBT persistence in the environment in Europe and worldwide.

  2. News on sputter theory: Molecular targets, nanoparticle desorption, rough surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Urbassek, Herbert M., E-mail: urbassek@rhrk.uni-kl.d [Fachbereich Physik und Forschungszentrum OPTIMAS, Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse, D-67663 Kaiserslautern (Germany); Anders, Christian [Fachbereich Physik und Forschungszentrum OPTIMAS, Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse, D-67663 Kaiserslautern (Germany); Rosandi, Yudi [Fachbereich Physik und Forschungszentrum OPTIMAS, Universitaet Kaiserslautern, Erwin-Schroedinger-Strasse, D-67663 Kaiserslautern (Germany); Department of Physics, Universitas Padjadjaran, Jatinangor, Sumedang 45363 (Indonesia)

    2011-05-01

    Sputtering theory has existed as a mature and well-understood field of physics since the theory of collision-cascade sputtering has been developed in the late 1960s. In this presentation we outline several directions, in which the basic understanding of sputter phenomena has been challenged and new insight has been obtained recently. Sputtering of molecular solids: after ion impact on a molecular solid, not all of the impact energy is available for inducing sputtering. Part of the energy is converted into internal (rotational and vibrational) excitation of the target molecules, and part is used for molecule dissociation. Furthermore, exothermic or endothermic chemical reactions may further change the energy balance in the irradiated target. Nanoparticle desorption: usually, the flux of sputtered particles is dominated by monatomics; in the case of a pronounced spike contribution to sputtering, the contribution of clusters in the sputtered flux may become considerable. Here, we discuss the situation that nanoparticles were present on the surface, and outline mechanisms of how these may be desorbed (more or less intact) by ion or cluster impact. Rough surfaces: real surfaces are rough and contain surface defects (adatoms, surface steps, etc.). For grazing ion incidence, these influence the energy input into the surface dramatically. For such incidence angles sputtering vanishes for a flat terrace; however, ion impact close to a defect may lead to sputter yields comparable to those at normal incidence. In such cases sputtering also exhibits a pronounced azimuth and temperature dependence.

  3. Pesticide sorption and desorption from soils having different land use

    Directory of Open Access Journals (Sweden)

    Ismael Madrigal Monárrez

    2010-05-01

    Full Text Available This study was carried out within the framework of a multidisciplinary project for evaluating buffer zones for combating pesticide contamination of surface water. Such areas are effective in removing pesticides transported by run-off; however, little information is available about the fate of the pesticides so intercepted. Two herbicides having contrasting properties (isoproturon, moderately hydrophobic (log Kow = 2.5, diflufenican, strongly hydrophobic (log K ow = 4.9 and isopropylaniline (an isoproturon metabolite were used for characterising sorption and desorption from soil having three different land uses: grass buffer strip, woodland and cultivated plot. The experiments were carried out in controlled laboratory conditions using isoproturon labelled with 14C in the benzene ring. The results demonstrated that diflufenican and isopropilaniline retention was more significant than isoproturon in three soils. The three molecules’ Kd values revealed that isoproturon and diflufenicanil retention was more important in woodland soil where carbon content was more significant (ZB 0-2: Kd IPU = 15.1 Ls kg-1; Kd DFF = 169.2 Ls kg-1. Isopropilanilina Kd was higher in grass buffer strip soil (BE 0-2: Kd IPA = 53.1 L kg-1. These differences were related to different organic matter content and nature according to the type of land use.

  4. Adsorption and desorption characteristics of diphenylarsenicals in two contrasting soils

    Institute of Scientific and Technical Information of China (English)

    Anan Wang; Shixin Li; Ying Teng; Wuxin Liu; Longhua Wu; Haibo Zhang; Yujuan Huang

    2013-01-01

    Diphenylarsinic acid (DPAA) is formed during the leakage of aromatic arsenic chemical weapons in soils,is persistent in nature,and results in arsenic contamination in the field.The adsorption and desorption characteristics of DPAA were investigated in two typical Chinese soils,an Acrisol (a variable-charge soil) and a Phaeozem (a constant-charge soil).Their thermodynamics and some of the factors influencing them (i.e.,initial pH value,ionic strength and phosphate) were also evaluated using the batch method in order to understand the environmental fate of DPAA in soils.The results indicate that Acrisol had a stronger adsorption capacity for DPAA than Phaeozem.Soil DPAA adsorption was a spontaneous and endothermic process and the amount of DPAA adsorbed was affected significantly by variation in soil pH and phosphate.In contrast,soil organic matter and ionic strength had no significant effect on adsorption.This suggests that DPAA adsorption may be due to specific adsorption on soil mineral surfaces.Therefore,monitoring the fate of DPAA in soils is recommended in areas contaminated by leakage from chemical weapons.

  5. Electrical Characteristics and Desorption Kinetics of Soil Boron

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The status and activities of boron in soils were studied by the approach of electro-ultrafiltration (EUF). The samples of soils, including brown-red soil and calcareous alluvial soil, were collected from Hubei Province of China. The soil samples were incubated in saturated water and then their nutrients were ultrafiltrated with EUF equipment. Filtration and extraction were conducted in accordance with routine process, but fractions in anode and cathode were all collected. Analyses of B, K+, Mg2+, Ca2+, C1- and pH in fractions supposed that boron existed not only in a simple form of borate but also in ion-pair with cations partly in acidic soil,and borate was the primary form existing in the calcareous soil. In studying desorption kinetics with EUF,the boron content of Fractions 2~6 was accumulated, and the accumulative quantities were fit to time factors in three kinetic equations: the zero-order, first-order, and arabolic diffusion equations. Fit degree of the parabolic diffusion equation was the best, followed by the zero-order quation, and the first-order equation was the worst.

  6. Temperature dependence of CO desorption kinetics at a novel Pt-on-Au/C PEM fuel cell anode

    DEFF Research Database (Denmark)

    Pitois, A.; Pilenga, A.; Pfrang, A.;

    2010-01-01

    techniques. The temperature dependence of the CO desorption process on this system has been investigated using isotopic exchange experiments. The CO desorption kinetics have been studied as a function of temperature and flow rate. Desorption rate constants have been measured for a temperature range between...... 25 and 150 degrees C. These desorption rate constants have been compared with the benchmarking desorption rate data obtained for the commercial Pt/C catalyst under similar experimental conditions. A comparable desorption rate constant for the Pt-on-Au/C and Pt/C systems has been obtained at 25...... degrees C. The dependence in temperature of the desorption rate constants for the novel Pt-on-Au/C system is however much lower than that observed for the Pt/C system. This suggests that the nature of the substrate has a significant influence on the catalyst surface properties. It shows that, in surface...

  7. Laser-induced acoustic desorption coupled with a linear quadrupole ion trap mass spectrometer.

    Science.gov (United States)

    Habicht, Steven C; Amundson, Lucas M; Duan, Penggao; Vinueza, Nelson R; Kenttämaa, Hilkka I

    2010-01-15

    In recent years, laser-induced acoustic desorption (LIAD) coupled with a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer has been demonstrated to provide a valuable technique for the analysis of a wide variety of nonvolatile, thermally labile compounds, including analytes that could not previously be analyzed by mass spectrometry. Although FT-ICR instruments are very powerful, they are also large and expensive and, hence, mainly used as research instruments. In contrast, linear quadrupole ion trap (LQIT) mass spectrometers are common due to several qualities that make these instruments attractive for both academic and industrial settings, such as high sensitivity, large dynamic range, and experimental versatility. Further, the relatively small size of the instruments, comparatively low cost, and the lack of a magnetic field provide some distinct advantages over FT-ICR instruments. Hence, we have coupled the LIAD technique with a commercial LQIT, the Thermo Fischer Scientific LTQ mass spectrometer. The LQIT was modified for a LIAD probe by outfitting the removable back plate of the instrument with a 6 in. ConFlat flange (CFF) port, gate valve, and sample lock. Reagent ions were created using the LQIT's atmospheric pressure ionization source and trapped in the mass analyzer for up to 10 s to allow chemical ionization reactions with the neutral molecules desorbed via LIAD. These initial experiments focused on demonstrating the feasibility of performing LIAD in the LQIT. Hence, the results are compared to those obtained using an FT-ICR mass spectrometer. Despite the lower efficiency in the transfer of desorbed neutral molecules into the ion trap, and the smaller maximum number of available laser pulses, the intrinsically higher sensitivity of the LQIT resulted in a higher sensitivity relative to the FT-ICR.

  8. Investigating potential sources of Mercury's exospheric Calcium: Photon-stimulated desorption of Calcium Sulfide

    Science.gov (United States)

    Bennett, Chris J.; McLain, Jason L.; Sarantos, Menelaos; Gann, Reuben D.; DeSimone, Alice; Orlando, Thomas M.

    2016-02-01

    Ground-based and MErcury Surface, Space ENvironment, GEochemistry, and Ranging observations detected Ca0 and Ca+ in the exosphere of Mercury as well as unexpectedly high levels of sulfur on Mercury's surface. The mineral oldhamite ((Mg,Ca)S) could be a predominant component of the Mercury surface, particularly within the hollows identified within craters, and could therefore serve as a source of the observed exospheric calcium. Laboratory measurements on the photon-stimulated desorption (PSD) of CaS powder (an analog for oldhamite) at a wavelength of λ = 355 nm have been conducted, utilizing resonance-enhanced multiphoton ionization time-of-flight mass spectrometry to determine the yields and velocity distributions of Ca0. The desorbing Ca0 could be fit using two Maxwell-Boltzmann components: a 600 (±30) K thermal component and a 1389 (±121) K nonthermal component, the latter accounting for ~25% of the observed signal. Cross sections for PSD using 3.4 eV photons were found to be 1.1 (±0.7) × 10-20 cm2 for Ca0 and 3.2 (±0.9) × 10-24 cm2 for Ca+. Adopting these cross sections, a Monte Carlo model of the release of Ca0 by PSD from the Tyagaraja crater finds the neutral microexosphere created from this process to be substantial even if only 1% CaS is assumed in the hollows. Diffuse reflectance UV-visible measurements were made on the CaS powder to determine a bandgap, Eg, of 2.81 (±0.14) eV via the Tauc method.

  9. The adsorption-desorption cycle. Reversibility of the BSA-silica system

    NARCIS (Netherlands)

    Giacomelli, CE; Norde, W

    2001-01-01

    The reversibility of the adsorption-desorption cycle was established by comparing the thermostability (determined by differential scanning calorimetry) and secondary structure (obtained by circular dichroism spectroscopy) of BSA before adsorption, adsorbed on, and exchanged from silica particles. Ci

  10. The adsorption-desorption cycle. Reversibility of the BSA-silica system

    NARCIS (Netherlands)

    Giacomelli, C.E.; Norde, W.

    2001-01-01

    The reversibility of the adsorption–desorption cycle was established by comparing the thermostability (determined by differential scanning calorimetry) and secondary structure (obtained by circular dichroism spectroscopy) of BSA before adsorption, adsorbed on, and exchanged from silica particles. Ci

  11. Impact of activated carbon, biochar and compost on the desorption and mineralization of phenanthrene in soil.

    Science.gov (United States)

    Marchal, Geoffrey; Smith, Kilian E C; Rein, Arno; Winding, Anne; Wollensen de Jonge, Lis; Trapp, Stefan; Karlson, Ulrich G

    2013-10-01

    Sorption of PAHs to carbonaceous soil amendments reduces their dissolved concentrations, limiting toxicity but also potentially biodegradation. Therefore, the maximum abiotic desorption of freshly sorbed phenanthrene (≤5 mg kg(-1)) was measured in three soils amended with activated carbon (AC), biochar or compost. Total amounts of phenanthrene desorbed were similar between the different soils, but the amendment type had a large influence. Complete desorption was observed in the unamended and compost amended soils, but this reduced for biochar (41% desorbed) and AC (8% desorbed). Cumulative amounts mineralized were 28% for the unamended control, 19% for compost, 13% for biochar and 4% for AC. Therefore, the effects of the amendments in soil in reducing desorption were also reflected in the extents of mineralization. Modeling was used to analyze key processes, indicating that for the AC and charcoal treatments bacterial activity did not limit mineralization, but rather desorption into the dissolved phase. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Threshold character of temperatures on deuterium desorption from the Mg-Zr composite

    Science.gov (United States)

    Neklyudov, I. M.; Morozov, O. M.; Kulish, V. G.; Zhurba, V. I.; Lomino, N. S.; Ovcharenko, V. D.; Kuprin, O. S.

    2011-06-01

    The plasma evaporation-sputtering method was used to manufacture composite materials of the Mg-Zr system. The ion-implanted deuterium desorption temperature variations depending on the component concentrations were studied. It has been established that the introduction of a Zr impurity to magnesium leads to the significant decrease of the deuterium desorption temperature (~400K) as compared to the release from Mg samples. A step-like form of the curve of the deuterium desorption temperature testifies to presence of two various structural conditions at composite Mg-Zr depending on the relation of components. The hydrogen desorption data obtained using Mg-Zr composites can be used for the further invrstigations into the hydrogen storage materials containing chemical elements with a low solubility in the alloy components.

  13. Threshold character of temperatures on deuterium desorption from the Mg-Zr composite

    Energy Technology Data Exchange (ETDEWEB)

    Neklyudov, I M; Morozov, O M; Kulish, V G; Zhurba, V I; Lomino, N S; Ovcharenko, V D; Kuprin, O S, E-mail: morozov@kipt.kharkov.ua [National Science Center ' Kharkov Institute of Physics and Technology' , 61108 Kharkov (Ukraine)

    2011-06-23

    The plasma evaporation-sputtering method was used to manufacture composite materials of the Mg-Zr system. The ion-implanted deuterium desorption temperature variations depending on the component concentrations were studied. It has been established that the introduction of a Zr impurity to magnesium leads to the significant decrease of the deuterium desorption temperature ({approx}400K) as compared to the release from Mg samples. A step-like form of the curve of the deuterium desorption temperature testifies to presence of two various structural conditions at composite Mg-Zr depending on the relation of components. The hydrogen desorption data obtained using Mg-Zr composites can be used for the further invrstigations into the hydrogen storage materials containing chemical elements with a low solubility in the alloy components.

  14. ESTIMATION OF ACTIVATED ENERGY OF DESORPTION OF n—HEXANE ON ACTIVATED CARBONS BY PTD TECHNIQUE

    Institute of Scientific and Technical Information of China (English)

    LIZhong; WANGHongjuan; 等

    2001-01-01

    In this paper,six kinds of activated carbons such as Ag+-activated carbon,Cu2+activated carbon,Fe3+-activated carbon,activated carbon,Ba2+-activated carbon and Ca2+activated carbon were prepared.The model for estimating activated energy of desorption was established.Temperature-programmed desorption(TPD)experiments were conducted to measure the TPD curves of n-hexanol and then estimate the activation energy for desorption of n-hexanol on the activated carbons.Results showed that the activation energy for the desorption of n-hexanol on the Ag+-activated carbon,the Cu2+-activated carbon and the Fe3+-activated carbon were higher than those of n-hexanol on the activated carbon,the Ca2+-activated carbon and the Ba2+-activated carbon.

  15. ESTIMATION OF ACTIVATED ENERGY OF DESORPTION OF n-HEXANE ON ACTIVATED CARBONS BY TPD TECHNIQUE

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In this paper, six kinds of activated carbons such as Ag+-activated carbon, Cu2+-activated carbon, Fe3+- activated carbon, activated carbon, Ba2+- activated carbon and Ca2+-activated carbon were prepared. The model for estimating activated energy of desorption was established. Temperature-programmed desorption (TPD) experiments were conducted to measure the TPD curves of n-hexanol and then estimate the activation energy for desorption of n-hexanol on the activated carbons. Results showed that the activation energy for the desorption of n-hexanol on the Ag+- activated carbon, the Cu2+- activated carbon and the Fe3+- activated carbon were higher than those of n-hexanol on the activated carbon, the Ca2+- activated carbon and the Ba2+- activated carbon.

  16. Study on impurity desorption induced by femtosecond pulse laser based on a stochastic process model

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    With the advantages on non-equilibrium heating and desorption induced by electronic transition, the femtosecond pulse laser introduces a new way for solving the problem of impurity pollution adsorbed on a solid thin film in micro-electro-mechanical systems (MEMS). A model based on stochastic processes was established for stimulated desorption induced by the femtosecond pulse laser to interpret the interaction of the optically excited hot electrons with the adsorbed molecules in a metal substrate. Numerical simulation results reveal a time-dependent desorption probability of adsorbed molecules and indicate that how key parameters of femtosecond pulse laser, such as incident laser energy flux, pulse duration, and wavelength of pulse, have a great effect on the desorption probability.

  17. Low energy electron stimulated desorption from DNA films dosed with oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Mirsaleh-Kohan, Nasrin; Bass, Andrew D.; Cloutier, Pierre; Massey, Sylvain; Sanche, Leon [Groupe en sciences des radiations, Faculte de medecine et des sciences de la sante, Universite de Sherbrooke, Sherbrooke, Quebec J1H 5N4 (Canada)

    2012-06-21

    Desorption of anions stimulated by 1-18 eV electron impact on self-assembled monolayer (SAM) films of single DNA strands is measured as a function of film temperature (50-250 K). The SAMs, composed of 10 nucleotides, are dosed with O{sub 2}. The OH{sup -} desorption yields increase markedly with exposure to O{sub 2} at 50 K and are further enhanced upon heating. In contrast, the desorption yields of O{sup -}, attributable to dissociative electron attachment to trapped O{sub 2} molecules decrease with heating. Irradiation of the DNA films prior to the deposition of O{sub 2} shows that this surprising increase in OH{sup -} desorption, at elevated temperatures, arises from the reaction of O{sub 2} with damaged DNA sites. These results thus appear to be a manifestation of the so-called 'oxygen fixation' effect, well known in radiobiology.

  18. Research on the gas desorption law of the consumingly destruct coal

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiang-jun; WANG Zhao-feng; YANG Hong-min; XIAO Dong-hui

    2008-01-01

    To solve the issues of calculating gas loss quantity during sampling, simulated gas desorption process of the consumingly destruct coal with the assembly simulation testing device. Through an analysis of the simulation test datum using SPSS software,established a new formula that can be better description on gas desorption process, more accurate calculation of the gas loss quantity during sampling process, and calculating releasable gas quantity during a certain period. Aimed at the new formula, the best time of taking sample is confirmed 3 minutes for consumingly destruct coal, the computative error is less than 10%. Through experiment at laboratory and locale, the new formula could well describe consumingly destruct coal gas desorption law, and it has high calculation precision of gas loss quantity in sampling and desorption quanlity.

  19. EFFECTS OF BIOSOLIDS ON SORPTION AND DESORPTION BEHAVIOR OF CADMIUM IN BIOSOLIDS-AMENDED SOILS

    Science.gov (United States)

    Cadmium sorption and desorption experiments were conducted on different fractions of soils amended with different biosolids with varying chemical properties and unamended soil (control). Biosolids addition increased the slope of the Cd sorption isotherms compared to the control s...

  20. omniSpect: an open MATLAB-based tool for visualization and analysis of matrix-assisted laser desorption/ionization and desorption electrospray ionization mass spectrometry images.

    Science.gov (United States)

    Parry, R Mitchell; Galhena, Asiri S; Gamage, Chaminda M; Bennett, Rachel V; Wang, May D; Fernández, Facundo M

    2013-04-01

    We present omniSpect, an open source web- and MATLAB-based software tool for both desorption electrospray ionization (DESI) and matrix-assisted laser desorption ionization (MALDI) mass spectrometry imaging (MSI) that performs computationally intensive functions on a remote server. These functions include converting data from a variety of file formats into a common format easily manipulated in MATLAB, transforming time-series mass spectra into mass spectrometry images based on a probe spatial raster path, and multivariate analysis. OmniSpect provides an extensible suite of tools to meet the computational requirements needed for visualizing open and proprietary format MSI data.

  1. Nanoporous GaN-Ag composite materials prepared by metal-assisted electroless etching for direct laser desorption-ionization mass spectrometry.

    Science.gov (United States)

    Nie, Bei; Duan, Barrett K; Bohn, Paul W

    2013-07-10

    Three-dimensional nanoporous gallium nitride(PGaN) produced by metal-assisted electroless etching is chemically embedded with silver nanoparticles via electroless deposition, forming a metallized semiconductor membrane with large surface area and nanoscale metal features. A new application utilizing the unique chemical and morphological features of these composite nanostructures is described here, laser induced desorption-ionization(LDI) of biomolecules(e.g., cholesterol and nucleotides) for direct mass analysis, without use of additional organic matrix. Although PGaN itself is a poor matrix for direct LDI mass spectrometry, the combination of Ag and PGaN greatly improves ion signals relative to PGaN or Ag nanostructure surfaces alone. This behavior is attributed to the combination of strong UV absorption, enhanced surface area, and favorable thermal properties of PGaN. Importantly, Ag-PGaN is shown to facilitate the formation of Ag adduct ions in some cases, for example adenine, where adducts are not observed from either porous anodic aluminum membranes or surfaces presenting Ag nanoparticles in isolation. Nanopore-embedded Ag nanostructures serve a dual role: as cationization agents and to assist thermal desorption under UV laser irradiation. The results reported here suggest that the combination of Ag nanostructures embedded in PGaN has the capacity for high quality matrix-free LDI mass analysis.

  2. Heavy-ion-induced desorption of organic molecules studied with Langmuir-Blodgett multilayer systems (DE)

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, R.; Schoppmann, C.; Brandl, D.; Ostrowski, A.; Voit, H. (Physikalisches Institut der Universitaet Erlangen-Nuernberg D-8520 Erlangen, (Germany)); Johannsmann, D.; Knoll, W. (Max-Planck-Institut fuer Polymerforschung Mainz D-6500 Mainz, (Germany))

    1991-07-01

    Heavy-ion-induced desorption has been studied with samples consisting of Langmuir-Blodgett films made from Cd salts of fatty acids. The experiments confirm the result of previous works that heavy ions drill a crater into the sample surface. The explicit dependence of the crater depth on the electronic energy loss could be determined from the experiments. The craters exhibit the shape of a symmetric cone as obtained from a desorption model applied to the experimental data.

  3. Oxygen Sorption and Desorption Properties of Selected Lanthanum Manganites and Lanthanum Ferrite Manganites

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Skou, Eivind M.; Jacobsen, Torben

    2015-01-01

    Temperature‐programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid‐oxide fuel cell (SOFC) cathode materials (La0.85Sr0.15)0.95MnO3+δ (LSM) and La0.60Sr0.40Fe0.80Mn0.20O3‐δ (LSFM). The powders were characteriz...

  4. Desorption of organo phosphorous pesticides from soil with wastewater and surfactant solution

    OpenAIRE

    Hernandez-Soriano, Maria del Carmen; Mingorance, Maria Dolores; Peña, Aranzazu

    2008-01-01

    Surfactants can be introduced in the environment by wastewater discharge, point-charge pollution or deliberate action, e.g. to remediate contaminated soil or groundwater. The irrigation of soil with wastewater containing surfactants may modify pesticide desorption from soil, thus affecting their environmental fate. Desorption from soil of the plain of Granada (South-eastern Spain) of two organophosphorous pesticides, diazinon and dimethoate, differing in solubility and hydrophobicity...

  5. Various causes behind the desorption hysteresis of carboxylic acids on mudstones.

    Science.gov (United States)

    Rasamimanana, S; Lefèvre, G; Dagnelie, R V H

    2017-02-01

    Adsorption desorption is a key factor for leaching, migration and (bio)degradation of organic pollutants in soils and sediments. Desorption hysteresis of apolar organic compounds is known to be correlated with adsorption/diffusion into soil organic matter. This work focuses on the desorption hysteresis of polar organic compounds on a natural mudstone sample. Acetic, citric and ortho-phthalic acids displayed adsorption-desorption hysteresis on Callovo-Oxfordian mudstone. The non-reversible behaviours resulted from three different mechanisms. Adsorption and desorption kinetics were evaluated using 14C- and 3H-labelled tracers and an isotopic exchange method. The solid-liquid distribution ratio of acetate decreased using a NaN3 bactericide, indicating a rapid bacterial consumption compared with negligible adsorption. The desorption hysteresis of phthalate was apparent and suppressed by the equilibration of renewal pore water with mudstone. This confirms the significant and reversible adsorption of phthalate. Finally, persistent desorption hysteresis was evidenced for citrate. In this case, a third mechanism should be considered, such as the incorporation of citrate in the solid or a chemical perturbation, leading to strong desorption resilience. The results highlighted the different pathways that polar organic pollutants might encounter in a similar environment. Data on phthalic acid is useful to predict the retarded transport of phthalate esters and amines degradation products in sediments. The behaviour of citric acid is representative of polydentate chelating agents used in ore and remediation industries. The impact of irreversible adsorption on solid/solution partitioning and transport deserves further investigation.

  6. A Monte Carlo study of temperature-programmed desorption spectra with attractive lateral interactions

    CERN Document Server

    Jansen, A P J

    1995-01-01

    We present results of a Monte Carlo study of temperature-programmed desorption in a model system with attractive lateral interactions. It is shown that even for weak interactions there are large shifts of the peak maximum temperatures with initial coverage. The system has a transition temperature below which the desorption has a negative order. An analytical expression for this temperature is derived. The relation between the model and real systems is discussed.

  7. Effect of pH on desorption of CO2 from alkanolamine - rich solvents

    Science.gov (United States)

    Du, Min

    2017-08-01

    Adipic acid was used as a pH regulator, which was added to 0.4 mol/L MEA, DEA and MDEA solvents during CO2 desorption process. It is found that when pH value of the solvents swing between 8-10, CO2 desorption rate enhanced, and energy consumption has declined obviously. This research may have reference significance on optimization of alkanolamine CO2 capture process.

  8. Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts

    OpenAIRE

    Gloria Lourdes Dimas-Rivera; Javier Rivera de la Rosa; Carlos J. Lucio-Ortiz; José Antonio De los Reyes Heredia; Virgilio González González; Tomás Hernández

    2014-01-01

    In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection betwe...

  9. Investigation of Catalytic Effects and Compositional Variations in Desorption Characteristics of LiNH2-nanoMgH2

    Directory of Open Access Journals (Sweden)

    Sesha S. Srinivasan

    2017-07-01

    Full Text Available LiNH2 and a pre-processed nanoMgH2 with 1:1 and 2:1 molar ratios were mechano-chemically milled in a high-energy planetary ball mill under inert atmosphere, and at room temperature and atmospheric pressure. Based on the thermogravimetric analysis (TGA experiments, 2LiNH2-nanoMgH2 demonstrated superior desorption characteristics when compared to the LiNH2-nanoMgH2. The TGA studies also revealed that doping 2LiNH2-nanoMgH2 base material with 2 wt. % nanoNi catalyst enhances the sorption kinetics at lower temperatures. Additional investigation of different catalysts showed improved reaction kinetics (weight percentage of H2 released per minute of the order TiF3 > nanoNi > nanoTi > nanoCo > nanoFe > multiwall carbon nanotube (MWCNT, and reduction in the on-set decomposition temperatures of the order nanoCo > TiF3 > nanoTi > nanoFe > nanoNi > MWCNT for the base material 2LiNH2-nanoMgH2. Pristine and catalyst-doped 2LiNH2-nanoMgH2 samples were further probed by X-ray diffraction, Fourier transform infrared spectroscopy, transmission and scanning electron microscopies, thermal programmed desorption and pressure-composition-temperature measurements to better understand the improved performance of the catalyst-doped samples, and the results are discussed.

  10. Electrothermal adsorption and desorption of volatile organic compounds on activated carbon fiber cloth.

    Science.gov (United States)

    Son, H K; Sivakumar, S; Rood, M J; Kim, B J

    2016-01-15

    Adsorption is an effective means to selectively remove volatile organic compounds (VOCs) from industrial gas streams and is particularly of use for gas streams that exhibit highly variable daily concentrations of VOCs. Adsorption of such gas streams by activated carbon fiber cloths (ACFCs) and subsequent controlled desorption can provide gas streams of well-defined concentration that can then be more efficiently treated by biofiltration than streams exhibiting large variability in concentration. In this study, we passed VOC-containing gas through an ACFC vessel for adsorption and then desorption in a concentration-controlled manner via electrothermal heating. Set-point concentrations (40-900 ppm(v)) and superficial gas velocity (6.3-9.9 m/s) were controlled by a data acquisition and control system. The results of the average VOC desorption, desorption factor and VOC in-and-out ratio were calculated and compared for various gas set-point concentrations and superficial gas velocities. Our results reveal that desorption is strongly dependent on the set-point concentration and that the VOC desorption rate can be successfully equalized and controlled via an electrothermal adsorption system.

  11. Photoinduced Br Desorption from CsBr Thin Films Grown on Cu(100)

    Energy Technology Data Exchange (ETDEWEB)

    Halliday, Matthew T.; Joly, Alan G.; Hess, Wayne P.; Shluger, AL

    2015-10-22

    Thin films of CsBr deposited onto metals such as copper are potential photocathode materials for light sources and other applications. We investigate desorption dynamics of Br atoms from CsBr films grown on insulator (KBr, LiF) and metal (Cu) substrates induced by sub-bandgap 6.4 eV laser pulses. The experimental results demonstrate that the peak kinetic energy of Br atoms desorbed from CsBr/Cu films is much lower than that for the hyperthermal desorption from CsBr/LiF films. Kelvin probe measurements indicate negative charge at the surface following Br desorption from CsBr/Cu films. Our ab initio calculations of excitons at CsBr surfaces demonstrate that this behavior can be explained by an exciton model of desorption including electron trapping at the CsBr surface. Trapped negative charges reduce the energy of surface excitons available for Br desorption. We examine the electron-trapping characteristics of low-coordinated sites at the surface, in particular, divacancies and kink sites. We also provide a model of cation desorption caused by Franck-Hertz excitation of F centers at the surface in the course of irradiation of CsBr/Cu films. These results provide new insights into the mechanisms of photoinduced structural evolution of alkali halide films on metal substrates and activation of metal photocathodes coated with CsBr.

  12. Characteristics and applications of gas desorption with excavation disturbances in coal mining

    Institute of Scientific and Technical Information of China (English)

    Jiachen Wang; Renlun Wu; Peng Zhang

    2015-01-01

    According to the deficiency of experiment system for gas adsorption and desorption in coal mass, a large scale experiment system is developed independently by researchers. This experiment system is composed of primary and auxiliary boxes, power transmission system, mining system, loading system, gas charging system, data monitoring and intelligent acquisition system. The maximum experiment coal consumption is 1200 kg, the mining system is developed to conduct experiment for gas desorption under excavating disturbance, and the plane-charging cribriform ventilation device is developed to realize uniform ventilation for experiment coal sample, which is accord with the actual gas source situation of coal bed. The desorption characteristics of gas in coal are experimentally studied under the conditions of nature and mining using the experiment system. The results show that, compare with nature condition, the permeability of coal and the velocity of gas desorption could significantly increase under the influence of coal pressure relief and destruction caused by mining, and the degree of gas desorption could somewhat increase too. Finally, pressure relief gas extraction of current seam and adjacent seams after mining in a certain coal mine of Yangquan mining area are introduced, and the gas desorption experiment results is verified by analyzing the effect of gas extraction.

  13. Enhanced hydrogen desorption property of MgH{sub 2} with the addition of cerium fluorides

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Huai-Jun, E-mail: huaijun.lin.489@s.kyushu-u.ac.jp [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Department of Mechanical Engineering, Faculty of Engineering, Kyushu University, Fukuoka 819-0395 (Japan); Matsuda, Junko [International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 819-0395 (Japan); Li, Hai-Wen [International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 819-0395 (Japan); International Research Center for Hydrogen Energy, Kyushu University, Fukuoka 819-0395 (Japan); Zhu, Min [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); China–Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510640 (China); Akiba, Etsuo [Department of Mechanical Engineering, Faculty of Engineering, Kyushu University, Fukuoka 819-0395 (Japan); International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka 819-0395 (Japan); International Research Center for Hydrogen Energy, Kyushu University, Fukuoka 819-0395 (Japan)

    2015-10-05

    Highlights: • Activation energy of MgH{sub 2} desorption is remarkably reduced with the dopant of CeF{sub 4}. • The improvement might be attributed to new Ce–F–Mg species at the CeF{sub 4}/MgH{sub 2} interface. • Easy electron transfer induced from the high valence Ce-cation benefits MgH{sub 2} desorption. - Abstract: Hydrogen desorption property of MgH{sub 2} doped with cerium fluorides with different valences prepared using ball milling has been studied. CeF{sub 4} is catalytically active for hydrogen desorption of MgH{sub 2}. Hydrogen desorption temperature and apparent activation energy of MgH{sub 2} are significantly reduced with dopant of 2 mol% of CeF{sub 4}, which might be attributed to the formation of a new Ce–F–Mg specie at the CeF{sub 4}/MgH{sub 2} interface and the easy electron transfer induced from the high valence Ce-cation. The apparent activation energy of hydrogen desorption of MgH{sub 2} is reduced from ∼160 kJ/mol to ∼110 kJ/mol with the dopant of CeF{sub 4}.

  14. Effects of organic acids on cadmium and copper sorption and desorption by two calcareous soils.

    Science.gov (United States)

    Najafi, Sarvenaz; Jalali, Mohsen

    2015-09-01

    Low molecular weight organic acids (LMWOAs) present in soil alter equilibrium pH of soil, and consequently, affect heavy metal sorption and desorption on soil constitutes. This study was conducted to investigate the effects of different concentrations (0.1, 1, 2.5, 5, 10, 30, 40, 50, 70, and 100 mM) of citric, malic, and oxalic acids on sorption and desorption of cadmium (Cd) and copper (Cu) in two calcareous soils. Increasing the concentrations of three LMWOAs decreased the equilibrium pH of soil solutions. The results indicated that increase in organic acids concentrations generally reduced Cd and Cu sorption in soils. Increase concentrations of LMWOAs generally promoted Cd and Cu desorption from soils. A valley-like curve was observed for desorption of Cu after the citric acid concentration increment in soil 2. Increasing the concentrations of three LMWOAs caused a marked decrease in Kd(sorp) values of Cd and Cu in soils. In general, citric acid was the most effective organic acid in reducing sorption and increasing desorption of both metals, and oxalic acid had the minimal impact. The results indicated that LMWOAs had a greater impact on Cu sorption and desorption than Cd, which can be attributed to higher stability constants of organic acids complexes with Cu compared to Cd. It can be concluded that by selecting suitable type and concentration of LMWOAs, mobility, and hence, bioavailability of heavy metals can be changed. So, environmental implications concerning heavy metals mobility might be derived from these findings.

  15. ATRAZINE ADSORPTION-DESORPTION BEHAVIOR IN DAREHASALUIE KAVAR CORN FIELD SOIL

    Directory of Open Access Journals (Sweden)

    M. Dehghani, S. Nasseri, S. Amin, K. Naddafi, M. Yunesian, M. Taghavi and N. Maleki

    2005-10-01

    Full Text Available Adsorption desorption behaviors of widely applied atrazine soil were studied, employing a batch technique as a case study in Darehasaluie Kavar corn field in Fars Province in 2005. Samples were collected into 0 to 20 cm soil depth, where was cultivated under a crop rotation (corn-wheat during the past 10 years. Sorption kinetics exhibited two phenomena: an immediate rapid sorption (1.31 µg/g soil after 12 hours followed by a slow sorption process (1.37 µg/g soil after 24 hours. Desorption behavior of atrazine was similar to its adsorption, but at a very slower rate. Atrazine desorption efficiencies were much less effective and incomplete even after a long equilibration time (only 9.16% after 96 hours. The adsorption-desorption rate for most of the time was positively related to the amount of applied atrazine and the time required for equilibration (P<0.01. Desorption data exhibited hysteresis phenomena. Atrazine adsorption data described well according to Freundlich (r2=0.95, Langmuir (r2=0.82 and Temkin (r2=0.84 isotherms. However, the fit to Freundlich adsorption model in a non linear form (1/n <1 was closer than the others. Desorption isotherm could be well described by the Temkin (r2=0.96 and Freundlich (r2=0.92 isotherms, but the fit to Temkin model was closer than that of Freundlich.

  16. Desorption of 3,3′-diindolylmethane from imprinted particles: An impact of cross-linker structure on binding capacity and selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Klejn, Dorota; Luliński, Piotr; Maciejewska, Dorota, E-mail: dorota.maciejewska@wum.edu.pl

    2015-11-01

    Here, seven cross-linkers (six polar diacrylates or dimethacrylates of different lengths between double bonds, and one aromatic-divinylbenzene) were used to examine the impact of the cross-linker on binding capacity and selectivity of 3,3′-diindolylmethane (DIM) imprinted material. DIM participates in the suppression of viability of human ovarian and human breast cancer cell lines, but has low bioavailability. The investigations of novel imprinted polymer matrices for improvement of DIM release could allow to utilize not only a potency of DIM but also similar alkaloids, which are the important compounds with pharmacological activity. The bulk, thermal radical copolymerization of the cross-linkers in the presence of 3,3′-diindolylmethane (the template) and allylamine (the functional monomer) in dimethyl sulfoxide or in carbon tetrachloride (porogens) was carried out. The binding capacities of imprinted and non-imprinted polymers were compared, and two polymers (these were prepared using ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate as the cross-linkers) with the highest selectivity and binding capacity were selected to desorption test. The desorption profile of polymer prepared using polyethylene glycol dimethacrylate as the cross-linker revealed sustained release of 3,3′-diindolylmethane, and this system was selected for further optimization of the cross-linker amounts. The morphology and structure of the selected particles were analyzed using SEM micrographs, {sup 13}C CP/MAS NMR spectroscopy, and BET measurements. The desorption of 3,3′-diindolylmethane from poly(allylamine-co-polyethylene glycol dimethacrylate) particles was in accordance with pseudo-second-order kinetics and the simplified Higuchi model indicated the diffusion controlled release of 3,3′-diindolylmethane. - Graphical abstract: Sustained release of 3,3′-diindolylmethane from cavity in imprinted poly(allylamine-co-polyethylene glycol dimethacrylate

  17. Desorption of a methamphetamine surrogate from wallboard under remediation conditions

    Science.gov (United States)

    Poppendieck, Dustin; Morrison, Glenn; Corsi, Richard

    2015-04-01

    Thousands of homes in the United States are found to be contaminated with methamphetamine each year. Buildings used to produce illicit methamphetamine are typically remediated by removing soft furnishings and stained materials, cleaning and sometimes encapsulating surfaces using paint. Methamphetamine that has penetrated into paint films, wood and other permanent materials can be slowly released back into the building air over time, exposing future occupants and re-contaminating furnishings. The objective of this study was to determine the efficacy of two wallboard remediation techniques for homes contaminated with methamphetamine: 1) enhancing desorption by elevating temperature and relative humidity while ventilating the interior space, and 2) painting over affected wallboard to seal the methamphetamine in place. The emission of a methamphetamine surrogate, N-isopropylbenzylamine (NIBA), from pre-dosed wallboard chambers over 20 days at 32 °C and two values of relative humidity were studied. Emission rates from wallboard after 15 days at 32 °C ranged from 35 to 1400 μg h-1 m-2. Less than 22% of the NIBA was removed from the chambers over three weeks. Results indicate that elevating temperatures during remediation and latex painting of impacted wallboard will not significantly reduce freebase methamphetamine emissions from wallboard. Raising the relative humidity from 27% to 49% increased the emission rates by a factor of 1.4. A steady-state model of a typical home using the emission rates from this study and typical residential building parameters and conditions shows that adult inhalation reference doses for methamphetamine will be reached when approximately 1 g of methamphetamine is present in the wallboard of a house.

  18. Carbon dioxide sorption/ desorption characteristics of coals in Taiwan

    Science.gov (United States)

    Chien-Hung, Hsiao; Loung-Yie, Tsai

    2013-04-01

    Geological sequestration of CO2 into depleted oil reservoir, saline aquifer or unmineable coal seam is now being actively investigated for the purpose of reducing greenhouse gas in the atmosphere. Understanding the physical, chemical, and thermodynamic phenomena occurred with CO2 injection is very important in marking a reliable prediction of sequestration. This study examined the feasibility of carbon dioxide sequestration into unmineable coal seams in Taiwan. A total of 20 Miocene-aged coal samples from Western Foothill Belt, NW Taiwan, were collected. The stratigraphy include Mushan, Shihti, and Nanchuang Formation from bottom up. Proximate and petrographic analyses include maceral composition, Vitrinite reflectance were also measured. Carbon dioxide adsorption isotherms were analyzed at 35 degrees Celsius and up to 800 psi, by using a gravimetric ad/desorption apparatus. Isotherms were then fitted with a modified Langmuir Isotherm model by using Langmuir Pressure and Langmuir Volume so the model can be applied to supercritical conditions. According to the result of adsorption experiment, the pressure and temperature were quite significant. The gas storage capacity of CO2 was about 400 600 scf/ton at pressure up to 800 psi. Comparing the results of adsorption capacity with Proximate analysis and vitrinite reflectance, the Langmuir Volume shows a strong positive correlation with fixed carbon and vitrinite content. Furthermore, Adsorption capacity is closely related to micropores which were also rank and maceral dependent. It is noticed that the observed coal pore structures were affected by rank, and then exhibit have different diffusion rate of CO2.Finally, images under SEM were evaluated to understand the pathways of gas sorption.

  19. Single Component Sorption-Desorption Test Experimental Design Approach Discussions

    Energy Technology Data Exchange (ETDEWEB)

    Phil WInston

    2011-09-01

    A task was identified within the fission-product-transport work package to develop a path forward for doing testing to determine behavior of volatile fission products behavior and to engage members of the NGNP community to advise and dissent on the approach. The following document is a summary of the discussions and the specific approaches suggested for components of the testing. Included in the summary isare the minutes of the conference call that was held with INL and external interested parties to elicit comments on the approaches brought forward by the INL participants. The conclusion was that an initial non-radioactive, single component test will be useful to establish the limits of currently available chemical detection methods, and to evaluated source-dispersion uniformity. In parallel, development of a real-time low-concentration monitoring method is believed to be useful in detecting rapid dispersion as well as desorption phenomena. Ultimately, the test cycle is expected to progress to the use of radio-traced species, simply because this method will allow the lowest possible detection limits. The consensus of the conference call was that there is no need for an in-core test because the duct and heat exchanger surfaces that will be the sorption target will be outside the main neutron flux and will not be affected by irradiation. Participants in the discussion and contributors to the INL approach were Jeffrey Berg, Pattrick Calderoni, Gary Groenewold, Paul Humrickhouse, Brad Merrill, and Phil Winston. Participants from outside the INL included David Hanson of General Atomics, Todd Allen, Tyler Gerczak, and Izabela Szlufarska of the University of Wisconsin, Gary Was, of the University of Michigan, Sudarshan Loyalka and Tushar Ghosh of the University of Missouri, and Robert Morris of Oak Ridge National Laboratory.

  20. Laser Desorption Supersonic Jet Spectroscopy of Hydrated Tyrosine

    Science.gov (United States)

    Oba, Hikari; Shimozono, Yoko; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Carcabal, Pierre

    2013-06-01

    The structure of tyrosine (tyr) consists of amino-acid chain and phenol, and it has roughly two possible binding sites for water, amino-acid site and phenolic OH site. Investigating how water molecule binds to tyr will give fundamental information for hydrations of peptide and protein. Resonance enhanced multi photon ionization (REMPI) spectrum of tyr-water 1:1 cluster has already been reported by de Vries and co-workers, however, no analysis on the hydrated structures has been reported. In the REMPI spectrum, two clusters of bands are observed; one appears at ˜35600 cm^{-1} energy region which is the almost same with 0-0 transitions of tyr monomer, and another is observed at ˜300 cm^{-1} lower than the former. Based on the electronic transition energy of phenylalanine and the hydrated clusters, the former is expected to be derived from a structure that water binds to amino acid site. On the other hand, it is plausibly predicted that the latter originates from a structure that water binds to phenolic OH group, because the electronic transition of mono hydrated phenol is ˜300 cm^{-1} red-shifted from the monomer. We applied IR dip spectroscopy which can measure conformer selective IR spectra to the tyr-(H_{2}O)_{1} clusters by using laser desorption supersonic jet technique to confirm the assignments. Especially in the phenolic OH bound isomer, it was found that the intra molecular hydrogen bond within amino-acid chain, which is far from the water molecule and cannot interact directly with each other, is strengthened by the hydration. A. Abio-Riziq et al., J. Phys. Chem. A, 115, 6077 (2011). Y. Shimozono, et al., Phys. Chem. Chem. Phys., (2013) DOI: 10.1039/c3cp43573c. T. Ebata et al., Phys. Chem. Chem. Phys., 8, 4783 (2006). T. Watanabe et al., J. Chem. Phys., 105, 408 (1996).

  1. Hydration–dehydration behavior and thermodynamics of MX-80 montmorillonite studied using thermal analysis

    Energy Technology Data Exchange (ETDEWEB)

    Tajeddine, L. [CNRS-IC2MP-UMR- Hydrasa, 5 Ave Albert, Turpain, (France); Gailhanou, H.; Blanc, P.; Lassin, A.; Gaboreau, S. [BRGM, 3 Av. Claude Guillemin, BP6009, Orléans F-45060 (France); Vieillard, P., E-mail: philippe.vieillard@univ-poitiers.fr [CNRS-IC2MP-UMR- Hydrasa, 5 Ave Albert, Turpain, (France)

    2015-03-20

    Highlights: • Adsorption–desorption of water on MX-80 is determined from TGA and DTA analysis. • From DTA analysis, three types of water behavior exist at various hydration states. • Surface area of DTA allows to determine the dehydration enthalpy per mole of water. • A maximum enthalpy is 12 kJ/mol for the adsorption and desorption processes. • Enthalpy of formation of water for adsorption and desorption processes are provided. - Abstract: The thermal dehydration of natural bentonite clay MX-80 chosen as a possible future backfill material, was investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The aim of this work is to provide a better understanding of the thermodynamics of the hydration–dehydration process of MX-80. The data obtained from thermogravimetry derivative curves at different relative humidities were used to determine the adsorption–desorption isotherm of MX-80. The total amount of water varies from 0.35 to 5.62 and from 0.78 to 6.12 mol adsorbed H{sub 2}O/mol of clay upon adsorption and desorption, respectively, for a RH between 11 and 91%. Furthermore, the heats released upon adsorption and desorption are not completely similar. Moreover, the analysis of DTA signals obtained at various hydration states provides insights about three types of water behavior in MX-80. Therefore, the surface area of DTA curves was taken into account to determine the dehydration enthalpy per mole of water; the values do not correlate with the amount of adsorbed water in MX-80, and the maximum enthalpy was approximately 12 kJ/mol for the adsorption and desorption studies. The values obtained were combined with the standard enthalpies of the formation of liquid water to obtain the corresponding enthalpy of the formation of water relative to dehydrated MX-80.

  2. Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Smith, R. Scott; May, Robert A.; Kay, Bruce D.

    2016-03-03

    The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multi- layer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The non-alignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.

  3. Fate and transport with material response characterization of green sorption media for copper removal via desorption process.

    Science.gov (United States)

    Chang, Ni-Bin; Houmann, Cameron; Lin, Kuen-Song; Wanielista, Martin

    2016-07-01

    Multiple adsorption and desorption cycles are required to achieve the reliable operation of copper removal and recovery. A green sorption media mixture composed of recycled tire chunk, expanded clay aggregate, and coconut coir was evaluated in this study for its desorptive characteristics as a companion study of the corresponding adsorption process in an earlier publication. We conducted a screening of potential desorbing agents, batch desorption equilibrium and kinetic studies, and batch tests through 3 adsorption/desorption cycles. The desorbing agent screening revealed that hydrochloric acid has good potential for copper desorption. Equilibrium data fit the Freundlich isotherm, whereas kinetic data had high correlation with the Lagergren pseudo second-order model and revealed a rapid desorption reaction. Batch equilibrium data over 3 adsorption/desorption cycles showed that the coconut coir and media mixture were the most resilient, demonstrating they could be used through 3 or more adsorption/desorption cycles. FE-SEM imaging, XRD, and EDS analyses supported the batch adsorption and desorption results showing significant surface sorption of CuO species in the media mixture and coconut coir, followed by partial desorption using 0.1 M HCl as a desorbing agent. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Thermal studies on natural polysaccharide

    Institute of Scientific and Technical Information of China (English)

    Sunil B Bothara; Sudarshan Singh

    2012-01-01

    Objective: To characterize thermal property of natural gums obtained from the seeds of Diospyros melonoxylon(D. melonoxylon) Roxb, Buchanania lanzan (B. lanzan) spreng and Manilkara zapota (M. zapota) (Linn.) P. Royen syn. Methods: Natural gums were thermally characterized using differential scanning calorimetry (DSC), differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA) under nitrogen atmosphere. Major thermal transitions as well as activation energies of the major decomposition stages were determined. Elemental analysis was performed in order to determine the composition of carbon, hydrogen, nitrogen and sulfur. Results: DSC traces indicated a major intense exothermic transition (around 200℃) followed by weaker exotherm(s). Thermogravimetric analysis showed two phase of weight loss. The first phase has minor weight loss in samples is attributed to the loss of adsorbed and structural water of biopolymers or due to desorption of moisture as hydrogen bound water to the saccharide structure. The second weight loss event may be attributed to the polysaccharide decomposition. The initial decomposition temperature (IDT) was calculated from thermograms obtained of TGA, seed Polysaccharide of D. melonoxylon (IDT 221.21℃), B. lanzan (IPDT 170.4℃) and M. zapota (IPDT 178.6℃) were obtained. According to the integral procedural decomposition temperature (IPDT) values calculated based on the TGA thermograms; D. melonoxylon (IPDT 563.3℃), B. lanzan (IPDT 598.1℃) and M. zapota (IPDT 600.6℃) were obtained respectively. The elemental analysis study shows that the isolated natural Polysaccharides consist of certain percentage of carbon, nitrogen, sulphur and hydrogen in all the gums. Conclusions: The results of the present investigation reveal that the natural gums are thermally stable and these gums can be used as release modifiers in various dosage forms.

  5. Optimization and kinetic modeling of cadmium desorption from citrus peels: A process for biosorbent regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Njikam, Eloh, E-mail: ennjikam@alaska.edu [Department of Civil and Environmental Engineering, University of Alaska Fairbanks, P.O. Box 755900, Fairbanks, AK 99775 (United States); Schiewer, Silke, E-mail: sschiewer@alaska.edu [Department of Civil and Environmental Engineering, University of Alaska Fairbanks, P.O. Box 755900, Fairbanks, AK 99775 (United States)

    2012-04-30

    Graphical abstract: Cadmium was completely and quickly desorbed from grapefruit peels using 0.01 M HNO{sub 3}. The kinetics followed a novel 1st or 2nd order kinetic model, related to the remaining metal bound as the rate-determining reactant concentration. For 0.001 M HNO{sub 3}, desorption was incomplete and the model fit less perfect. Highlights: Black-Right-Pointing-Pointer Metal desorption was over 90% complete within 50 min for most desorbents. Black-Right-Pointing-Pointer Models for biosorbent desorption kinetics were developed. Black-Right-Pointing-Pointer Desorption kinetics best fit a novel first-order model related to remaining metal bound. Black-Right-Pointing-Pointer Cd uptake after desorption by HNO{sub 3} was similar to the original uptake. Black-Right-Pointing-Pointer The optimal desorbent was 0.1 or 0.01 M acid, being fast, efficient and cheap. - Abstract: Citrus peel biosorbents are efficient in removing heavy metals from wastewater. Heavy metal recovery and sorbent regeneration are important for the financial competitiveness of biosorption with other processes. The desorbing agents HNO{sub 3}, NaNO{sub 3}, Ca(NO{sub 3}){sub 2}, EDTA, S, S-EDDS, and Na-Citrate were studied at different concentrations to optimize cadmium elution from orange or grapefruit peels. In most cases, desorption was fast, being over 90% complete within 50 min. However sodium nitrate and 0.001 M nitric acid were less efficient. Several new models for desorption kinetics were developed. While zero-, first- and second-order kinetics are commonly applied for modeling adsorption kinetics, the present study adapts these models to describe desorption kinetics. The proposed models relate to the number of metal-filled binding sites as the rate-determining reactant concentration. A model based on first order kinetics with respect to the remaining metal bound performed best. Cd bound in subsequent adsorption after desorption was similar to the original amount bound for desorption by

  6. Evaluation of sorption-desorption processes for metalaxyl in natural and artificial soils.

    Science.gov (United States)

    Sukul, Premasis; Lamshöft, Marc; Zühlke, Sebastian; Spiteller, Michael

    2013-01-01

    The main process controlling soil-pesticide interaction is the sorption-desorption as influenced by active soil surfaces. The sorption phenomena can influence translocation, volatility, persistence and bioactivity of a pesticide in soil. The present investigation was conducted on natural and artificial soils in order to enumerate the effect of soil components such as montmorillonite and ferrihydrite on the sorption behaviour of the fungicide metalaxyl and if sorption-desorption of the chiral pesticide affects the enantiomeric ratio. The sorption-desorption characteristics of metalaxyl were investigated by batch equilibration technique in a natural soil, two artificial soils, and in pure montmorillonite and ferrihydrite. After extraction, pesticide residues were analyzed by conventional and chiral chromatography using tandem mass spectrometry. A KdSorp (2.3-6.5) suggests low level sorption of metalaxyl with an appreciable risk of run-off and leaching. Thus, metalaxyl poses a threat to surface and ground water contamination. Furthermore, desorption tests revealed a hysteretic effect (H ≤ 0.8) in natural and artificial soils. Significant amount of metalaxyl was found tightly bound to the adsorbents without desorbing readily after desorption cycle. Desorption of 22-56% of the total amount of the retained metalaxyl was determined. This study reveals that an artificial soil derived from different soil constituents can be used to assess their influence on sorption/desorption processes. The present investigation showed that both montmorillonite and ferrihydrite play a significant role in the sorption of metalaxyl. The sorption doesn't influence the enantiomeric ratio of racemic metalaxyl.

  7. Characteristics and influencing factors of tetrachloroethylene sorption-desorption on soil and its components.

    Science.gov (United States)

    Qiu, Zhaofu; Yang, Weiwei; He, Long; Zhao, Zhexuan; Lu, Shuguang; Sui, Qian

    2016-02-01

    To investigate the effects of soil structure, soil organic carbon (SOC), minerals, initial tetrachloroethylene (PCE) concentration (C0), and ionic strength (Ci) on PCE sorption-desorption, six types of soil were adopted as adsorbents, including two types of natural soil and four types of soil with most of the "soft carbon" pre-treated by H2O2 or with all SOC removed from the original soil by 600 °C ignition. The results showed that all of the sorption-desorption isotherms of PCE were non-linear within the experimental range, and the H2O2-treated samples exhibited higher non-linear sorption isotherms than those of the original soils. The hysteresis index of PCE sorption to original soil is less pronounced than that of the H2O2-treated and 600 °C-heated samples due to the entrapment of sorbate molecules in the "hard carbon" domain, together with the meso- and microporous structures within the 600 °C-heated samples. Both SOC and minerals have impacts on the sorption-desorption of PCE, and the sorption-desorption contribution rate of minerals increased with decreasing SOC content. C0 has almost no influence on the sorption to minerals of the soils, but the contribution rate of minerals decreased with increasing C0 in the desorption stage. As a result of the salting-out effect, PCE sorption capacity was increased by increasing Ci, especially when Ci ≥ 0.1 M. Moreover, desorption increased and hysteresis weakened with increasing Ci, except for the 600 °C-heated samples. In addition, no significant effect of Ci on desorption of PCE and no hysteresis was observed in this experimental range for the 600 °C-heated samples.

  8. Surface Potential Control on Thin Oxide Films with Respect to Electron Stimulated Desorption Studies

    Science.gov (United States)

    Bernheim, Marc; Rousse, Gilles

    1995-09-01

    These experiments deal with the study of desorption of negative ions stimulated by low energy electron collisions on insulating surfaces covered with various adsorbates. For such investigation a careful control of the sample surface potential is required to set the incident electron energy accurately as well as to identify the desorbed species by mass spectrometry. Most of the reported experiments concern this surface potential control. We show that, for very thin SiO2 films thermally grown on silicon substrates, a tunnel conduction might set the surface potential accurately. This assertion mainly relies on recording the intensity of electrons transmitted through thin oxides as well as the intensity of backscattered and secondary electrons re-emitted from the surface. A direct comparison of the O^- ion energy distributions confirms the correct control of the surface potential for a large range of incident electron energies. In such condition we noticed that the O^- desorption yields just swiftly varied with incident electron energy. In particular no modification could be detected as the incident electron energy passed the various Auger excitation levels. The discrepancy between this last result and the published data is discussed in the last part of this paper. Des collisions électroniques sur des surfaces peuvent provoquer une éjection d'ions négatifs formés à partir des molécules adsorbées suivant un processus résonnant à très basse énergie. Pour étendre ces études expérimentales aux surfaces isolantes, un contrôle précis du potentiel superficiel devient indispensable tant pour fixer l'énergie finale des électrons sur la surface que pour effectuer la spectrométrie des ions désorbés. L'examen de surfaces de silice en couche mince montre comment une conduction tunnel intervient pour fixer le potentiel des surfaces examinées. Ces travaux expérimentaux effectués dans une configuration de miroir électrostatique reposent principalement sur l

  9. Surface and Particle-Size Effects on Hydrogen Desorption from Catalyst-Doped MgH2

    Energy Technology Data Exchange (ETDEWEB)

    Reich, J.M.; Wang, Lin-Lin; Johnson, Duane D.

    2012-09-04

    With their high capacity, light-metal hydrides like MgH2 remain under scrutiny as reversible H-storage materials, especially to develop control of H-desorption properties by decreasing size (ball-milling) and/or adding catalysts. By employing density functional theory and simulated annealing, we study initial H2 desorption from semi-infinite stepped rutile (110) surface and Mg31H62 nanoclusters, with(out) transition-metal catalyst dopants (Ti or Fe). While Mg31H62 structures are disordered (amorphous), the semi-infinite surfaces and nanoclusters have similar single, double, and triple H-to-metal bond configurations that yield similar H-desorption energies. Hence, there is no size effect on desorption energetics with reduction in sample size, but dopants do reduce the H-desorption energy. All desorption energies are endothermic, in contrast to a recent report.

  10. SORPTION AND DESORPTION OF GLYPHOSATE IN MOLLISOLS AND ULTISOLS SOILS OF ARGENTINA.

    Science.gov (United States)

    Gómez Ortiz, Ana Maria; Okada, Elena; Bedmar, Francisco; Costa, José Luis

    2017-05-08

    In Argentina, glyphosate use has increased exponentially in the past years due to the widespread adoption of no-till management combined with genetically modified glyphosate-resistant crops. This massive use of glyphosate has created concern about its potential environmental impact. Sorption-desorption of glyphosate was studied in three Argentinean soils with contrasting characteristics. Glyphosate sorption isotherms were modeled using the Freundlich equation to estimate the sorption coefficient (Kf ). Glyphosate sorption was high and the Kf varied from 115.6 to 1612 mg (1-1/n) L(1/n) /Kg. Cerro Azul soil had the highest glyphosate sorption capacity due to a combination of factors such as higher clay content, CEC, total Fe, Al oxides and lower available phosphorous and pH. Desorption isotherms were also modeled using the Freundlich equation. In general, desorption was very low (glyphosate strongly sorbs to the soils and that it is almost an irreversible process. Anguil soil had a significant higher desorption coefficient (Kfd ) than the other soils, associated with its lower clay content and higher pH and phosphorous. Glyphosate high sorption and low desorption to the studied soils may prevent groundwater contamination. However, it may also affect its bioavailability increasing its persistence and favoring its accumulation in environment. Results of this study contribute to the knowledge and characterization of glyphosate retention in different soils. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  11. Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System

    Directory of Open Access Journals (Sweden)

    Hiroki Miyaoka

    2015-06-01

    Full Text Available Various synthesis and rehydrogenation processes of lithium hydride (LiH and magnesium amide (Mg(NH22 system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH22 lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH22 system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H2 at 150 °C.

  12. Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System.

    Science.gov (United States)

    Miyaoka, Hiroki; Wang, Yongming; Hino, Satoshi; Isobe, Shigehito; Tokoyoda, Kazuhiko; Ichikawa, Takayuki; Kojima, Yoshitsugu

    2015-06-29

    Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH₂)₂) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH₂)₂ lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH₂)₂ system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H₂ at 150 °C.

  13. Hydrogen desorption properties of magnesium hydride catalyzed multiply with carbon and silicon

    Energy Technology Data Exchange (ETDEWEB)

    Klimkowicz, Alicja [AGH University of Science and Technology Faculty of Energy and Fuels, al. A. Mickiewicza 30, 30-059 Krakow (Poland); Shibaura Institute of Technology, Department of Engineering Science and Mechanics, 3-7-5 Toyosu, Koto-ku 135-8548, Tokyo (Japan); Takasaki, Akito, E-mail: takasaki@sic.shibaura-it.ac.jp [Shibaura Institute of Technology, Department of Engineering Science and Mechanics, 3-7-5 Toyosu, Koto-ku 135-8548, Tokyo (Japan); Gondek, Łukasz; Figiel, Henryk [AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, al. A. Mickiewicza 30, 30-059 Krakow (Poland); Świerczek, Konrad [AGH University of Science and Technology Faculty of Energy and Fuels, al. A. Mickiewicza 30, 30-059 Krakow (Poland)

    2015-10-05

    Highlights: • Crystal structure of 2 mol MgH{sub 2} + (1 − X) mol C + X mol Si (for X = 0, 0.25, 0.5, 0.75 and 1). • Enhanced hydrogen desorption properties. • Lowered temperature of hydrogen desorption for MgH{sub 2} with the multiple addition of C and Si. • Distribution of Si and C on MgH{sub 2} particles after mechanical milling. - Abstract: Magnesium hydride (MgH{sub 2}) is considered as one of hydrogen storage materials. However, the application is limited because of slow hydrogen kinetics and high thermodynamic stability. In this study, MgH{sub 2} powders were mechanically milled with graphite (C) and/or silicon (Si) powders, and effect of multiple addition of C and Si on hydrogen desorption properties was investigated. The multiple addition caused a decrease of the hydrogen desorption (onset and peak) temperatures more than single addition, and the lowest activation energy for hydrogen desorption, 62 kJ/mol, was obtained from sample powders of (2 mol MgH{sub 2} + 0.5 mol C + 0.5 mol Si). The surface of the sample powders after mechanical milling revealed a good distribution of C on the MgH{sub 2} surface and a presence of finer Si particles.

  14. Long-term tillage effects on soil metolachlor sorption and desorption behavior.

    Science.gov (United States)

    Ding, Guangwei; Novak, Jeffrey M; Herbert, Stephen; Xing, Baoshan

    2002-09-01

    Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.

  15. Adsorption and Desorption of Ammonium in Wetland Soils Subject to Freeze-Thaw Cycles