National Library of Energy BETA

Sample records for benzene toluene ethylbenzene

  1. Mobility of Supercooled liquid Toluene, Ethylbenzene, and Benzene...

    Office of Scientific and Technical Information (OSTI)

    and Benzene near their Glass Transition Temperatures Investigated using Inert Gas Permeation Citation Details In-Document Search Title: Mobility of Supercooled liquid...

  2. Mobility of Supercooled liquid Toluene, Ethylbenzene, and Benzene near their Glass Transition Temperatures Investigated using Inert Gas Permeation

    SciTech Connect (OSTI)

    May, Robert A.; Smith, R. Scott; Kay, Bruce D.

    2013-11-21

    We investigate the mobility of supercooled liquid toluene, ethylbenzene, and benzene near their respective glass transition temperatures (Tg). The permeation rate of Ar, Kr, and Xe through the supercooled liquid created when initially amorphous overlayers heated above their glass transition temperature is used to determine the diffusivity. Amorphous benzene crystallizes at temperatures well below its Tg and as a result the inert gas underlayer remains trapped until the onset of benzene desorption. In contrast, for toluene and ethylbenzene the onset of inert gas permeation is observed at temperatues near Tg. The inert gas desorption peak temperature as a function of the heating rate and overlayer thickness is used to quantify the diffusivity of supercooled liquid toluene and ethylbenzene from 115 K to 135 K. In this temperature range, diffusivities are found to vary across five orders of magnitude (~10-14 to 10-9 cm2/s). These data are compared to viscosity measurements and used to determine the low temperature fractional Stokes-Einstein exponent. Efforts to determine the diffusivity of a mixture of benzene and ethylbenzene are detailed, and the effect of mixing these materials on benzene crystallization is explored using infrared spectroscopy.

  3. Headspace solid-phase microextraction (HS-SPME) for the determination of benzene, toluene, ethylbenzene, and xylenes (BTEX) in foundry molding sand

    SciTech Connect (OSTI)

    Dungan, R.S. [USDA ARS, Beltsville, MD (United States). Environmental Management & Byproducts Utilization Laboratory

    2005-07-01

    The use of headspace solid-phase microextraction (HS-SPME) to determine benzene, toluene, ethylbenzene, and xylenes (BTEX) in foundry molding sand, specifically a 'green sand' (clay-bonded sand) was investigated. The BTEX extraction was conducted using a 75 {mu} M carboxen-polydimethylsiloxane (CAR-PDMS) fiber, which was suspended above 10 g of sample. The SPME fiber was desorbed in a gas chromatograph injector port (280{sup o}C for 1 min) and the analytes were characterized by mass spectrometry. The effects of extraction time and temperature, water content, and clay and bituminous coal percentage on HS-SPME of BTEX were investigated. Because green sands contain bentonite clay and carbonaceous material such as crushed bituminous coal, a matrix effect was observed. The detection limits for BTEX were determined to be {lt}= 0.18 ng g{sup -1} of green sand.

  4. Solubilities of Toluene, Benzene and TCE in High-Biomass Systems

    SciTech Connect (OSTI)

    Barton, John W.; Vodraska, Christopher D; Flanary, Sandie A.; Davison, Brian H

    2008-01-01

    We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g/mL. The solubility limit increased from 20 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE was most heavily impacted by biomass levels, changing by two orders of magnitude.

  5. Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

    SciTech Connect (OSTI)

    Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

    2009-12-23

    Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

  6. Genotoxicity and apoptosis in Drosophila melanogaster exposed to benzene, toluene and xylene: Attenuation by quercetin and curcumin

    SciTech Connect (OSTI)

    Singh, Mahendra P.; Mishra, M.; Sharma, A.; Shukla, A.K.; Mudiam, M.K.R.; Patel, D.K.; Ram, K. Ravi; Chowdhuri, D. Kar

    2011-05-15

    Monocyclic aromatic hydrocarbons (MAHs) such as benzene, toluene and xylene are being extensively used for various industrial and household purposes. Exposure to these hydrocarbons, occupationally or non-occupationally, is harmful to organisms including human. Several studies tested for toxicity of benzene, toluene and xylene, and interestingly, only a few studies looked into the attenuation. We used Drosophila model to test the genotoxic and apoptotic potential of these compounds and subsequently evaluated the efficiency of two phytochemicals, namely, quercetin and curcumin in attenuating test chemical induced toxicity. We exposed third instar larvae of wild type Drosophila melanogaster (Oregon R{sup +}) to 1.0-100.0 mM benzene, toluene or xylene, individually, for 12, 24 and 48 h and examined their apoptotic and genotoxic potential. We observed significantly (P < 0.001) increased apoptotic markers and genotoxicity in a concentration- and time-dependent manner in organisms exposed to benzene, toluene or xylene. We also observed significantly (P < 0.001) increased cytochrome P450 activity in larvae exposed to test chemicals and this was significantly reduced in the presence of 3',4'-dimethoxyflavone, a known Aryl hydrocarbon receptor (AhR) blocker. Interestingly, we observed a significant reduction in cytochrome P450 activity, GST levels, oxidative stress parameters, genotoxic and apoptotic endpoints when organisms were exposed simultaneously to test chemical along with quercetin or curcumin. The study further suggests the suitability of D. melanogaster as an alternate animal model for toxicological studies involving benzene, toluene and xylene and its potential in studying the protective role(s) of phytochemicals.

  7. Toluene pyrolysis studies and high temperature reactions of propargyl chloride

    SciTech Connect (OSTI)

    Kern, R.D.; Chen, H.; Qin, Z.

    1993-12-01

    The main focus of this program is to investigate the thermal decompositions of fuels that play an important role in the pre-particle soot formation process. It has been demonstrated that the condition of maximum soot yield is established when the reaction conditions of temperature and pressure are sufficient to establish a radical pool to support the production of polyaromatic hydrocarbon species and the subsequent formation of soot particles. However, elevated temperatures result in lower soot yields which are attributed to thermolyses of aromatic ring structures and result in the bell-shaped dependence of soot yield on temperature. The authors have selected several acyclic hydrocarbons to evaluate the chemical thermodynamic and kinetic effects attendant to benzene formation. To assess the thermal stability of the aromatic ring, the authors have studied the pyrolyses of benzene, toluene, ethylbenzene, chlorobenzene and pyridine. Time-of-flight mass spectrometry (TOF) is employed to analyze the reaction zone behind reflected shock waves. Reaction time histories of the reactants, products, and intermediates are constructed and mechanisms are formulated to model the experimental data. The TOF work is often performed with use of laser schlieren densitometry (LS) to measure density gradients resulting from the heats of various reactions involved in a particular pyrolytic system. The two techniques, TOF and LS, provide independent and complementary information about ring formation and ring rupture reactions.

  8. DISCLAIMER

    Office of Legacy Management (LM)

    ... VOC U.S. Atomic Energy Commission Austral Oil Company Benzene, toluene, ethylbenzene, and ... predecessor agency to the DOE) and Austral Oil Company (Austral). 1. I Site Location. ...

  9. Polyfunctional catalyst for processiing benzene fractions

    SciTech Connect (OSTI)

    G. Byakov; B.D. Zubitskii; B.G. Tryasunov; I.Ya. Petrov

    2009-05-15

    A by-product of the coke industry is a raw benzene fraction benzene- 1 which may serve as for catalytic processes. The paper reports a study on the influence of the composition and temperatures on the activity and selectivity of NiO-V{sub 2}O{sub 6}-MoO{sub 3}/{gamma}-Al{sub 2}O{sub 3} catalysts and the corresponding binary and tertiary subsystems are studied by a pulse method in model reactions; the hydrodealkylating of toluene and the hydrodesulfurizing of thioprhene. The optimal catalyst composition is established. The new catalyst is compared with industrial catalysts.

  10. Investigation of critical equivalence ratio and chemical speciation in flames of ethylbenzene-ethanol blends

    SciTech Connect (OSTI)

    Therrien, Richard J.; Ergut, Ali; Levendis, Yiannis A.; Richter, Henning; Howard, Jack B.; Carlson, Joel B.

    2010-02-15

    This work investigates five different one-dimensional, laminar, atmospheric pressure, premixed ethanol/ethylbenzene flames (0%, 25%, 50%, 75% and 90% ethanol by weight) at their soot onset threshold ({phi}{sub critical}). Liquid ethanol/ethylbenzene mixtures were pre-vaporized in nitrogen, blended with an oxygen-nitrogen mixture and, upon ignition, burned in premixed one-dimensional flames at atmospheric pressure. The flames were controlled so that each was at its visual soot onset threshold, and all had similar temperature profiles (determined by thermocouples). Fixed gases, light volatile hydrocarbons, polycyclic aromatic hydrocarbons (PAH), and oxygenated aromatic hydrocarbons were directly sampled at three locations in each flame. The experimental results were compared with a detailed kinetic model, and the modeling results were used to perform a reaction flux analysis of key species. The critical equivalence ratio was observed to increase in a parabolic fashion as ethanol concentration increased in the fuel mixture. The experimental results showed increasing trends of methane, ethane, and ethylene with increasing concentrations of ethanol in the flames. Carbon monoxide was also seen to increase significantly with the increase of ethanol in the flame, which removes carbon from the PAH and soot formation pathways. The PAH and oxygenated aromatic hydrocarbon values were very similar in the 0%, 25% and 50% ethanol flames, but significantly lower in the 75% and 90% ethanol flames. These results were in general agreement with the model and were reflected by the model soot predictions. The model predicted similar soot profiles for the 0%, 25% and 50% ethanol flames, however it predicted significantly lower values in the 75% and 90% ethanol flames. The reaction flux analysis revealed benzyl to be a major contributor to single and double ring aromatics (i.e., benzene and naphthalene), which was identified in a similar role in nearly sooting or highly sooting

  11. Degradative capacities and bioaugmentation potential of an anaerobic benzene-degrading bacterium strain DN11

    SciTech Connect (OSTI)

    Yuki Kasai; Yumiko Kodama; Yoh Takahata; Toshihiro Hoaki; Kazuya Watanabe

    2007-09-15

    Azoarcus sp. strain DN11 is a denitrifying bacterium capable of benzene degradation under anaerobic conditions. The present study evaluated strain DN11 for its application to bioaugmentation of benzene-contaminated underground aquifers. Strain DN11 could grow on benzene, toluene, m-xylene, and benzoate as the sole carbon and energy sources under nitrate-reducing conditions, although o- and p-xylenes were transformed in the presence of toluene. Phenol was not utilized under anaerobic conditions. Kinetic analysis of anaerobic benzene degradation estimated its apparent affinity and inhibition constants to be 0.82 and 11 {mu}M, respectively. Benzene-contaminated groundwater taken from a former coal-distillation plant site in Aichi, Japan was anaerobically incubated in laboratory bottles and supplemented with either inorganic nutrients (nitrogen, phosphorus, and nitrate) alone, or the nutrients plus strain DN11, showing that benzene was significantly degraded only when DN11 was introduced. Denaturing gradient gel electrophoresis of PCR-amplified 16S rRNA gene fragments, and quantitative PCR revealed that DN11 decreased after benzene was degraded. Following the decrease in DN11 16S rRNA gene fragments corresponding to bacteria related to Owenweeksia hongkongensis and Pelotomaculum isophthalicum, appeared as strong bands, suggesting possible metabolic interactions in anaerobic benzene degradation. Results suggest that DN11 is potentially useful for degrading benzene that contaminates underground aquifers at relatively low concentrations. 50 refs., 6 figs., 1 tab.

  12. Modeling theta-theta Interactions with the Effective Fragment Potential Method: The Benzene Dimer and Substituents

    SciTech Connect (OSTI)

    Toni Smithl; Lyudmila V. Slipchenko; Mark S. Gordon

    2008-02-27

    This study compares the results of the general effective fragment potential (EFP2) method to the results of a previous combined coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] and symmetry-adapted perturbation theory (SAPT) study [Sinnokrot and Sherrill, J. Am. Chem. Soc., 2004, 126, 7690] on substituent effects in {pi}-{pi} interactions. EFP2 is found to accurately model the binding energies of the benzene-benzene, benzene-phenol, benzene-toluene, benzene-fluorobenzene, and benzene-benzonitrile dimers, as compared with high-level methods [Sinnokrot and Sherrill, J. Am. Chem. Soc., 2004, 126, 7690], but at a fraction of the computational cost of CCSD(T). In addition, an EFP-based Monte Carlo/simulated annealing study was undertaken to examine the potential energy surface of the substituted dimers.

  13. Environmental Groundwater Monitoring Report

    Office of Legacy Management (LM)

    ... O F U.S. Atomic Energy Commission Austral Oil Company Benzene, toluene, ethylbenzene, and ... agency to the DOE), and Austral Oil Company (Austral). 1 I Site Location The ...

  14. I I

    Office of Legacy Management (LM)

    ... VOC U.S. Atomic Energy Commission Austral Oil Company Benzene, toluene, ethylbenzene, and ... predecessor agency to the DOE, and Austral Oil Company (Austral). 1 7 Site Location The ...

  15. A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

    SciTech Connect (OSTI)

    Tian, Z; Pitz, W J; Fournet, R; Glaude, P; Battin-Leclerc, F

    2009-12-18

    An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene, decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C{sub 4} + C{sub 2} species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C{sub 6}H{sub 4}CH{sub 3} radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C{sub 6}H{sub 4}CH{sub 3} radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics.

  16. Soot precursor measurements in benzene and hexane diffusion flames

    SciTech Connect (OSTI)

    Kobayashi, Y.; Furuhata, T.; Amagai, K.; Arai, M.

    2008-08-15

    To clarify the mechanism of soot formation in diffusion flames of liquid fuels, measurements of soot and its precursors were carried out. Sooting diffusion flames formed by a small pool combustion equipment system were used for this purpose. Benzene and hexane were used as typical aromatic and paraffin fuels. A laser-induced fluorescence (LIF) method was used to obtain spatial distributions of polycyclic aromatic hydrocarbons (PAHs), which are considered as soot particles. Spatial distributions of soot in test flames were measured by a laser-induced incandescence (LII) method. Soot diameter was estimated from the temporal change of LII intensity. A region of transition from PAHs to soot was defined from the results of LIF and LII. Flame temperatures, PAH species, and soot diameters in this transition region were investigated for both benzene and hexane flames. The results show that though the flame structures of benzene and hexane were different, the temperature in the PAHs-soot transition region of the benzene flame was similar to that of the hexane flame. Furthermore, the relationship between the PAH concentrations measured by gas chromatography in both flames and the PAH distributions obtained from LIF are discussed. It was found that PAHs with smaller molecular mass, such as benzene and toluene, remained in both the PAHs-soot transition and sooting regions, and it is thought that molecules heavier than pyrene are the leading candidates for soot precursor formation. (author)

  17. Fuel Dependence of Benzene Pathways

    SciTech Connect (OSTI)

    Zhang, H; Eddings, E; Sarofim, A; Westbrook, C

    2008-07-14

    The relative importance of formation pathways for benzene, an important precursor to soot formation, was determined from the simulation of 22 premixed flames for a wide range of equivalence ratios (1.0 to 3.06), fuels (C{sub 1}-C{sub 12}), and pressures (20 to 760 torr). The maximum benzene concentrations in 15 out of these flames were well reproduced within 30% of the experimental data. Fuel structural properties were found to be critical for benzene production. Cyclohexanes and C{sub 3} and C{sub 4} fuels were found to be among the most productive in benzene formation; and long-chain normal paraffins produce the least amount of benzene. Other properties, such as equivalence ratio and combustion temperatures, were also found to be important in determining the amount of benzene produced in flames. Reaction pathways for benzene formation were examined critically in four premixed flames of structurally different fuels of acetylene, n-decane, butadiene, and cyclohexane. Reactions involving precursors, such as C{sub 3} and C{sub 4} species, were examined. Combination reactions of C{sub 3} species were identified to be the major benzene formation routes with the exception of the cyclohexane flame, in which benzene is formed exclusively from cascading fuel dehydrogenation via cyclohexene and cyclohexadiene intermediates. Acetylene addition makes a minor contribution to benzene formation, except in the butadiene flame where C{sub 4}H{sub 5} radicals are produced directly from the fuel, and in the n-decane flame where C{sub 4}H{sub 5} radicals are produced from large alkyl radical decomposition and H atom abstraction from the resulting large olefins.

  18. Collision lifetimes of polyatomic molecules at low temperatures: Benzenebenzene vs benzenerare gas atom collisions

    SciTech Connect (OSTI)

    Cui, Jie; Krems, Roman V.; Li, Zhiying

    2014-10-28

    We use classical trajectory calculations to study the effects of the interaction strength and the geometry of rigid polyatomic molecules on the formation of long-lived collision complexes at low collision energies. We first compare the results of the calculations for collisions of benzene molecules with rare gas atoms He, Ne, Ar, Kr, and Xe. The comparison illustrates that the mean lifetimes of the collision complexes increase monotonically with the strength of the atommolecule interaction. We then compare the results of the atombenzene calculations with those for benzenebenzene collisions. The comparison illustrates that the mean lifetimes of the benzenebenzene collision complexes are significantly reduced due to non-ergodic effects prohibiting the molecules from sampling the entire configuration space. We find that the thermally averaged lifetimes of the benzenebenzene collisions are much shorter than those for Xe with benzene and similar to those for Ne with benzene.

  19. Process for the preparation of ethyl benzene

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1995-01-01

    Ethyl benzene is produced in a catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 50.degree. C. to 300.degree. C., using as the catalyst a mole sieve characterized as acidic by feeding ethylene to the catalyst bed while benzene is conveniently added through the reflux to result in a molar excess present in the reactor to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene and diethyl benzene in the bottoms. The bottoms are fractionated, the ethyl benzene recovered and the bottoms are contacted with benzene in the liquid phase in a fixed bed straight pass reactor under conditions to transalkylate the benzene thereby converting most of the diethyl benzene to ethyl benzene which is again separated and recovered.

  20. Process for the preparation of ethyl benzene

    DOE Patents [OSTI]

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1995-12-19

    Ethyl benzene is produced in a catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 50 C to 300 C, using as the catalyst a mole sieve characterized as acidic by feeding ethylene to the catalyst bed while benzene is conveniently added through the reflux to result in a molar excess present in the reactor to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene and diethyl benzene in the bottoms. The bottoms are fractionated, the ethyl benzene recovered and the bottoms are contacted with benzene in the liquid phase in a fixed bed straight pass reactor under conditions to transalkylate the benzene thereby converting most of the diethyl benzene to ethyl benzene which is again separated and recovered. 2 figs.

  1. Evaluation of a Polyvinyl Toluene Neutron Counter Array (Conference...

    Office of Scientific and Technical Information (OSTI)

    Utilizing a compact array of borated Polyvinyl Toluene light pipes and Photomultiplier Tubes, pulse shape analysis, standard spectral histogramming, and multiplicity counting can ...

  2. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

    SciTech Connect (OSTI)

    Zhang, Li; Wu, Zili; Nelson, Nicholas; Sadow, Aaron D.; Slowing, Igor I.; Overbury, Steven H.

    2015-09-22

    Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODH reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.

  3. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zhang, Li; Wu, Zili; Nelson, Nicholas; Sadow, Aaron D.; Slowing, Igor I.; Overbury, Steven H.

    2015-09-22

    Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

  4. Low level benzene exposure in Sweden: effect on blood elements and body burden of benzene

    SciTech Connect (OSTI)

    Berlin, M.

    1985-01-01

    Measurements for benzene exposure were performed for different work places. In addition, breath benzene concentrations were measured in different occupations in order to establish toxico-kinetics of benzene in man; chromosomal aberrations in lymphocytes of exposed workers were also examined. Smoking appears to result in a large increase in benzene concentration in exhaled breath. The smoke from one cigarette contains 60-80 micrograms of benzene. It was found that exposure levels of 10 ppm are rather uncommon among workers handling gasoline or gasoline equipment. It was concluded that the gasoline load of road tankers cannot be responsible for chromosome changes of the driver, as milk truck drivers showed the same changes. These results did not prove that benzene was the cause of the observed changes. Smoking is the confounding factor, with a potency of at least the same order of magnitude as benzene. In addition, our present knowledge about mechanisms of benzene is not sufficiently developed to permit quantitative conclusions as to the human health risks.

  5. Indirect validation of benzene exposure assessment by association with benzene poisoning

    SciTech Connect (OSTI)

    Dosemeci, M.; Linet, M.; Wacholder, S.

    1996-12-01

    We present a validation study of a quantitative retrospective exposure assessment method used in a follow-up study of workers exposed to benzene. Assessment of exposure to benzene was carried out in 672 factories in 12 cities in China. Historical exposure data were collected for 3179 unique job titles. The basic unit for exposure assessment was a factory/work unit/job title combination over seven periods between 1949 and 1987. A total of 18,435 exposure estimates was developed, using all available historical information, including 8477 monitoring data. Overall, 38% of the estimates were based on benzene monitoring data. The highest time-weighted average exposures were observed for the rubber industry (30.7 ppm) and for rubber glue applicators (52.6 ppm). Because of its recognized link with benzene exposure, the association between a clinical diagnosis of benzene poisoning and benzene exposure was evaluated to validate the assessment method that we used in the cohort study. Our confidence in the assessment method is supported by the observation of a strong positive trend between benzene poisoning and various measures, especially recent intensity of exposure to benzene. 23 refs., 6 figs., 2 tabs.

  6. Exposure Evaluation for Benzene, Lead and Noise in Vehicle and Equipment Repair Shops

    SciTech Connect (OSTI)

    Sweeney, Lynn C.

    2013-04-01

    An exposure assessment was performed at the equipment and vehicle maintenance repair shops operating at the U. S. Department of Energy Hanford site, in Richland, Washington. The maintenance shops repair and maintain vehicles and equipment used in support of the Hanford cleanup mission. There are three general mechanic shops and one auto body repair shop. The mechanics work on heavy equipment used in construction, cranes, commercial motor vehicles, passenger-type vehicles in addition to air compressors, generators, and farm equipment. Services include part fabrication, installation of equipment, repair and maintenance work in the engine compartment, and tire and brake services. Work performed at the auto body shop includes painting and surface preparation which involves applying body filler and sanding. 8-hour time-weighted-average samples were collected for benzene and noise exposure and task-based samples were collected for lead dust work activities involving painted metal surfaces. Benzene samples were obtained using 3M™ 3520 sampling badges and were analyzed for additional volatile organic compounds. These compounds were selected based on material safety data sheet information for the aerosol products used by the mechanics for each day of sampling. The compounds included acetone, ethyl ether, toluene, xylene, VM&P naphtha, methyl ethyl ketone, and trichloroethylene. Laboratory data for benzene, VM&P naphtha, methyl ethyl ketone and trichloroethylene were all below the reporting detection limit. Airborne concentrations for acetone, ethyl ether, toluene and xylene were all less than 10% of their occupational exposure limit. The task-based samples obtained for lead dusts were submitted for a metal scan analysis to identify other metals that might be present. Laboratory results for lead dusts were all below the reporting detection limit and airborne concentration for the other metals observed in the samples were less than 10% of the occupational exposure limit

  7. Benzene reduction in RFG, a new low cost route

    SciTech Connect (OSTI)

    Gildert, R.; Gildert, G.

    1994-12-31

    Benzene has been targeted for reduction in reformulated gasoline because it is the largest single contributor to the toxic emissions group. This presentation describes processes of benzene removal for the petroleum refiner. By making maximum use of existing equipment, the refiner can minimize the changes necessary to produce reformulated gasoline with a reduction in benzene levels.

  8. Pilot-Scale Benzene Retention and Release Demonstration

    SciTech Connect (OSTI)

    Marek, J.C.

    2003-11-10

    During the initial months of In-Tank Precipitation radioactive operation in 1995 the process experienced high rates of tetraphenylborate decomposition with assumed corresponding high rates of benzene generation. In March 1996 after a two month quiescent period, a water addition to Tank 48H resulted in an unexpected benzene release to the tank vapor phase. This was the first time a low energy input resulted in a significant release rate. This led to questions about how benzene, generated in-situ by TPB decomposition, was retained in the surrounding potassium tetraphenylborate slurry. It was postulated the retention mechanism may have changed during the quiescent period prior to March so the benzene present became readily releasable to the vapor phase with low energy input to the slurry or that enough benzene accumulated that some of it was in a different, more releasable form. Readily releasable is a qualitative term defined as a rapid release of benzene at a rate approaching evaporation of a free benzene layer. It is intended to distinguish between benzene in a form with high liquid phase resistance to mass transfer diffusion controlled from benzene in a form with minimal liquid phase resistance to mass transfer free benzene layer evaporation. If a readily releasable form of benzene was present, the vapor space profile during release tests was anticipated to have an initial benzene vapor space concentration peak followed by a lower vapor concentration, longer duration release.

  9. Toluene nitration in irradiated nitric acid and nitrite solution

    SciTech Connect (OSTI)

    Gracy Elias; Bruce J. Mincher; Stephen P. Mezyk; Jim Muller; Leigh R. Martin

    2011-04-01

    The kinetics, mechanisms, and stable products produced for the aryl alkyl mild ortho-para director - toluene, in irradiated nitric acid and neutral nitrite solutions were investigated using ?, and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection was primarily used to assess the stable reaction products. GC-MS and LC-MS were used to confirm the results from HPLC. Free-radical nitration reaction products were found in irradiated acidic and neutral media. In acidic medium, the ring substitution and side chain substitution and oxidation produced different nitro products. In ring substitution, nitrogen oxide radicals were added mainly to hydroxyl radical-produced cyclohexadienyl radical, and in side chain substitution they were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite toluene solution, radiolytic ring nitration products approached a statistically random distribution, suggesting a free-radical reaction involving addition of the NO2 radical.

  10. Biofiltration control of VOC emissions: Butane and benzene

    SciTech Connect (OSTI)

    Allen, E.R.

    1995-12-31

    Laboratory studies were conducted on the biological elimination of n-butane and benzene from air streams using activated sludge-treated compost biofilters. Four types of experimental biofilter systems were developed: a bench scale packed tower system used primarily for kinetic studies; a small scale column system used to study the effects of different filter media on n-butane removal; a three stage system used to study benzene elimination; and a static batch biofilter system used to study the effects of temperature, compost water content, compost pH, and initial benzene concentrations on benzene elimination. Removal efficiencies greater than 90% were obtained for n-butane. Removal followed first order kinetics at inlet concentrations less than 25 ppM n-butane and zero order kinetics above 100 ppM n-butane. Removal of benzene followed fractional order kinetics for inlet concentrations from 15 to 200 ppM benzene. Thus, the removal of benzene is both mass transfer and bioreaction limited for the concentration range studied. The removal efficiency of benzene was found to be highly dependent on compost water content, compost pH, and temperature. Compost showed a low capacity for benzene removal, which suggested that degradation of these hydrocarbons required different species of microorganisms.

  11. Catalytic conversion of alcohols to hydrocarbons with low benzene content

    DOE Patents [OSTI]

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

    2016-03-08

    A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

  12. In situ BTEX biotransformation under enhanced nitrate- and sulfate-reducing conditions

    SciTech Connect (OSTI)

    Reinhard, M.; Shang, S.; Kitanidis, P.K.; Orwin, E.; Hopkins, G.D.; LeBron, C.A.

    1997-01-01

    In situ anaerobic biotransformation of BTEX (benzene, toluene, ethylbenzene, o-xylene, and m-xylene) was investigated under enhanced nitrate- and sulfate-reducing conditions. Controlled amounts of BTEX compounds added to slugs of treated groundwater were released into a gasoline-contaminated aquifer at Seal Beach, CA. In a series of studies, the slugs, 470-1700 L in volume, were released into the aquifer through a multi-port injection/extraction well and were subsequently withdrawn over a 2-3 month period. To evaluate unamended in situ conditions, the injectate was treated with granular activated carbon (GAC) and augmented with bromide as a tracer. To evaluate nitrate- and sulfate-reducing conditions, the injectate was also deionized and augmented with 200-300 {mu}g/L BTEX, nitrate or sulfate, and background electrolytes. Under unamended conditions, transformation appeared to be limited to the slow removal of toluene and m,p-xylene (i.e. sum of m+p-xylene). Under nitrate-reducing conditions, toluene, ethylbenzene, and m-xylene were transformed without a lag phase in less than 10 days, and o-xylene was transformed in 72 days. Under sulfate-reducing conditions, toluene, m-xylene and o-xylene were completely transformed in less then 50 days, and ethylbenzene was removed in 60 days. Benzene appeared to be removed under sulfate-reducing conditions, but the trend was pronounced only at some levels. 47 refs., 11 figs., 2 tabs.

  13. Method of removing benzene from petroleum desalter brine

    SciTech Connect (OSTI)

    Hart, P.R.

    1993-08-17

    A method is described for removing benzene from petroleum refinery desalter effluent brine containing dispersed oil, solids, oily solids and benzene comprising contacting the brine with a sufficient amount for the purpose of flocculating oily solids of a combination of a aluminum chlorohydrate and a water soluble cationic polymer selected from the group consisting of polyamines and dialkyldiallylammonium polymers, in a ratio of from 1:10 to 100:1 at a temperature of about 250 F, separating the resulting floc from the brine; and thereafter contacting the brine with a sufficient amount for the purpose of reducing benzene levels in the brine of an oil solvent in combination with a demulsifier.

  14. Control of benzene waste NESHAP emissions from a petroleum refinery

    SciTech Connect (OSTI)

    Truelove, R.D. )

    1992-02-01

    This paper discusses the control of benzene emissions from a petroleum refinery as regulated by the National Emission Standards for Hazardous Air Pollutants (NESHAO) Subpart FF - National Standard for Benzene Waste Operations. This regulation is complex and confusing, but it provides flexibility to achieve compliance through various strategies to control benzene emissions. The first step to achieve compliance with the benzene waste NESHAP is understanding the regulation itself. Therefore, this paper summarizes the regulation to provide the reader with sufficient background to understand why specific controls are required for specific processes. The flexibility provided by the regulation to achieve compliance is not always readily apparent. This paper summarizes some of these subtleties. The author's involvement with an industry trade association in meetings with the Environmental Protection Agency during the development of the regulation allows some of EPA's expressions of their intent and internal interpretation to also be contained in the summary. The second step to achieve compliance with the benzene waste NESHAP is to actually design and operate a cost effective solution for a specific set of existing conditions within a refinery. This paper provides a case study of the equipment necessary to achieve compliance with the substantive requirements of the regulation at a large, integrated refinery. The retrofit requirements are very specific to the circumstances of this facility. Therefore, they will not be a universal, cost effective means of compliance for other refineries.

  15. Products of the Benzene + O(3P) Reaction

    SciTech Connect (OSTI)

    Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Meloni, Giovanni; Trevitt, Adam J.; Epifanovsky, Evgeny; Krylov, Anna I.; Sirjean, Baptiste; Dames, Enoch; Wang, Hai

    2009-12-21

    The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming an initial triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom, or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range of 300 to 1000 K and pressure range of 1 to 10 Torr. The reactions were initiated by pulsed-laser photolysis of NO2 in the presence of benzene and helium buffer in a slow-flow reactor, and reaction products were identified by using the multiplexed chemical kinetics photoionization mass spectrometer operating at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory. Phenol and phenoxy radical were detected and quantified. Cyclopentadiene and cyclopentadienyl radical were directly identified for the first time. Finally, ab initio calculations and master equation/RRKM modeling were used to reproduce the experimental branching ratios, yielding pressure-dependent rate expressions for the reaction channels, including phenoxy + H, phenol, cyclopentadiene + CO, which are proposed for kinetic modeling of benzene oxidation.

  16. Effect of ozonation on the composition of crude coal-tar benzene

    SciTech Connect (OSTI)

    Semenova, S.A.; Patrakov, Y.F.

    2007-05-15

    The effect of ozonation on the composition of crude benzene produced by the coal-tar chemical industry was studied.

  17. New packing in absorption systems for trapping benzene from coke-oven gas

    SciTech Connect (OSTI)

    V.V. Grabko; V.M. Li; T.A. Shevchenko; M.A. Solov'ev

    2009-07-15

    The efficiency of benzene removal from coke-oven gas in absorption units OAO Alchevskkoks with new packing is assessed.

  18. Designed synthesis of multifunctional Fe{sub 3}O{sub 4}@SiO{sub 2}–NH{sub 2}@CS–Co(II) towards efficient oxidation of ethylbenzene

    SciTech Connect (OSTI)

    Li, Shi; Zhai, Shang-Ru; An, Qing-Da; Li, Ming-Hui; Song, Yu; Song, Xiao-Wei

    2014-12-15

    Highlights: • Cooperative integration of magnetic cores and chitosan layers. • Efficient and durable catalyst for the oxidation of ethylbenzene to acetophenone. • Exceptional results of 82.5% EB conversion and 80.4% AP selectivity. • Magnetic recoverable catalyst with excellent reusability even after 10 times run. - Abstract: The preparation of Co(II) supported magnetic heterogeneous catalyst, i.e. Fe{sub 3}O{sub 4}@SiO{sub 2}–NH{sub 2}@CS–Co, and its efficient and selective catalytic properties toward the oxidation of ethylbenzene to acetophenone are presented. The materials were characterized by various physicochemical techniques such as scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, vibrating sample magnetometer, elemental analysis, inductively coupled plasma-atomic emission spectrometer and X-ray photoelectron spectroscopy, etc. The reaction conditions were thoroughly investigated and highly improved catalytic performance (82.5% conversion of ethylbenzene and 80.1% selectivity to acetophenone) was gained under more mild reaction conditions of lower temperature (70 °C), shorter reaction period (60 min) and cheaper and greener oxygen source (H{sub 2}O{sub 2}). More importantly, it could be reused successively at least 10 times when more than 80% of its catalytic activity maintained.

  19. Molecular dynamics simulations of the effects of salts on the aggregation properties of benzene in water.

    SciTech Connect (OSTI)

    Smith, P. E.

    2003-07-16

    The specific aims of the project were: to provide an atomic level description of the interactions between benzene, water and ions in solutions. To determine the degree of association between two benzene molecules in aqueous and salt solutions. To investigate the structure and dynamics of the interface between benzene and water or salt solution.

  20. Biocatalytic conversion of ethylene to ethylene oxide using an engineered toluene monooxygenase

    SciTech Connect (OSTI)

    Carlin, DA; Bertolani, SJ; Siegel, JB

    2015-01-01

    Mutants of toluene o-xylene monooxygenase are demonstrated to oxidize ethylene to ethylene oxide in vivo at yields of >99%. The best mutant increases ethylene oxidation activity by >5500-fold relative to the native enzyme. This is the first report of a recombinant enzyme capable of carrying out this industrially significant chemical conversion.

  1. Benzene distribution in product streams from in-tank processing

    SciTech Connect (OSTI)

    Walker, D.D.

    1987-01-15

    Benzene is the major product of radiolytic decomposition of tetraphenylborate salts during in-tank salt decontamination. Its production rate has been measured at the Savannah River Laboratory (SR) and at the University of Florida under various conditions of importance to the in-tank process. Recent work has been concerned with the extent of decomposition for long storage periods, and the composition of the product streams from the process. The major results from this work are: the stored potassium tetraphenylborate precipitate will decompose at a rate of 7.3 {plus minus} 1.1% per year; the major products of the decomposition are benzene, phenol, biphenyl, and phenylboric acid; decomposition is directly proportional to the total dose and is unaffected by dose rate; the decomposition produces acidic compounds which will cause a decrease in the pH of the storage tank. 13 refs., 6 figs., 6 tabs.

  2. Tip-contact related low-bias negative differential resistance and rectifying effects in benzeneporphyrinbenzene molecular junctions

    SciTech Connect (OSTI)

    Cheng, Jue-Fei; Zhou, Liping E-mail: leigao@suda.edu.cn; Liu, Man; Yan, Qiang; Han, Qin; Gao, Lei E-mail: leigao@suda.edu.cn

    2014-11-07

    The electronic transport properties of benzeneporphyrinbenzene (BPB) molecules coupled to gold (Au) electrodes were investigated. By successively removing the front-end Au atoms, several BPB junctions with different molecule-electrode contact symmetries were constructed. The calculated currentvoltage (IV) curves depended strongly on the contact configurations between the BPB molecules and the Au electrodes. In particular, a significant low-voltage negative differential resistance effect appeared at ?0.3 V in the junctions with pyramidal electrodes on both sides. Along with the breaking of this tip-contact symmetry, the low-bias negative differential resistance effect gradually disappeared. This tip-contact may be ideal for use in the design of future molecular devices because of its similarity with experimental processes.

  3. Occupational Exposure to Benzene from Painting with Epoxy and Other High Performance Coatings

    SciTech Connect (OSTI)

    JAHN, STEVEN

    2005-04-20

    Following the discovery of trace benzene in paint products, an assessment was needed to determine potential for benzene exposures to exceed the established ACGIH Threshold Limit Value (TLV) during painting operations. Sample data was collected by area industrial hygienists for benzene during routine maintenance and construction activities at Savannah River Site. A set of available data from the IH database, Sentry, was analyzed to provide guidance to the industrial hygiene staff and draw conclusions on the exposure potential during typical painting operations.

  4. Decomposition of toluene in a steady-state atmospheric-pressure glow discharge

    SciTech Connect (OSTI)

    Trushkin, A. N.; Grushin, M. E.; Kochetov, I. V.; Trushkin, N. I.; Akishev, Yu. S.

    2013-02-15

    Results are presented from experimental studies of decomposition of toluene (C{sub 6}H{sub 5}CH{sub 3}) in a polluted air flow by means of a steady-state atmospheric pressure glow discharge at different water vapor contents in the working gas. The experimental results on the degree of C{sub 6}H{sub 5}CH{sub 3} removal are compared with the results of computer simulations conducted in the framework of the developed kinetic model of plasma chemical decomposition of toluene in the N{sub 2}: O{sub 2}: H{sub 2}O gas mixture. A substantial influence of the gas flow humidity on toluene decomposition in the atmospheric pressure glow discharge is demonstrated. The main mechanisms of the influence of humidity on C{sub 6}H{sub 5}CH{sub 3} decomposition are determined. The existence of two stages in the process of toluene removal, which differ in their duration and the intensity of plasma chemical decomposition of C{sub 6}H{sub 5}CH{sub 3} is established. Based on the results of computer simulations, the composition of the products of plasma chemical reactions at the output of the reactor is analyzed as a function of the specific energy deposition and gas flow humidity. The existence of a catalytic cycle in which hydroxyl radical OH acts a catalyst and which substantially accelerates the recombination of oxygen atoms and suppression of ozone generation when the plasma-forming gas contains water vapor is established.

  5. First Principals and Classical Molecular Dynamics Simulations of Solvated Benzene

    SciTech Connect (OSTI)

    Allesch, M; Lightstone, F; Schwegler, E; Galli, G

    2007-09-11

    We have performed extensive ab initio and classical MD simulations of benzene in water in order to examine the unique solvation structures that are formed. Qualitative differences between classical and ab initio MD simulations are found and the importance of various technical simulation parameters is examined. Our comparison indicates that non-polarizable classical models are not capable of describing the solute-water interface correctly if local interactions become energetically comparable to water hydrogen bonds. In addition, a comparison is made between a rigid water model and fully flexible water within ab initio MD simulations which shows that both models agree qualitatively for this challenging system.

  6. Location of MTBE and toluene in the channel system of the zeolite mordenite: Adsorption and host-guest interactions

    SciTech Connect (OSTI)

    Arletti, Rossella; Martucci, Annalisa; Alberti, Alberto; Pasti, Luisa; Nassi, Marianna; Bagatin, Roberto

    2012-10-15

    This paper reports a study of the location of Methyl Tertiary Butyl Ether (MTBE) and toluene molecules adsorbed in the pores of the organophylic zeolite mordenite from an aqueous solution. The presence of these organic molecules in the zeolite channels was revealed by structure refinement performed by the Rietveld method. About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the cavities of mordenite, representing 75% and 80% of the total absorption capacity of this zeolite. In both cases a water molecule was localized inside the side pocket of mordenite. The saturation capacity determined by the adsorption isotherms, obtained by batch experiments, and the weight loss given by thermogravimetric (TG) analyses were in very good agreement with these values. The interatomic distances obtained after the structural refinements suggest MTBE could be connected to the framework through a water molecule, while toluene could be bonded to framework oxygen atoms. The rapid and high adsorption of these hydrocarbons into the organophylic mordenite zeolite makes this cheap and environmental friendly material a suitable candidate for the removal of these pollutants from water. - graphical abstract: Location of MTBE (a) and toluene (b) in mordenite channels (projection along the [001] direction). Highlights: Black-Right-Pointing-Pointer We investigated the MTBE and toluene adsorption process into an organophilic zeolite mordenite. Black-Right-Pointing-Pointer The presence of MTBE and toluene in mordenite was determined by X-ray diffraction studies. Black-Right-Pointing-Pointer About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the zeolite cavities. Black-Right-Pointing-Pointer MTBE is connected to the framework through a water molecule. Black-Right-Pointing-Pointer Toluene is directly bonded to framework oxygen atoms.

  7. Simulation of toluene decomposition in a pulse-periodic discharge operating in a mixture of molecular nitrogen and oxygen

    SciTech Connect (OSTI)

    Trushkin, A. N.; Kochetov, I. V.

    2012-05-15

    The kinetic model of toluene decomposition in nonequilibrium low-temperature plasma generated by a pulse-periodic discharge operating in a mixture of nitrogen and oxygen is developed. The results of numerical simulation of plasma-chemical conversion of toluene are presented; the main processes responsible for C{sub 6}H{sub 5}CH{sub 3} decomposition are identified; the contribution of each process to total removal of toluene is determined; and the intermediate and final products of C{sub 6}H{sub 5}CH{sub 3} decomposition are identified. It was shown that toluene in pure nitrogen is mostly decomposed in its reactions with metastable N{sub 2}(A{sub 3}{Sigma}{sub u}{sup +}) and N{sub 2}(a Prime {sup 1}{Sigma}{sub u}{sup -}) molecules. In the presence of oxygen, in the N{sub 2} : O{sub 2} gas mixture, the largest contribution to C{sub 6}H{sub 5}CH{sub 3} removal is made by the hydroxyl radical OH which is generated in this mixture exclusively due to plasma-chemical reactions between toluene and oxygen decomposition products. Numerical simulation showed the existence of an optimum oxygen concentration in the mixture, at which toluene removal is maximum at a fixed energy deposition.

  8. Anaerobic biodegradation of BTEX in aquifer material. Environmental research brief

    SciTech Connect (OSTI)

    Borden, R.C.; Hunt, M.J.; Shafer, M.B.; Barlaz, M.A.

    1997-08-01

    Laboratory and field experiments were conducted in two petroleum-contaminated aquifers to examine the anaerobic biodegradation of benzene, toluene, ethylbenzene and xylene isomers (BTEX) under ambient conditions. Aquifer material was collected from locations at the source, mid-plume and end-plume at both sites, incubated under ambient conditions, and monitored for disappearance of the test compounds. In the mid-plume location at the second site, in-situ column experiments were also conducted for comparison with the laboratory microscosm and field-scale results. In the end-plume microcosms, biodegradation was variable with extensive biodegradation in some microcosms and little or no biodegradation in others.

  9. Intermolecular C?H bond activation of benzene and pyridines by a vanadium(III) alkylidene including a stepwise conversion of benzene to a vanadium-benzyne complex

    SciTech Connect (OSTI)

    Andino, Jos G.; Kilgore, Uriah J.; Pink, Maren; Ozarowski, Andrew; Krzystek, J.; Telser, Joshua; Baik, Mu-Hyun; Mindiola, Daniel J.

    2012-01-20

    Breaking of the carbon-hydrogen bond of benzene and pyridine is observed with (PNP)V(CH{sub 2}tBu){sub 2} (1), and in the case of benzene, the formation of an intermediate benzyne complex (C) is proposed, and indirect proof of its intermediacy is provided by identification of (PNP)VO({eta}{sup 2}-C{sub 6}H{sub 4}) in combination with DFT calculations.

  10. The relationship between low-level benzene exposure and leukemia in Canadian petroleum distribution workers

    SciTech Connect (OSTI)

    Schnatter, A.R.; Armstrong, T.W.; Nicolich, M.J.

    1996-12-01

    This study was conducted to evaluate the relationship between leukemia occurrence and long-term, low-level benzene exposures in petroleum distribution workers. Fourteen cases were identified among a previously studied cohort. Four controls per case were selected from the same cohort, controlling for birth year and time at risk. Industrial hygienists estimated workplace exposures for benzene, without knowledge of case-control status. Average benzene concentrations ranged from 0.01 to 6.2 ppm. Company medical records were used to abstract information on other potential confounders such as cigarette smoking. Odds ratios were calculated for several exposure metrics. Conditional logistic regression modeling was used to control for potential confounders. The risk of leukemia was not associated with increasing cumulative exposure to benzene for these exposure levels. Duration of benzene exposure was more closely associated with leukemia risk than other exposure metrics, although results were not statistically significant. A family history of cancer and cigarette smoking were the two strongest risk factors for leukemia, with cumulative benzene exposure showing no additional risk when considered in the same models. This study is consistent with other data in that it was unable to demonstrate a relationship between leukemia and long-term, low-level benzene exposures. The power of the study was limited. Thus, further study on benzene exposures in this concentration range are warranted. 20 refs., 1 fig., 6 tabs.

  11. Geographical distribution of benzene in air in northwestern Italy and personal exposure

    SciTech Connect (OSTI)

    Gilli, G.; Scursatone, E.; Bono, R.

    1996-12-01

    Benzene is a solvent strictly related to some industrial activities and to automotive emissions. After the reduction in lead content of fuel gasoline, and the consequent decrease in octane number, an increase in benzene and other aromatic hydrocarbons in gasoline occurred. Therefore, an increase in the concentration of these chemicals in the air as primary pollutants and as precursors of photochemical smog could occur in the future. The objectives of this study were to describe the benzene air pollution at three sites in northwestern Italy throughout 1991 and 1994; to examine the relationship between benzene air pollution in indoor, outdoor, and personal air as measured by a group of nonsmoking university students; and to determine the influence of environmental tobacco smoke on the level of benzene exposure in indoor air environments. The results indicate a direct relationship between population density and levels of contamination; an indoor/outdoor ratio of benzene air pollution higher than 1 during day and night; a similar level of personal and indoor air contamination; and a direct relationship between levels of personal exposure to benzene and intensity of exposure to tobacco smoke. Human exposure to airborne benzene has been found to depend principally on indoor air contamination not only in the home but also in many other confined environments. 29 refs., 2 figs., 6 tabs.

  12. Site-specific variability in BTEX biodegradation under denitrifying conditions

    SciTech Connect (OSTI)

    Kao, C.M.; Borden, R.C.

    1997-03-01

    Laboratory microcosm experiments were conducted to evaluate the feasibility of benzene, toluene, ethylbenzene, m-xylene, and o-xylene (BTEX) biodegradation under denitrifying conditions. Nine different sources of inocula, including contaminated and uncontaminated soil cores from four different sites and activated sludge, were used to establish microcosms. BTEX was not degraded under denitrifying conditions in microcosms inoculated with aquifer material from Rocky Point and Traverse City. However, rapid depletion of glucose under denitrifying conditions was observed in microcosms containing Rocky Point aquifer material. TEX degradation was observed in microcosms containing Rocky Point aquifer material. TEX degradation was observed in microcosms containing aquifer material from Fort Bragg and Sleeping Bear Dunes and sewage sludge. Benzene was recalcitrant in all microcosms tested. The degradation of o-xylene ceased after toluene, ethylbenzene, and m-xylene were depleted in the Fort Bragg and sludge microcosms, but o-xylene continued to degrade in microcosms with contaminated Sleeping Bear Dunes soil. The most probable number (MPN) of denitrifiers in these nine different inocula were measured using a microtiter technique. There was no correlation between the MPN of denitrifiers and the TEX degradation rate under denitrifying conditions. Experimental results indicate that the degradation sequence and TEX degradation rate under denitrifying conditions may differ among sites. Results also indicate that denitrification alone may not be a suitable bioremediation technology for gasoline-contaminated aquifers because of the inability of denitrifiers to degrade benzene.

  13. Process for hydrocracking carbonaceous material to provide fuels or chemical feed stock

    DOE Patents [OSTI]

    Duncan, Dennis A.

    1980-01-01

    A process is disclosed for hydrocracking coal or other carbonaceous material to produce various aromatic hydrocarbons including benzene, toluene, xylene, ethylbenzene, phenol and cresols in variable relative concentrations while maintaining a near constant maximum temperature. Variations in relative aromatic concentrations are achieved by changing the kinetic severity of the hydrocracking reaction by altering the temperature profile up to and quenching from the final hydrocracking temperature. The relative concentration of benzene to the alkyl and hydroxyl aromatics is increased by imposing increased kinetic severity above that corresponding to constant heating rate followed by immediate quenching at about the same rate to below the temperature at which dehydroxylation and dealkylation reactions appreciably occur. Similarly phenols, cresols and xylenes are produced in enhanced concentrations by adjusting the temperature profile to provide a reduced kinetic severity relative to that employed when high benzene concentrations are desired. These variations in concentrations can be used to produce desired materials for chemical feed stocks or for fuels.

  14. Solubilities of toluene and n-octane in aqueous protosurfactant and surfactant solutions

    SciTech Connect (OSTI)

    Ho, P.C.

    1985-01-01

    The solubilities of toluene and n-octane in aqueous protosurfactant and surfactant solutins were determined at 25/sup 0/C. The protosurfactants studied are sodium salts of cyclohexanecarboxylic acid, 2,5-diisopropylbenzenesulfonic acid, and 3,5-diisopropyisalicylic acid. Each of them has six alkyl carbons (S /SUB AC/ =6) and does not form micelles in water. The two micelle-forming surfactants used are sodium n-hexanoate with six alkyl carbons (S /SUB AC/ =6) and sodium n-octanoate with eight alkyl carbons (S /SUB AC/ =8). In three-component systems of toluene or n-octane with water and organic salt (either protosurfactant or surfactant), the solubility of the hydrocarbon in the aqueous phase increases as the number of alkyl carbons of the organic salt and as the aqueous concentration of the organic salt increases. However, in this study we found that sodium 3,5-diisopropyisalicylate causes much more pronounced increases in hydrocarbon solubility than these two surfactants. Sodium 2,5-diisopropylbenzenesulfonate, although not as effective in solubilization as the salicylate, has much stronger hydrotropic properties for hydrocarbons than either of these two surfactants. Sodium cyclohexanoate, with a compact arrangement of the six alkyl carbons, shows a higher hydrotropic effect than sodium n-hexanoate.

  15. Interaction of toluene with two-color asymmetric laser fields: Controlling the directional emission of molecular hydrogen fragments

    SciTech Connect (OSTI)

    Kaziannis, S.; Kotsina, N.; Kosmidis, C.

    2014-09-14

    The interaction of toluene with strong asymmetric two-color laser irradiation of 40 fs duration is studied by means of Time of flight mass spectrometry. Highly energetic H{sub 2}{sup +} and H{sub 3}{sup +} fragment ions are produced through an isomerization process taking place within transient multiply charged parent ions. Comparative study of deuterium labeled toluene isotopes enables the discrimination between molecular hydrogen fragments formed exclusively within the CH{sub 3}- part from those that require hydrogen atom exchange between the former and the phenyl moiety. It is demonstrated that by manipulating the relative phase of the ω/2ω field components the selective ionization of oriented toluene molecules can be used as a tool to control the directional emission of the H{sub 2}{sup +}, H{sub 3}{sup +} species.

  16. Numerical analysis of the effect of acetylene and benzene addition to low-pressure benzene-rich flat flames on polycyclic aromatic hydrocarbon formation

    SciTech Connect (OSTI)

    Kunioshi, Nilson; Komori, Seisaku; Fukutani, Seishiro

    2006-10-15

    A modification of the CHEMKIN II package has been proposed for modeling addition of an arbitrary species at an arbitrary temperature to an arbitrary distance from the burner along a flat flame. The modified program was applied to the problem of addition of acetylene or benzene to different positions of a 40-Torr, {phi}=2.4 benzene/O{sub 2}/40%-N{sub 2} premixed flame to reach final equivalence ratios of {phi}=2.5 and 2.681. The results obtained showed that acetylene addition to early positions of the flame led to significant increase in pyrene production rates, but pyrene concentrations were lower in the flames with acetylene addition in both the {phi}=2.5 and 2.681 cases. Addition of benzene to the flame did not alter pyrene production rates in either the {phi}=2.5 or 2.681 cases; however, for {phi}=2.5, pyrene concentrations increased with benzene addition, while for {phi}=2.681, pyrene contents decreased in comparison to the correspondent flames with no addition. Acetylene addition led to a significant increase in pyrene production rates, but the pyrene levels dropped due to increase in the flow velocity. Pyrene production rates were not sensitive to benzene addition, but pyrene contents increased with benzene addition when the flow velocity decreased. These results show that PAH concentration changes accompanying species addition to flames should be interpreted carefully, because an increase or decrease in the content of a PAH species does not necessarily reflect an effect on its formation rate or mechanism. (author)

  17. COSMIC-RAY-MEDIATED FORMATION OF BENZENE ON THE SURFACE OF SATURN'S MOON TITAN

    SciTech Connect (OSTI)

    Zhou Li; Zheng Weijun; Kaiser, Ralf I.; Landera, Alexander; Mebel, Alexander M.; Liang, Mao-Chang; Yung, Yuk L.

    2010-08-01

    The aromatic benzene molecule (C{sub 6}H{sub 6})-a central building block of polycyclic aromatic hydrocarbon molecules-is of crucial importance for the understanding of the organic chemistry of Saturn's largest moon, Titan. Here, we show via laboratory experiments and electronic structure calculations that the benzene molecule can be formed on Titan's surface in situ via non-equilibrium chemistry by cosmic-ray processing of low-temperature acetylene (C{sub 2}H{sub 2}) ices. The actual yield of benzene depends strongly on the surface coverage. We suggest that the cosmic-ray-mediated chemistry on Titan's surface could be the dominant source of benzene, i.e., a factor of at least two orders of magnitude higher compared to previously modeled precipitation rates, in those regions of the surface which have a high surface coverage of acetylene.

  18. Electron localization in a mixed-valence diniobium benzene complex

    SciTech Connect (OSTI)

    Gianetti, Thomas L.; Nocton, Grgory; Minasian, Stefan G.; Kaltsoyannis, Nikolas; Kilcoyne, A. L. David; Kozimor, Stosh A.; Shuh, David K.; Tyliszczak, Tolek; Bergman, Robert G.; Arnold, John

    2014-11-11

    Reaction of the neutral diniobium benzene complex {[Nb(BDI)NtBu]2(?-C6H6)} (BDI = N,N'-diisopropylbenzene-?-diketiminate) with Ag[B(C6F5)4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)NtBu]2(?-C6H6)}{B(C6F5)4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the ?-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.

  19. Electron localization in a mixed-valence diniobium benzene complex

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.; Kaltsoyannis, Nikolas; Kilcoyne, A. L. David; Kozimor, Stosh A.; Shuh, David K.; Tyliszczak, Tolek; Bergman, Robert G.; Arnold, John

    2014-11-11

    Reaction of the neutral diniobium benzene complex {[Nb(BDI)NtBu]2(μ-C6H6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C6F5)4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)NtBu]2(μ-C6H6)}{B(C6F5)4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment of a diniobium complex, in which one Nb atom carries a single unpaired electron that ismore » not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

  20. Diffusion of benzene confined in the oriented nanochannels of chrysotile asbestos fibers

    SciTech Connect (OSTI)

    Mamontov, E.; Kumzerov, Yu.A.; Vakhrushev, S.B.

    2005-11-01

    We used quasielastic neutron scattering to study the dynamics of benzene that completely fills the nanochannels of chrysotile asbestos fibers with a characteristic diameter of about 5 nm. The macroscopical alignment of the nanochannels in fibers provided an interesting opportunity to study anisotropy of the dynamics of confined benzene by means of collecting the data with the scattering vector either parallel or perpendicular to the fibers axes. The translational diffusive motion of benzene molecules was found to be isotropic. While bulk benzene freezes at 278.5 K, we observed the translational dynamics of the supercooled confined benzene on the time scale of hundreds of picoseconds even below 200 K, until at about 160 K its dynamics becomes too slow for the {mu}eV resolution of the neutron backscattering spectrometer. The residence time between jumps for the benzene molecules measured in the temperature range of 260 K to 320 K demonstrated low activation energy of 2.8 kJ/mol.

  1. Hoe Creek groundwater restoration, 1989

    SciTech Connect (OSTI)

    Renk, R.R.; Crader, S.E.; Lindblom, S.R.; Covell, J.R.

    1990-01-01

    During the summer of 1989, approximately 6.5 million gallons of contaminated groundwater were pumped from 23 wells at the Hoe Creek underground coal gasification site, near Gillette, Wyoming. The organic contaminants were removed using activated carbon before the water was sprayed on 15.4 acres at the sites. Approximately 2647 g (5.8 lb) of phenols and 10,714 g (23.6 lb) of benzene were removed from the site aquifers. Phenols, benzene, toluene, ethylbenzene, and naphthalene concentrations were measured in 43 wells. Benzene is the only contaminant at the site exceeds the federal standard for drinking water (5 {mu}g/L). Benzene leaches into the groundwater and is slow to biologically degrade; therefore, the benzene concentration has remained high in the groundwater at the site. The pumping operation affected groundwater elevations across the entire 80-acre site. The water levels rebounded quickly when the pumping operation was stopped on October 1, 1989. Removing contaminated groundwater by pumping is not an effective way to clean up the site because the continuous release of benzene from coal tars is slow. Benzene will continue to leach of the tars for a long time unless its source is removed or the leaching rate retarded through mitigation techniques. The application of the treated groundwater to the surface stimulated plant growth. No adverse effects were noted or recorded from some 60 soil samples taken from twenty locations in the spray field area. 20 refs., 52 figs., 8 tabs.

  2. Test of electron beam technology on Savannah River Laboratory low-activity aqueous waste for destruction of benzene, benzene derivatives, and bacteria

    SciTech Connect (OSTI)

    Dougal, R.A.

    1993-08-01

    High energy radiation was studied as a means for destroying hazardous organic chemical wastes. Tests were conducted at bench scale with a {sup 60}Co source, and at full scale (387 l/min) with a 1.5 MV electron beam source. Bench scale tests for both benzene and phenol included 32 permutations of water quality factors. For some water qualities, as much as 99.99% of benzene or 90% of phenol were removed by 775 krads of {sup 60}Co irradiation. Full scale testing for destruction of benzene in a simulated waste-water mix showed loss of 97% of benzene following an 800 krad dose and 88% following a 500 krad dose. At these loss rates, approximately 5 Mrad of electron beam irradiation is required to reduce concentrations from 100 g/l to drinking water quality (5 {mu}g/l). Since many waste streams are also inhabited by bacterial populations which may affect filtering operations, the effect of irradiation on those populations was also studied. {sup 60}Co and electron beam irradiation were both lethal to the bacteria studied at irradiation levels far lower than were necessary to remove organic contaminants.

  3. In utero exposure to benzene increases embryonic c-Myb and Pim-1 protein levels in CD-1 mice

    SciTech Connect (OSTI)

    Wan, Joanne; Winn, Louise M.

    2008-05-01

    Benzene is a known human leukemogen, but its role as an in utero leukemogen remains controversial. Epidemiological studies have correlated parental exposure to benzene with an increased incidence of childhood leukemias. We hypothesize that in utero exposure to benzene may cause leukemogenesis by affecting the embryonic c-Myb/Pim-1 signaling pathway and that this is mediated by oxidative stress. To investigate this hypothesis, pregnant CD-1 mice were treated with either 800 mg/kg of benzene or corn oil (i.p.) on days 10 and 11 of gestation and in some cases pretreated with 25 kU/kg of PEG-catalase. Phosphorylated and total embryonic c-Myb and Pim-1 protein levels were assessed using Western blotting and maternal and embryonic oxidative stress were assessed by measuring reduced to oxidized glutathione ratios. Our results show increased oxidative stress at 4 and 24 h after exposure, increased phosphorylated Pim-1 protein levels 4 h after benzene exposure, and increased Pim-1 levels at 24 and 48 h after benzene exposure. Embryonic c-Myb levels were elevated at 24 h after exposure. PEG-catalase pretreatment prevented benzene-mediated increases in embryonic c-Myb and Pim-1 protein levels, and benzene-induced oxidative stress. These results support a role for ROS in c-Myb and Pim-1 alterations after in utero benzene exposure.

  4. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-05

    Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combinationmore » of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  5. THE INFLUENCE OF BENZENE AS A TRACE REACTANT IN TITAN AEROSOL ANALOGS

    SciTech Connect (OSTI)

    Trainer, Melissa G.; Sebree, Joshua A.; Heidi Yoon, Y.; Tolbert, Margaret A.

    2013-03-20

    Benzene has been detected in Titan's atmosphere by Cassini instruments, with concentrations ranging from sub-ppb in the stratosphere to ppm in the ionosphere. Sustained levels of benzene in the haze formation region could signify that it is an important reactant in the formation of Titan's organic aerosol. To date, there have not been laboratory investigations to assess the influence of benzene on aerosol properties. We report a laboratory study on the chemical composition of organic aerosol formed from C{sub 6}H{sub 6}/CH{sub 4}/N{sub 2} via far ultraviolet irradiation (120-200 nm). The compositional results are compared to those from aerosol generated by a more ''traditional Titan'' mixture of CH{sub 4}/N{sub 2}. Our results show that even a trace amount of C{sub 6}H{sub 6} (10 ppm) has significant impact on the chemical composition and production rates of organic aerosol. There are several pathways by which photolyzed benzene may react to form larger molecules, both with and without the presence of CH{sub 4}, but many of these reaction mechanisms are only beginning to be explored for the conditions at Titan. Continued work investigating the influence of benzene in aerosol growth will advance understanding of this previously unstudied reaction system.

  6. Hydrogen-terminated silicon nanowire photocatalysis: Benzene oxidation and methyl red decomposition

    SciTech Connect (OSTI)

    Lian, Suoyuan; School of Chemical Engineering and Materials, Dalian Polytechnic University, Dalian 116034 ; Tsang, Chi Him A.; Centre of Super Diamond and Advanced Films, City University of Hong Kong, Hong Kong ; Kang, Zhenhui; Liu, Yang; Wong, Ningbew; Lee, Shuit-Tong; Centre of Super Diamond and Advanced Films, City University of Hong Kong, Hong Kong

    2011-12-15

    Graphical abstract: H-SiNWs can catalyze hydroxylation of benzene and degradation of methyl red under visible light irradiation. Highlights: Black-Right-Pointing-Pointer Hydrogen-terminated silicon nanowires were active photocatalyst in the hydroxylation of benzene under light. Black-Right-Pointing-Pointer Hydrogen-terminated silicon nanowires were also effective in the decomposition of methyl red dye. Black-Right-Pointing-Pointer The Si/SiO{sub x} core-shell structure is the main reason of the obtained high selectivity during the hydroxylation. -- Abstract: Hydrogen-terminated silicon nanowires (H-SiNWs) were used as heterogeneous photocatalysts for the hydroxylation of benzene and for the decomposition of methyl red under visible light irradiation. The above reactions were monitored by GC-MS and UV-Vis spectrophotometry, respectively, which shows 100% selectivity for the transformation of benzene to phenol. A complete decomposition of a 2 Multiplication-Sign 10{sup -4} M methyl red solution was achieved within 30 min. The high selectivity for the hydroxylation of benzene and the photodecomposition demonstrate the catalytic activity of ultrafine H-SiNWs during nanocatalysis.

  7. Total cross sections for positron scattering from benzene, cyclohexane, and aniline

    SciTech Connect (OSTI)

    Zecca, Antonio; Moser, Norberto; Perazzolli, Chiara; Salemi, Alessandro; Brunger, Michael J.

    2007-08-15

    We use a linear transmission technique to measure total cross sections for positron scattering from benzene, cyclohexane, and aniline. In the case of cyclohexane, the energy range of the present study is 0.1-20 eV, while for benzene and aniline it is 0.2-20 eV. With respect to benzene and cyclohexane, comparison is made to the only other existing results we know of [Makochekanwa and co-workers, Phys. Rev. A 68, 032707 (2003); 72, 042705 (2005)]. Agreement with those data is only marginal, being particularly poor at the overlap lower energies. Unlike Kimura et al. [J. Phys. B 37, 1461 (2004)], we find the low-energy dependence of the positron-benzene total cross sections to be qualitatively similar to those found in the electron channel [Gulley et al., J. Phys. B 31, 2735 (1998)]. We believe that the present positron-aniline total cross sections represent the first time such data have been measured. These cross sections are almost identical to those we found for benzene, suggesting that substitution of hydrogen by the amine group on the aromatic ring is largely irrelevant to the scattering process in the energy regimes considered.

  8. Toluene diisocyanate: Induction of the autotaxin-lysophosphatidic acid axis and its association with airways symptoms

    SciTech Connect (OSTI)

    Broström, Julia M.; Ye, Zhi-wei; Axmon, Anna; Littorin, Margareta; Tinnerberg, Håkan; Lindh, Christian H.; Zheng, Huiyuan; Ghalali, Aram; Stenius, Ulla; Jönsson, Bo A.G.; Högberg, Johan

    2015-09-15

    Diisocyanates are industrial chemicals which have a wide range of applications in developed and developing countries. They are notorious lung toxicants and respiratory sensitizers. However, the mechanisms behind their adverse effects are not adequately characterized. Autotaxin (ATX) is an enzyme producing lysophosphatidic acid (LPA), and the ATX-LPA axis has been implicated in lung related inflammatory conditions and diseases, including allergic asthma, but not to toxicity of environmental low-molecular-weight chemicals. We investigated effects of toluene diisocyanate (TDI) on ATX induction in human lung epithelial cell models, and we correlated LPA-levels in plasma to biomarkers of TDI exposure in urine collected from workers exposed to < 5 ppb (parts per billion). Information on workers' symptoms was collected through interviews. One nanomolar TDI robustly induced ATX release within 10 min in vitro. A P2X7- and P2X4-dependent microvesicle formation was implicated in a rapid ATX release and a subsequent protein synthesis. Co-localization between purinergic receptors and ATX was documented by immunofluorescence and confocal microscopy. The release was modulated by monocyte chemoattractant protein-1 (MCP-1) and by extracellular ATP. In workers, we found a dose–response relationship between TDI exposure biomarkers in urine and LPA levels in plasma. Among symptomatic workers reporting “sneezing”, the LPA levels were higher than among non-symptomatic workers. This is the first report indicating induction of the ATX-LPA axis by an environmental low-molecular-weight chemical, and our data suggest a role for the ATX-LPA axis in TDI toxicity. - Highlights: • Human epithelial cells release autotaxin in response to 1 nM toluene diisocyanate (TDI). • The release involves P2X4 and P2X7 receptors and is modulated by ATP and MCP-1. • Lysophosphatidic acid (LPA) was measured in workers exposed to < 5 ppb TDI. • LPA in plasma correlated to TDI exposure biomarkers in

  9. Theoretical study of reactions of HO{sub 2} in low-temperature oxidation of benzene

    SciTech Connect (OSTI)

    Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.; Kennedy, Eric M.; Mackie, John C.

    2010-07-15

    We have generated a set of thermodynamic and kinetic parameters for the reactions involving HO{sub 2} in the very early stages of benzene oxidation at low temperatures using density functional theory (DFT). In particular, we report the rate constants for the reactions of HO{sub 2} with benzene and phenyl. The calculated reaction rate constant for the abstraction of H-C{sub 6}H{sub 5} by HO{sub 2} is found to be in good agreement with the limited experimental values. HO{sub 2} addition to benzene is found to be more important than direct abstraction. We show that the reactions of HO{sub 2} with the phenyl radical generate the propagating radical OH in a highly exoergic reaction. The results presented herein should be useful in modeling the oxidation of aromatic compounds at low temperatures. (author)

  10. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kim, M. J.; Zoerb, M. C.; Campbell, N. R.; Zimmermann, K. J.; Blomquist, B. W.; Huebert, B. J.; Bertram, T. H.

    2015-10-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e. DMS, ?-caryophyllene) as well as previously studied VOCs (i.e., isoprene, ?-pinene). Using a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt?1) to DMS, isoprene, and ?-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a weaker electric field, demonstrated that ion-molecule reactions likely proceed through amorecombination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (R2=0.80) over a wide range of sampling conditions.less

  11. Mechanism reduction for multicomponent surrogates: A case study using toluene reference fuels

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Niemeyer, Kyle E.; Sung, Chih-Jen

    2014-11-01

    Strategies and recommendations for performing skeletal reductions of multicomponent surrogate fuels are presented, through the generation and validation of skeletal mechanisms for a three-component toluene reference fuel. Using the directed relation graph with error propagation and sensitivity analysis method followed by a further unimportant reaction elimination stage, skeletal mechanisms valid over comprehensive and high-temperature ranges of conditions were developed at varying levels of detail. These skeletal mechanisms were generated based on autoignition simulations, and validation using ignition delay predictions showed good agreement with the detailed mechanism in the target range of conditions. When validated using phenomena other than autoignition, suchmore » as perfectly stirred reactor and laminar flame propagation, tight error control or more restrictions on the reduction during the sensitivity analysis stage were needed to ensure good agreement. In addition, tight error limits were needed for close prediction of ignition delay when varying the mixture composition away from that used for the reduction. In homogeneous compression-ignition engine simulations, the skeletal mechanisms closely matched the point of ignition and accurately predicted species profiles for lean to stoichiometric conditions. Furthermore, the efficacy of generating a multicomponent skeletal mechanism was compared to combining skeletal mechanisms produced separately for neat fuel components; using the same error limits, the latter resulted in a larger skeletal mechanism size that also lacked important cross reactions between fuel components. Based on the present results, general guidelines for reducing detailed mechanisms for multicomponent fuels are discussed.« less

  12. Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2015-07-24

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OSc), and mass yield. The OA oxidation state generally increased duringmore » photo-oxidation, and the final OA OSc ranged from -0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

  13. Mechanism reduction for multicomponent surrogates: A case study using toluene reference fuels

    SciTech Connect (OSTI)

    Niemeyer, Kyle E.; Sung, Chih-Jen

    2014-11-01

    Strategies and recommendations for performing skeletal reductions of multicomponent surrogate fuels are presented, through the generation and validation of skeletal mechanisms for a three-component toluene reference fuel. Using the directed relation graph with error propagation and sensitivity analysis method followed by a further unimportant reaction elimination stage, skeletal mechanisms valid over comprehensive and high-temperature ranges of conditions were developed at varying levels of detail. These skeletal mechanisms were generated based on autoignition simulations, and validation using ignition delay predictions showed good agreement with the detailed mechanism in the target range of conditions. When validated using phenomena other than autoignition, such as perfectly stirred reactor and laminar flame propagation, tight error control or more restrictions on the reduction during the sensitivity analysis stage were needed to ensure good agreement. In addition, tight error limits were needed for close prediction of ignition delay when varying the mixture composition away from that used for the reduction. In homogeneous compression-ignition engine simulations, the skeletal mechanisms closely matched the point of ignition and accurately predicted species profiles for lean to stoichiometric conditions. Furthermore, the efficacy of generating a multicomponent skeletal mechanism was compared to combining skeletal mechanisms produced separately for neat fuel components; using the same error limits, the latter resulted in a larger skeletal mechanism size that also lacked important cross reactions between fuel components. Based on the present results, general guidelines for reducing detailed mechanisms for multicomponent fuels are discussed.

  14. In utero and in vitro effects of benzene and its metabolites on erythroid differentiation and the role of reactive oxygen species

    SciTech Connect (OSTI)

    Badham, Helen J.; Winn, Louise M.

    2010-05-01

    Benzene is a ubiquitous occupational and environmental toxicant. Exposures to benzene both prenatally and during adulthood are associated with the development of disorders such as aplastic anemia and leukemia. Mechanisms of benzene toxicity are unknown; however, generation of reactive oxygen species (ROS) by benzene metabolites may play a role. Little is known regarding the effects of benzene metabolites on erythropoiesis. Therefore, to determine the effects of in utero exposure to benzene on the growth and differentiation of fetal erythroid progenitor cells (CFU-E), pregnant CD-1 mice were exposed to benzene and CFU-E numbers were assessed in fetal liver (hematopoietic) tissue. In addition, to determine the effect of benzene metabolite-induced ROS generation on erythropoiesis, HD3 chicken erythroblast cells were exposed to benzene, phenol, or hydroquinone followed by stimulation of erythrocyte differentiation. Our results show that in utero exposure to benzene caused significant alterations in female offspring CFU-E numbers. In addition, exposure to hydroquinone, but not benzene or phenol, significantly reduced the percentage of differentiated HD3 cells, which was associated with an increase in ROS. Pretreatment of HD3 cells with polyethylene glycol-conjugated superoxide dismutase (PEG-SOD) prevented hydroquinone-induced inhibition of erythropoiesis, supporting the hypothesis that ROS generation is involved in the development of benzene erythrotoxicity. In conclusion, this study provided evidence that ROS generated as a result of benzene metabolism may significantly alter erythroid differentiation, potentially leading to the development of Blood Disorders.

  15. Formation of the diphenyl molecule in the crossed beam reaction of phenyl radicals with benzene

    SciTech Connect (OSTI)

    Zhang Fangtong; Gu Xibin; Kaiser, Ralf I.

    2008-02-28

    The chemical dynamics to form the D5-diphenyl molecule, C{sub 6}H{sub 5}C{sub 6}D{sub 5}, via the neutral-neutral reaction of phenyl radicals (C{sub 6}H{sub 5}) with D6-benzene (C{sub 6}D{sub 6}), was investigated in a crossed molecular beams experiment at a collision energy of 185 kJ mol{sup -1}. The laboratory angular distribution and time-of-flight spectra of the C{sub 6}H{sub 5}C{sub 6}D{sub 5} product were recorded at mass to charge m/z of 159. Forward-convolution fitting of our data reveals that the reaction dynamics are governed by an initial addition of the phenyl radical to the {pi} electron density of the D6-benzene molecule yielding a short-lived C{sub 6}H{sub 5}C{sub 6}D{sub 6} collision complex. The latter undergoes atomic deuterium elimination via a tight exit transition state located about 30 kJ mol{sup -1} above the separated reactants; the overall reaction to form D5-diphenyl from phenyl and D6-benzene was found to be weakly exoergic. The explicit identification of the D5-biphenyl molecules suggests that in high temperature combustion flames, a diphenyl molecule can be formed via a single collision event between a phenyl radical and a benzene molecule.

  16. Biofiltration control of VOC and air toxic emissions: n-Butane and benzene

    SciTech Connect (OSTI)

    Allen, E.R.

    1996-12-31

    n-Butane and benzene vapors are routinely observed in urban atmospheres. Their presence in urban airsheds is of concern because of their ozone production potential as volatile organic compounds (VOCs) and/or potential toxicity. Also, these saturated hydrocarbons are representative of airborne aliphatic and aromatic compounds. Separate laboratory studies have been conducted on the biological elimination of n-butane (n-C{sub 4}H{sub 10}) and benzene (C{sub 6}H{sub 6}) from airstreams using treated compost biofilters. The removal efficiencies were found to exceed 90% for a conditioned biofilter medium and pollutant low concentrations (< 25 ppm) and zeroth order kinetics at higher concentrations (> 100 ppm), whereas benzene vapor elimination followed zeroth order kinetics at concentrations up to 200 ppm. The maximum n-butane and benzene elimination capacities observed for the compost biofilters and conditions employed were 25 and 70 g pollutant m{sup -3} h{sup -1}, respectively. 13 refs., 6 figs., 2 tabs.

  17. Comparative Investigation of Benzene Steam Reforming over Spinel Supported Rh and Ir Catalysts

    SciTech Connect (OSTI)

    Mei, Donghai; Lebarbier, Vanessa M.; Rousseau, Roger; Glezakou, Vassiliki-Alexandra; Albrecht, Karl O.; Kovarik, Libor; Flake, Matt; Dagle, Robert A.

    2013-06-07

    In a combined experimental and first-principles density functional theory (DFT) study, benzene steam reforming (BSR) over MgAl2O4 supported Rh and Ir catalysts was investigated. Experimentally, it has been found that both highly dispersed Rh and Ir clusters (1-2 nm) on the MgAl2O4 spinel support are stable during the BSR in the temperature range of 700-850°C. Compared to the Ir/MgAl2O4 catalyst, the Rh/MgAl2O4 catalyst is more active with higher benzene turnover frequency and conversion. At typical steam conditions with the steam-to-carbon ratio > 12, the benzene conversion is only a weak function of the H2O concentration in the feed. This suggests that the initial benzene decomposition step rather than the benzene adsorption is most likely the rate-determined step in BSR over supported Rh and Ir catalysts. In order to understand the differences between the two catalysts, we followed with a comparative DFT study of initial benzene decomposition pathways over two representative model systems for each supported metal (Rh and Ir) catalysts. A periodic terrace (111) surface and an amorphous 50-atom metal cluster with a diameter of 1.0 nm were used to represent the two supported model catalysts under low and high dispersion conditions. Our DFT results show that the decreasing catalyst particle size enhances the benzene decomposition on supported Rh catalysts by lowering both C-C and C-H bond scission. The activation barriers of the C-C and the C-H bond scission decrease from 1.60 and 1.61 eV on the Rh(111) surface to 1.34 and 1.26 eV on the Rh50 cluster. For supported Ir catalysts, the decreasing particle size only affects the C-C scission. The activation barrier of the C-C scission of benzene decreases from 1.60 eV on the Ir(111) surface to 1.35 eV on the Ir50 cluster while the barriers of the C-H scission are practically the same. The experimentally measured higher BSR

  18. Products of the Benzene + O(3P) Reaction

    SciTech Connect (OSTI)

    Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Meloni, Giovanni; Trevitt, Adam J.; Epifanovsky, Evgeny; Krylov, Anna I.; Sirjean, Baptiste; Dames, Enoch; Wang, Hai

    2010-03-11

    The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming an initial triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range 300-1000 K and pressure range 1-10 Torr. The reactions were initiated by pulsed-laser photolysis of NO2 in the presence of benzene and helium buffer in a slow-flow reactor, and reaction products were identified by using the multiplexed chemical kinetics photoionization mass spectrometer operating at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory. Phenol and phenoxy radical were detected and quantified. Cyclopentadiene and cyclopentadienyl radical were directly identified for the first time. Finally, ab initio calculations and master equation/RRKM modeling were used to reproduce the experimental branching ratios, yielding pressure-dependent rate expressions for the reaction channels, including phenoxy + H, phenol, cyclopentadiene + CO, which are proposed for kinetic modeling of benzene oxidation.

  19. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-01-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and directmore » charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  20. On the role of delocalization in benzene: Theoretical and experimental investigation of the effects of strained ring fusion

    SciTech Connect (OSTI)

    Faust, R.

    1993-04-01

    When an important compound`s discovery dates back as far as 1825, one would imagine that every facet of its chemical and physical properties has been illuminated in the meantime. Benzene, however, has not ceased to challenge the chemist`s notion of structure and bonding since its first isolation by Michael Faraday. This report is divided into the following six chapters: 1. Aromaticity -- Criteria, manifestations, structural limitations; 2. The role of delocalization in benzene; 3. The thermochemical properties of benzocyclobutadienologs; 4. Ab initio study of benzenes fused to four-membered rings; 5. Non-planar polycyclic aromatic hydrocarbons; and 6. Experimental details and input decks. 210 Refs.

  1. Crystallographic Analysis of Active Site Contributions to Regiospecificity in the Diiron Enzyme Toluene 4-Monooxygenase

    SciTech Connect (OSTI)

    Bailey, Lucas J.; Acheson, Justin F.; McCoy, Jason G.; Elsen, Nathaniel L.; Phillips, Jr., George N.; Fox, Brian G.

    2014-10-02

    Crystal structures of toluene 4-monooxygenase hydroxylase in complex with reaction products and effector protein reveal active site interactions leading to regiospecificity. Complexes with phenolic products yield an asymmetric {mu}-phenoxo-bridged diiron center and a shift of diiron ligand E231 into a hydrogen bonding position with conserved T201. In contrast, complexes with inhibitors p-NH{sub 2}-benzoate and p-Br-benzoate showed a {mu}-1,1 coordination of carboxylate oxygen between the iron atoms and only a partial shift in the position of E231. Among active site residues, F176 trapped the aromatic ring of products against a surface of the active site cavity formed by G103, E104 and A107, while F196 positioned the aromatic ring against this surface via a {pi}-stacking interaction. The proximity of G103 and F176 to the para substituent of the substrate aromatic ring and the structure of G103L T4moHD suggest how changes in regiospecificity arise from mutations at G103. Although effector protein binding produced significant shifts in the positions of residues along the outer portion of the active site (T201, N202, and Q228) and in some iron ligands (E231 and E197), surprisingly minor shifts (<1 {angstrom}) were produced in F176, F196, and other interior residues of the active site. Likewise, products bound to the diiron center in either the presence or absence of effector protein did not significantly shift the position of the interior residues, suggesting that positioning of the cognate substrates will not be strongly influenced by effector protein binding. Thus, changes in product distributions in the absence of the effector protein are proposed to arise from differences in rates of chemical steps of the reaction relative to motion of substrates within the active site channel of the uncomplexed, less efficient enzyme, while structural changes in diiron ligand geometry associated with cycling between diferrous and diferric states are discussed for their potential

  2. Molecular Characterization of Brown Carbon (BrC) Chromophores in Secondary Organic Aerosol Generated From Photo-Oxidation of Toluene

    SciTech Connect (OSTI)

    Lin, Peng; Liu, Jiumeng; Shilling, John E.; Kathmann, Shawn M.; Laskin, Julia; Laskin, Alexander

    2015-09-28

    Atmospheric Brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365nm = 0.78 m2 g-1) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

  3. Modeling Studies on the Transport of Benzene and H2S in CO2-Water Systems

    SciTech Connect (OSTI)

    Zheng, L.; Spycher, N.; Xu, T.; Apps, J.; Kharaka, Y.; Birkholzer, J.T.

    2010-11-05

    In this study, reactive transport simulations were used to assess the mobilization and transport of organics with supercritical CO{sub 2} (SCC), and the co-injection and transport of H{sub 2}S with SCC. These processes were evaluated at conditions of typical storage reservoirs, and for cases of hypothetical leakage from a reservoir to an overlying shallower fresh water aquifer. Modeling capabilities were developed to allow the simulation of multiphase flow and transport of H{sub 2}O, CO{sub 2}, H{sub 2}S, as well as specific organic compounds (benzene), coupled with multicomponent geochemical reaction and transport. This included the development of a new simulator, TMVOC-REACT, starting from existing modules of the TOUGH2 family of codes. This work also included an extensive literature review, calculation, and testing of phase-partitioning properties for mixtures of the phases considered. The reactive transport simulations presented in this report are primarily intended to illustrate the capabilities of the new simulator. They are also intended to help evaluate and understand various processes at play, in a more qualitative than quantitative manner, and only for hypothetical scenarios. Therefore, model results are not intended as realistic assessments of groundwater quality changes for specific locations, and they certainly do not provide an exhaustive evaluation of all possible site conditions, especially given the large variability and uncertainty in hydrogeologic and geochemical parameter input into simulations. The first step in evaluating the potential mobilization and transport of organics was the identification of compounds likely to be present in deep storage formations, and likely to negatively impact freshwater aquifers if mobilized by SCC. On the basis of a literature review related to the occurrence of these organic compounds, their solubility in water and SCC, and their toxicity (as reflected by their maximum contaminant levels MCL), benzene was

  4. Leukemia mortality by cell type in petroleum workers with potential exposure to benzene

    SciTech Connect (OSTI)

    Raabe, G.K.; Wong, O.

    1996-12-01

    Workers in the petroleum industry are potentially exposed to a variety of petrochemicals, including benzene or benzene-containing liquids. Although a large number of studies of petroleum workers have been conducted to examine leukemia and other cancer risks, few existing studies have investigated cell-type-specific leukemias. One of the major reasons for the lack of cell-type-specific analysis was the small number of deaths by cell type in individual studies. In the present investigation, all cohort studies of petroleum workers in the United States and the United Kingdom were combined into a single database for cell-type-specific leukemia analysis. The majority of these workers were petroleum refinery employees, but production, pipeline, and distribution workers in the petroleum industry were also included. The combined cohort consisted of more than 208,000 petroleum workers, who contributed more than 4.6 million person-years of observation. Based on a meta-analysis of the combined data, cell-type-specific leukemia risks were expressed in terms of standardized mortality ratios (meta-SMRs). The meta-SMR for acute myeloid leukemia was 0.96. The lack of an increase of acute myeloid leukemia was attributed to the low levels of benzene exposure in the petroleum industry, particularly in comparison to benzene exposure levels in some previous studies of workers in other industries, who had been found to experience an increased risk of acute myeloid leukemia. Similarly, no increase in chronic myeloid, acute lymphocytic, or chronic lymphocytic leukemias was found in petroleum workers (meta-SMRs of 0.89, 1.16, and 0.84, respectively). Stratified meta-analyses restricted to refinery studies or to studies with at least 15 years of follow-up yielded similar results. The findings are consistent with those from several recent case-control studies of cell-type-specific leukemia. 95 refs., 4 figs., 10 tabs.

  5. Carbon Nanothreads from Compressed Benzene | U.S. DOE Office of Science

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    (SC) Carbon Nanothreads from Compressed Benzene Basic Energy Sciences (BES) BES Home About Research Facilities Science Highlights Benefits of BES Funding Opportunities Basic Energy Sciences Advisory Committee (BESAC) Community Resources Contact Information Basic Energy Sciences U.S. Department of Energy SC-22/Germantown Building 1000 Independence Ave., SW Washington, DC 20585 P: (301) 903-3081 F: (301) 903-6594 E: Email Us More Information » 04.01.15 Carbon Nanothreads from Compressed

  6. Adsorption characteristics of benzene on biosolid adsorbent and commercial activated carbons

    SciTech Connect (OSTI)

    Hung-Lung Chiang; Kuo-Hsiung Lin; Chih-Yu Chen; Ching-Guan Choa; Ching-Shyung Hwu; Nina Lai

    2006-05-15

    This study selected biosolids from a petrochemical wastewater treatment plant as the raw material. The sludge was immersed in 0.5-5 M of zinc chloride (ZnCl{sub 2}) solutions and pyrolyzed at different temperatures and times. Results indicated that the 1-M ZnCl{sub 2}-immersed biosolids pyrolyzed at 500{sup o}C for 30 min could be reused and were optimal biosolid adsorbents for benzene adsorption. Pore volume distribution analysis indicated that the mesopore contributed more than the macropore and micropore in the biosolid adsorbent. The benzene adsorption capacity of the biosolid adsorbent was 65 and 55% of the G206 (granular-activated carbon) and BPL (coal-based activated carbon; Calgon, Carbon Corp.) activated carbons, respectively. Data from the adsorption and desorption cycles indicated that the benzene adsorption capacity of the biosolid adsorbent was insignificantly reduced compared with the first-run capacity of the adsorbent; therefore, the biosolid adsorbent could be reused as a commercial adsorbent, although its production cost is high. 18 refs., 9 figs., 3 tabs.

  7. Testing of stripping columns for the removal of benzene from aqueous radioactive salt solution

    SciTech Connect (OSTI)

    Georgeton, G.K.; Taylor, G.A.; Gaughan, T.P.

    1995-06-27

    Radioactive high level wastes (HLW) generated from production of special nuclear materials at the Savannah River Site (SRS) are held in interim storage in 51 underground, million gallon tanks. Radioactive cesium ({sup 137}Cs) is segregated by evaporation of aqueous waste solution for interim storage in a salt matrix comprised of Na and K salts or in concentrated salt solution. The saltcake will be dissolved and {sup 137}Cs will be separated from the nonradioactive salts in solution in the In-Tank Precipitation (ITP) Process. The cesium will be combined with other radioactive species and glass formers to be melted and poured into stainless steel canisters in the Defense Waste Processing Facility (DWPF). The salt solution remaining after decontamination in the ITP process will be incorporated into grout for disposal at the site`s Saltstone facility. In the ITP facility, sodium tetraphenylborate (STPB) will be added to precipitate the cesium. Potassium in the waste solution also reacts with STPB and precipitates. Due to radiolytic and chemical degradation of the tetraphenylborate (TPB) precipitate, benzene is generated. The benzene dissolves into the decontaminated salt solution (DSS) and into water (WW) used to {open_quotes}wash{close_quotes} the precipitate to lower the soluble salt content of the slurry. Safety and processing requirements for disposal of the DSS and for temporary storage of the WW dictate that the benzene concentration be reduced.

  8. Comparative pharmacokinetic study of the role of gender and developmental differences in occupational and environmental exposure to benzene. Master's thesis

    SciTech Connect (OSTI)

    Brown, E.A.

    1994-09-01

    The purpose of this study is two-fold. First, it shows that physiological differences between men and women result in gender-specific exposures with respect to benzene. Second, it assesses the potential for a lactating woman's occupational and personal benzene exposure to impact a nursing infant's exposure, highlighting the possibility of subjecting an infant to the effects of industrial chemicals via breast feeding. This study employs physiologically based pharmacokinetic (PBPK) modeling to investigate the influence of physiological parameters and to evaluate the ability of inhaled benzene to transfer from mother to infant through breastmilk. The models are run through scenarios that simulate occupational, smoking, and background exposures. The gender comparison is facilitated by a sensitivity analysis. The blood/air partition coefficient and maximum velocity of metabolism were found to substantially impact model output. These values were both higher in women and caused an increase in the percentage of benzene metabolized in all of the exposure scenarios. The study of lactating women and infants is essentially theoretical. There is evidence that over 65% of an infant's benzene exposure can be attributed to contaminated breastmilk. A large portion of the ingested exposure can be eliminated by adjusting the mother's working or nursing schedule. Benzene, Physiologically based pharmacokinetics, PBPK.

  9. An Order-of-Magnitude Estimation of Benzene Concentration in Saltstone Vault

    SciTech Connect (OSTI)

    CHOI, A

    2006-03-20

    The contents of Tank 48H that include the tetraphenylborate (TPB) precipitates of potassium and cesium will be grouted and stored in the Saltstone vault. The grouting process is exothermic, which should accelerate the rate of decomposition of TPB precipitates eventually to benzene. Because the vault is not currently outfitted with an active ventilation system, there is a concern that a mixture of flammable gases may form in the vapor space of each cell filled with the curing grout. The purpose of this study was to determine if passive breathing induced by the diurnal fluctuations of barometric pressure would provide any mitigating measure against potential flammability in the cell vapor space. In Revision 0 of this document, a set of algorithms were presented that would predict the equilibrium concentration of benzene in the cell vapor space as a function of benzene generation rate, fill height, and passive breathing rate. The algorithms were derived based on several simplifying assumptions so that order of magnitude estimates could be made quickly for scoping purposes. In particular, it was assumed that passive breathing would occur solely due to barometric pressure fluctuations that were sinusoidal; the resulting algorithm for estimating the rate of passive breathing into or out of each cell is given in Eq. (10). Since Revision 0 was issued, the validity of this critical assumption on the mode of passive breathing was checked against available passive ventilation data for the Hanford waste tanks. It was found that the passive breathing rates estimated from Eq. (10) were on average 50 to 90% lower than those measured for 5 out of 6 Hanford tanks considered in this study (see Table 1); for Tank U-106, the estimated passive breathing rates were on average 20% lower than the measured data. These results indicate that Eq. (10) would most likely under predict passive breathing rates of the Saltstone vault. At a given fill height and benzene generation rate, under

  10. Benzene under high pressure: A story of molecular crystals transforming to saturated networks, with a possible intermediate metallic phase

    SciTech Connect (OSTI)

    Wen, Xiao-Dong; Hoffmann, Roald; Ashcroft, N. W.

    2011-01-01

    In a theoretical study, benzene is compressed up to 300 GPa. The transformations found between molecular phases generally match the experimental findings in the moderate pressure regime (<20 GPa): phase I (Pbca) is found to be stable up to 4 GPa, while phase II (P43212) is preferred in a narrow pressure range of 47 GPa. Phase III (P21/c) is at lowest enthalpy at higher pressures. Above 50 GPa, phase V (P21 at 0 GPa; P21/c at high pressure) comes into play, slightly more stable than phase III in the range of 5080 GP, but unstable to rearrangement to a saturated, four-coordinate (at C), one-dimensional polymer. Actually, throughout the entire pressure range, crystals of graphane possess lower enthalpy than molecular benzene structures; a simple thermochemical argument is given for why this is so. In several of the benzene phases there nevertheless are substantial barriers to rearranging the molecules to a saturated polymer, especially at low temperatures. Even at room temperature these barriers should allow one to study the effect of pressure on the metastable molecular phases. Molecular phase III (P21/c) is one such; it remains metastable to higher pressures up to ~200 GPa, at which point it too rearranges spontaneously to a saturated, tetracoordinate CH polymer. At 300 K the isomerization transition occurs at a lower pressure. Nevertheless, there may be a narrow region of pressure, between P = 180 and 200 GPa, where one could find a metallic, molecular benzene state. We explore several lower dimensional models for such a metallic benzene. We also probe the possible first steps in a localized, nucleated benzene polymerization by studying the dimerization of benzene molecules. Several new (C6H6)2 dimers are predicted.

  11. The flash pyrolysis and methanolysis of biomass (wood) for production of ethylene, benzene and methanol

    SciTech Connect (OSTI)

    Steinberg, M.; Fallon, P.T.; Sundaram, M.S.

    1990-02-01

    The process chemistry of the flash pyrolysis of biomass (wood) with the reactive gases, H{sub 2} and CH{sub 4} and with the non-reactive gases He and N{sub 2} is being determined in a 1 in. downflow tubular reactor at pressures from 20 to 1000 psi and temperatures from 600 to 1000{degrees}C. With hydrogen, flash hydropyrolysis leads to high yields of methane and CO which can be used for SNG and methanol fuel production. With methane, flash methanolysis leads to high yields of ethylene, benzene and CO which can be used for the production of valuable chemical feedstocks and methanol transportation fuel. At reactor conditions of 50 psi and 1000{degrees}C and approximately 1 sec residence time, the yields based on pine wood carbon conversion are up to 25% for ethylene, 25% for benzene, and 45% for CO, indicating that over 90% of the carbon in pine is converted to valuable products. Pine wood produces higher yields of hydrocarbon products than Douglas fir wood; the yield of ethylene is 2.3 times higher with methane than with helium or nitrogen, and for pine, the ratio is 7.5 times higher. The mechanism appears to be a free radical reaction between CH{sub 4} and the pyrolyzed wood. There appears to be no net production or consumption of methane. A preliminary process design and analysis indicates a potentially economical competitive system for the production of ethylene, benzene and methanol based on the methanolysis of wood. 10 refs., 18 figs., 1 tab.

  12. The benzene metabolite trans,trans-muconaldehyde blocks gap junction intercellular communication by cross-linking connexin43

    SciTech Connect (OSTI)

    Rivedal, Edgar Leithe, Edward

    2008-11-01

    Benzene is used at large volumes in many different human activities. Hematotoxicity and cancer-causation as a result of benzene exposure was recognized many years ago, but the mechanisms involved remain unclear. Aberrant regulation of gap junction intercellular communication (GJIC) has been linked to both cancer induction and interference with normal hematopoietic development. We have previously suggested that inhibition of GJIC may play a role in benzene toxicity since benzene metabolites were found to block GJIC, the ring-opened trans,trans-muconaldehyde (MUC) being the most potent metabolite. In the present work we have studied the molecular mechanisms underlying the MUC-induced inhibition of gap junctional communication. We show that MUC induces cross-linking of the gap junction protein connexin43 and that this is likely to be responsible for the induced inhibition of GJIC, as well as the loss of connexin43 observed in Western blots. We also show that glutaraldehyde possesses similar effects as MUC, and we compare the effects to that of formaldehyde. The fact that glutaraldehyde and formaldehyde have been associated with induction of leukemia as well as disturbance of hematopoiesis, strengthens the possible link between the effect of MUC on gap junctions, and the toxic effects of benzene.

  13. JV Task 86 - Identifying the Source of Benzene in Indoor Air Using Different Compound Classes from TO-15 Data

    SciTech Connect (OSTI)

    Steven B. Hawthorne

    2007-04-15

    Volatile organic compound (VOC) data that had already been collected using EPA method TO-15 at four different sites under regulatory scrutiny (a school, strip mall, apartment complex, and business/residential neighborhood) were evaluated to determine whether the source of indoor air benzene was outdoor air or vapor intrusion from contaminated soil. Both the use of tracer organics characteristic of different sources and principal component statistical analysis demonstrated that the source of indoor air at virtually all indoor sampling locations was a result of outdoor air, and not contaminated soil in and near the indoor air-sampling locations. These results show that proposed remediation activities to remove benzene-contaminated soil are highly unlikely to reduce indoor air benzene concentrations. A manuscript describing these results is presently being prepared for submission to a peer-reviewed journal.

  14. Exposure to methyl tert-butyl ether, benzene, and total hydrocarbons at the Singapore-Malaysia causeway immigration checkpoint

    SciTech Connect (OSTI)

    Tan, C.; Ong, H.Y.; Kok, P.W.

    1996-12-31

    The primary aim of this study was to determine the extent and levels of exposure to volatile organic compounds (VOCs) from automobile emissions in a group of immigration officers at a busy cross-border checkpoint. A majority (80%) of the workers monitored were exposed to benzene at levels between 0.01 and 0.5 ppm, with only 1.2% exceeding the current Occupational Safety and Health Administration occupational exposure limit of 1 ppm. The geometric mean (GM) concentrations of 8-hr time-weighted average exposure were 0.03 ppm, 0.9 ppm, and 2.46 ppm for methyl-tert-butyl ether (MTBE), benzene, and total hydrocarbons (THC), respectively. The highest time-weighted average concentrations measured were 1.05 ppm for MTBE, 2.01 ppm for benzene, and 34 ppm for THC. It was found that motorbikes emitted a more significant amount of pollutants compared with motor cars. On average, officers at the motorcycle booths were exposed to four to five times higher levels of VOCs (GMs of 0.07 ppm, 0.23 ppm, and 4.7 ppm for MTBE, benzene, and THC) than their counterparts at the motor car booths (GMs of 0.01 ppm, 0.05 ppm, and 1.5 ppm). The airborne concentrations of all three pollutants correlated with the flow of vehicle traffic. Close correlations were also noted for the concentrations in ambient air for the three pollutants measured. Benzene and MTBE had a correlation coefficient of 0.97. The overall findings showed that the concentrations of various VOCs were closely related to the traffic density, suggesting that they were from a common source, such as exhaust emissions from the vehicles. The results also indicated that although benzene, MTBE, and THC are known to be volatile, a significant amount could still be detected in the ambient environment, thus contributing to our exposure to these compounds. 4 refs., 6 figs.

  15. Evolution of soot size distribution in premixed ethylene/air and ethylene/benzene/air flames: Experimental and modeling study

    SciTech Connect (OSTI)

    Echavarria, Carlos A.; Sarofim, Adel F.; Lighty, JoAnn S.; D'Anna, Andrea

    2011-01-15

    The effect of benzene concentration in the initial fuel on the evolution of soot size distribution in ethylene/air and ethylene/benzene/air flat flames was characterized by experimental measurements and model predictions of size and number concentration within the flames. Experimentally, a scanning mobility particle sizer was used to allow spatially resolved and online measurements of particle concentration and sizes in the nanometer-size range. The model couples a detailed kinetic scheme with a discrete-sectional approach to follow the transition from gas-phase to nascent particles and their coagulation to larger soot particles. The evolution of soot size distribution (experimental and modeled) in pure ethylene and ethylene flames doped with benzene showed a typical nucleation-sized (since particles do not actually nucleate in the classical sense particle inception is often used in place of nucleation) mode close to the burner surface, and a bimodal behavior at greater height above burner (HAB). However, major features were distinguished between the data sets. The growth of nucleation and agglomeration-sized particles was faster for ethylene/benzene/air flames, evidenced by the earlier presence of bimodality in these flames. The most significant changes in size distribution were attributed to an increase in benzene concentration in the initial fuel. However, these changes were more evident for high temperature flames. In agreement with the experimental data, the model also predicted the decrease of nucleation-sized particles in the postflame region for ethylene flames doped with benzene. This behavior was associated with the decrease of soot precursors after the main oxidation zone of the flames. (author)

  16. In situ thermally enhanced biodegradation of petroleum fuel hydrocarbons and halogenated organic solvents

    DOE Patents [OSTI]

    Taylor, R.T.; Jackson, K.J.; Duba, A.G.; Chen, C.I.

    1998-05-19

    An in situ thermally enhanced microbial remediation strategy and a method for the biodegradation of toxic petroleum fuel hydrocarbon and halogenated organic solvent contaminants are described. The method utilizes nonpathogenic, thermophilic bacteria for the thermal biodegradation of toxic and carcinogenic contaminants, such as benzene, toluene, ethylbenzene and xylenes, from fuel leaks and the chlorinated ethenes, such as trichloroethylene, chlorinated ethanes, such as 1,1,1-trichloroethane, and chlorinated methanes, such as chloroform, from past solvent cleaning practices. The method relies on and takes advantage of the pre-existing heated conditions and the array of delivery/recovery wells that are created and in place following primary subsurface contaminant volatilization efforts via thermal approaches, such as dynamic underground steam-electrical heating. 21 figs.

  17. In situ thermally enhanced biodegradation of petroleum fuel hydrocarbons and halogenated organic solvents

    DOE Patents [OSTI]

    Taylor, Robert T.; Jackson, Kenneth J.; Duba, Alfred G.; Chen, Ching-I

    1998-01-01

    An in situ thermally enhanced microbial remediation strategy and a method for the biodegradation of toxic petroleum fuel hydrocarbon and halogenated organic solvent contaminants. The method utilizes nonpathogenic, thermophilic bacteria for the thermal biodegradation of toxic and carcinogenic contaminants, such as benzene, toluene, ethylbenzene and xylenes, from fuel leaks and the chlorinated ethenes, such as trichloroethylene, chlorinated ethanes, such as 1,1,1-trichloroethane, and chlorinated methanes, such as chloroform, from past solvent cleaning practices. The method relies on and takes advantage of the pre-existing heated conditions and the array of delivery/recovery wells that are created and in place following primary subsurface contaminant volatilization efforts via thermal approaches, such as dynamic underground steam-electrical heating.

  18. Eielson Air Force Base Operable Unit 2 baseline risk assessment

    SciTech Connect (OSTI)

    Lewis, R.E.; Jarvis, T.T.; Jarvis, M.R.; Whelan, G.

    1994-10-01

    Operable Unit 2 at Eielson Air Force Base (AFB) near Fairbanks, is one of several operable units characterized by petroleum, oil, and lubricant contamination, and by the presence of organic products floating at the water table, as a result of Air Force operations since the 1940s. The base is approximately 19,270 acres in size, and comprises the areas for military operations and a residential neighborhood for military dependents. Within Operable Unit 2, there are seven source areas. These source areas were grouped together primarily because of the contaminants released and hence are not necessarily in geographical proximity. Source area ST10 includes a surface water body (Hardfill Lake) next to a fuel spill area. The primary constituents of concern for human health include benzene, toluene, ethylbenzene, and xylenes (BTEX). Monitored data showed these volatile constituents to be present in groundwater wells. The data also showed an elevated level of trace metals in groundwater.

  19. Health assessment for Vogel Paint and Wax, Maurice, Sioux County, Iowa, Region 7. CERCLIS No. IAD980630487. Final report

    SciTech Connect (OSTI)

    Not Available

    1989-04-29

    The Vogel Paint and Wax National Priority List site is situated in northwest Iowa in Sioux County. Contaminants found at the site consist of heavy metals (particularly cadmium, chromium, lead, and mercury) and volatile organic compounds (benzene, ethylbenzene, methyl ethyl ketone, toluene, and xylene). Two towns, Maurice and Struble, and the Southern Sioux County Rural Water System well field are located within three miles of the site, and two families live within 1600 feet of the waste-disposal site. Environmental pathways include contaminated soil and ground water, as well as potential surface water and air contamination. Although there does not appear to be any immediate public health threat, the site is of potential health concern because of the possibility for further off-site migration of contaminants into the ground water aquifer and for direct on-site contact.

  20. Natural bioreclamation of alkylbenzenes (BTEX) from a gasoline spill in methanogenic groundwater. Book chapter

    SciTech Connect (OSTI)

    Wilson, J.T.; Kampbell, D.H.; Armstrong, J.

    1994-01-01

    A spill of gasoline from underground storage tanks (USTS) at the Sleeping Bear Dunes National Lakeshore in Benzie County, Michigan, produced a plume of contamination that reached the banks of the Platte River. The plume was short (70 feet) and it had a short residence time (5 to 53 weeks). The plume was in transmissive glacial sands and gravels. The groundwater is cold (10 to 11 C), hard (alkalinity 200 to 350 milligrams/L), and well buffered (pH 6.1 to 7.6). Along the most contaminated flow path, methanogenesis, nitrate reduction, sulfate reduction, iron reduction, and oxygen respiration accepted enough electrons to destroy 30, 14, 4.2, 1.1, and 0.8 milligrams/L of benzene, toluene, ethylbenzene, and xylenes (BTEX compounds) respectively. The actual concentration of BTEX compounds consumed was 42 milligrams/L.

  1. Solubilities and other physical parameters of aromatic hydrocarbons in water and aqueous sodium chloride solutions as determined by headspace analysis

    SciTech Connect (OSTI)

    Lowry, M.A.H.

    1991-12-31

    The solubility, Henry`s law constant, aqueous-vapor partition coefficients, and oil-aqueous distribution coefficients of benzene, toluene, ethylbenzene, o-xylene,m-xylene and p-xylene were determined in water and aqueous sodium chloride solutions at 25C. Values are in agreement with using gas chromatography of headspace literature. The salting-out effect of sodium chloride on the solute properties measured was illustrated using the empirical relationship deduced by Setschenow (1889). The empirical relationship predicts that the logarithm of solubility will be a function of ionic strength. The solubility data obtained in this work obeys this relationship. It was also found that the logarithm of the Henry`s law constant, partition coefficient, and distribution coefficient are linear functions of ionic strength. 10 tabs, 6 figs.

  2. Effect of Key Parameters on the Photocatalytic Oxidation of Toluene at Low Concentrations in Air under 254 + 185 nm UV Irradiation

    SciTech Connect (OSTI)

    Quici, Natalia; Vera, Maria L.; Choi, Hyeok; Puma, Gianluca Li; Dionysiou, Dionysios D.; Litter, Marta I.; Destaillats, Hugo

    2009-07-01

    The effect of key experimental parameters on the removal of toluene under 254 + 185 nm irradiation was investigated using a benchtop photocatalytic flow reactor. Toluenewas introduced at low concentrations between 10 and 500 ppbv, typical of indoorenvironments, and reacted on TiO2-coated Raschig rings. Two different TiO2-coated rings were prepared: in one case, by dip-coating using a P25 aqueous suspension and, on the other, using an organic/inorganic sol-gel method that produced thin films of mesoporous anatase. Flow rates in the photoreactor varied between 4 L min-1 and 125 mL min-1, leading to residence times in the range 100 ms< tau< 2 s. For these conditions, toluene removal efficiencies were between 30 and 90percent, indicating that the system did not achieve total conversion in any case. For each air flow rate, the conversion oftoluene was significantly higher when the reactor length was 10 cm, as compared with 5 cm; however, only marginal increases in conversions were achieved in the two reactor lengths at equal residence time and different concentration of toluene, suggesting that that the reactor is effectively behaving as an ideal reactor and that the reaction is first-order in the concentration of toluene. Experiments were carried out between 0 and 66percent relative humidity (RH), the fastest reaction rate being observed at moderately low humidity conditions (10percent RH), with respect to both dry air and higher humidity levels. Formaldehyde was formed as a partial oxidation byproduct at low and at high residence times (240 and 960 ms), although higher formaldehyde molar yields (up to 20percent) were observed at low tau (240 ms) and moderate humidity conditions (10 and 33percent), suggesting that both tau and RH can be optimized toreduce the formation of harmful intermediates. Toluene removal efficiency increased with the TiO2 thickness (i.e., mass) until a maximum value of 500 nm, beyond which the removal efficiency decreased. This should be

  3. Adsorption, Desorption, and Dissociation of Benzene on TiO2(110) and Pd/TiO2(110)

    SciTech Connect (OSTI)

    Zhou, Jing; Dag, Sefa; Senanayake, Sanjaya D; Hathorn, Bryan C; Kalinin, Sergei V; Meunier, Vincent; Mullins, David R; Overbury, Steven {Steve} H; Baddorf, Arthur P

    2006-01-01

    Adsorption and reaction of benzene molecules on clean TiO{sub 2}(110) and on TiO{sub 2}(110) with deposited Pd nanoparticles are investigated using a combination of scanning tunneling microscopy (STM), temperature-programmed desorption, and first-principles calculations. Above {approx}50 K, the one-dimensional motion of benzene between bridging oxygen rows is shown to be too fast for STM imaging. At 40 K benzene molecules form chains on top of titanium rows, with calculations indicating every other benzene is rotated 30{sup o}. Both experimental and theoretical studies find no dissociative reactivity of benzene on the clean TiO{sub 2}(110) surface, due to little hybridization between TiO{sub 2} and benzene electronic states. After deposition of Pd nanoparticles, molecular benzene is observed with STM both on the substrate and adjacent to metallic particles. Upon heating to 800 K, benzene fully breaks down into its atomic constituents in a multistep decomposition process.

  4. Spectroscopic study on deuterated benzenes. I. Microwave spectra and molecular structure in the ground state

    SciTech Connect (OSTI)

    Kunishige, Sachi; Katori, Toshiharu; Baba, Masaaki; Nakajima, Masakazu; Endo, Yasuki

    2015-12-28

    We observed microwave absorption spectra of some deuterated benzenes and accurately determined the rotational constants of all H/D isotopomers in the ground vibrational state. Using synthetic analysis assuming that all bond angles are 120°, the mean bond lengths were obtained to be r{sub 0}(C–C) = 1.3971 Å and r{sub 0}(C–H) = r{sub 0}(C–D) = 1.0805 Å. It has been concluded that the effect of deuterium substitution on the molecular structure is negligibly small and that the mean bond lengths of C–H and C–D are identical unlike small aliphatic hydrocarbons, in which r{sub 0}(C–D) is about 5 mÅ shorter than r{sub 0}(C–H). It is considered that anharmonicity is very small in the C–H stretching vibration of aromatic hydrocarbons.

  5. Photocatalytic degradation of gaseous toluene over TiO{sub 2}-SiO{sub 2} composite nanotubes synthesized by sol-gel with template technique

    SciTech Connect (OSTI)

    Zou, Xuejun [State Key Laboratory of Fine Chemical and Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian, 116024 (China)] [State Key Laboratory of Fine Chemical and Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian, 116024 (China); Li, Xinyong, E-mail: xyli@dlut.edu.cn [State Key Laboratory of Fine Chemical and Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian, 116024 (China) [State Key Laboratory of Fine Chemical and Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian, 116024 (China); Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia); Qu, Zhenping; Zhao, Qidong; Shi, Yong; Chen, Yongying [State Key Laboratory of Fine Chemical and Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian, 116024 (China)] [State Key Laboratory of Fine Chemical and Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian, 116024 (China); Tade, Moses [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia)] [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia); Liu, Shaomin, E-mail: shaomin.liu@curtin.edu.au [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia)] [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia)

    2012-02-15

    Graphical abstract: TiO{sub 2}-SiO{sub 2} nanotubes (b) were fabricated by sol-gel method using ZnO nanowires (a) as template. Highlights: Black-Right-Pointing-Pointer A simple method to prepare TiO{sub 2}-SiO{sub 2} nanotubes for photocatalytic toluene removal. Black-Right-Pointing-Pointer The TiO{sub 2}-SiO{sub 2} nanotubes have a small blue shift and higher absorption intensity. Black-Right-Pointing-Pointer The TiO{sub 2}-SiO{sub 2} nanotubes have an enhanced photoactivity in degrading gaseous toluene. -- Abstract: TiO{sub 2}-SiO{sub 2} composite nanotubes were successfully synthesized by a facile sol-gel technique utilizing ZnO nanowires as template. The nanotubes were well characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2} adsorption-desorption analysis and UV-vis diffuse reflectance spectroscopy. The nanotubular TiO{sub 2}-SiO{sub 2} composite photocatalysts showed diameter of 300-325 nm, fine mesoporous structure and high specific surface area. The results indicated that the degradation efficiency of gaseous toluene could get 65% after 4 h reaction using the TiO{sub 2}-SiO{sub 2} composite as the photocatalyst under UV light illumination, which was higher than that of P25.

  6. Thermodynamic Features of Benzene-1,2-Diphosphonic Acid Complexes with Several Metal Ions

    SciTech Connect (OSTI)

    Syouhei Nishihama; Ryan P. Witty; Leigh R Martin; Kenneth L. Nash

    2013-08-01

    Among his many contributions to the advancement of f-element chemistry and separation science, Professor Gregory R. Choppins research group completed numerous investigations featuring the application of distribution techniques to the determination of metal complexation equilibrium quotients. Most of these studies focused on the chemistry of lanthanide and actinide complexes. In keeping with that tradition, this report discusses the complex formation equilibrium constants for complexes of trivalent europium (Eu3+) with benzene-1,2-diphosphonic acid (H4BzDP) determined using solvent extraction distribution experiments in 0.2 M (Na,H)ClO4 media in the temperature range of 5 45 degrees C. Protonation constants for HnBzDP4-n and stoichiometry and stability of BzDP4- complexes with Zn2+, Ni2+, and Cu2+ have also been determined using potentiometric titration (at I = 0.1 M) and 31P NMR spectroscopy. Heats of protonation of HnBzDPn-4 species have been determined by titration calorimetry. From the temperature dependence of the complex Eu3+-HnBzDPn-4 equilibrium constant, a composite enthalpy (?H = -15.1 (+/-1.0) kJ mol-1) of complexation has been computed. Comparing these thermodynamic parameters with literature reports on other diphosphonic acids and structurally similar carboxylic acids indicates that exothermic heats of complexation are unique to the Eu-BzDP system. Comparisons with thermodynamic data from the literature indicate that the fixed geometry imposed by the benzene ring enhances complex stability.

  7. Changes in the peripheral blood transcriptome associated with occupational benzene exposure identified by cross-comparison on two microarray platforms

    SciTech Connect (OSTI)

    McHale, Cliona M.; Zhang, Luoping; Lan, Qing; Li, Guilan; Hubbard, Alan E.; Forrest, Matthew S.; Vermeulen, Roel; Chen, Jinsong; Shen, Min; Rappaport, Stephen M.; Yin, Songnian; Smith, Martyn T.; Rothman, Nathaniel

    2009-03-01

    Benzene is an established cause of leukemia and a possible cause of lymphoma in humans but the molecular pathways underlying this remain largely undetermined. This study sought to determine if the use of two different microarray platforms could identify robust global gene expression and pathway changes associated with occupational benzene exposure in the peripheral blood mononuclear cell (PBMC) gene expression of a population of shoe-factory workers with well-characterized occupational exposures to benzene. Microarray data was analyzed by a robust t-test using a Quantile Transformation (QT) approach. Differential expression of 2692 genes using the Affymetrix platform and 1828 genes using the Illumina platform was found. While the overall concordance in genes identified as significantly associated with benzene exposure between the two platforms was 26% (475 genes), the most significant genes identified by either array were more likely to be ranked as significant by the other platform (Illumina = 64%, Affymetrix = 58%). Expression ratios were similar among the concordant genes (mean difference in expression ratio = 0.04, standard deviation = 0.17). Four genes (CXCL16, ZNF331, JUN and PF4), which we previously identified by microarray and confirmed by real-time PCR, were identified by both platforms in the current study and were among the top 100 genes. Gene Ontology analysis showed over representation of genes involved in apoptosis among the concordant genes while Ingenuity{reg_sign} Pathway Analysis (IPA) identified pathways related to lipid metabolism. Using a two-platform approach allows for robust changes in the PBMC transcriptome of benzene-exposed individuals to be identified.

  8. Sodium dodecyl benzene sulfonate-assisted synthesis through a hydrothermal reaction

    SciTech Connect (OSTI)

    Sobhani, Azam; Salavati-Niasari, Masoud; Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 8731751167, Islamic Republic of Iran

    2012-08-15

    Graphical abstract: Reaction of a SeCl{sub 4} aqueous solution with a NiCl{sub 2}6H{sub 2}O aqueous solution in presence of sodium dodecyl benzene sulfonate (SDBS) as capping agent and hydrazine (N{sub 2}H{sub 4}H{sub 2}O) as reductant, produces nanosized nickel selenide through a hydrothermal method. The effect of temperature, reaction time and amounts of reductant on the morphology, particle sizes of NiSe nanostructures has been investigated. Highlights: ? NiSe nanostructures were synthesized by hydrothermal method. ? A novel Se source was used to synthesize NiSe. ? SDBS as capping agent plays a crucial role on the morphology of products. ? A mixture of Ni{sub 3}Se{sub 2} and NiSe was prepared in the presence of 2 ml hydrazine. ? A pure phase of NiSe was prepared in the presence of 4 or 6 ml hydrazine. -- Abstract: The effects of the anionic surfactant on the morphology, size and crystallization of NiSe precipitated from NiCl{sub 2}6H{sub 2}O and SeCl{sub 4} in presence of hydrazine (N{sub 2}H{sub 4}H{sub 2}O) as reductant were investigated. The products have been successfully synthesized in presence of sodium dodecyl benzene sulfonate (SDBS) as surfactant via an improved hydrothermal route. A variety of synthesis parameters, such as reaction time and temperature, capping agent and amount of reducing agent have a significant effect on the particle size, phase purity and morphology of the obtained products. The sample size became bigger with decreasing reaction temperature and increasing reaction time. In the presence of 2 ml hydrazine, the samples were found to be the mixture of Ni{sub 3}Se{sub 2} and NiSe. With increasing the reaction time and amount of hydrazine a pure phase of hexagonal NiSe was obtained. X-ray diffraction analysis (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) images indicate phase, particle size and morphology of the products. Chemical composition and purity of the products were characterized by X

  9. Benzene metabolite levels in blood and bone marrow of B6C3F{sub 1} mice after low-level exposure

    SciTech Connect (OSTI)

    Bechtold, W.E.; Strunk, M.R.; Thornton-Manning, J.R.

    1995-12-01

    Studies at the Inhalation Toxicology Research Institute (ITRI) have explored the species-specific uptake and metabolism of benzene. Results have shown that metabolism is dependent on both dose and route of administration. Of particular interest were shifts in the major metabolic pathways as a function of exposure concentration. In these studies, B6C3F{sub 1} mice were exposed to increasing levels of benzene by either gavage or inhalation. As benzene internal dose increased, the relative amounts of muconic acid and hydroquinone decreased. In contrast, the relative amount of catechol increased with increasing exposure. These results show that the relative levels of toxic metabolites are a function of exposure level. Based on these results and assuming a linear relationship between exposure concentration and levels of bone marrow metabolites, it would be difficult to detect an elevation of any phenolic metabolites above background after occupational exposures to the OSHA Permissible Exposure Limit of 1 ppm benzene.

  10. Photocatalytic degradation of gaseous toluene over hollow spindle-like ?-Fe{sub 2}O{sub 3} loaded with Ag

    SciTech Connect (OSTI)

    Li, Hong [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China) [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Department of Basic, Dalian Naval Academy, Dalian 116018 (China); Zhao, Qidong [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China)] [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Li, Xinyong, E-mail: xyli@dlut.edu.cn [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China) [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia); Shi, Yong [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China)] [State Key Laboratory of Fine Chemical, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Zhu, Zhengru [Research Center of Hydrology and Engineering, Academy of City and Environment, Liaoning Normal University, Dalian 116029 (China)] [Research Center of Hydrology and Engineering, Academy of City and Environment, Liaoning Normal University, Dalian 116029 (China); Tade, Moses [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia)] [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia); Liu, Shaomin, E-mail: shaomin.liu@curtin.edu.au [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia)] [Department of Chemical Engineering, Curtin University, Perth, WA 6845 (Australia)

    2012-06-15

    Highlights: ? Hollow ?-Fe{sub 2}O{sub 3} spindle-shaped microparticles were prepared for Ag support. ? The hollow ?-Fe{sub 2}O{sub 3} and Ag/?-Fe{sub 2}O{sub 3} materials were used to degrade gaseous toluene. ? Complete degradation of toluene occurred on the Ag/?-Fe{sub 2}O{sub 3} surface. -- Abstract: In this work, hollow spindle-like ?-Fe{sub 2}O{sub 3} nanoparticles were synthesized by a hydrothermal route. The Ag/?-Fe{sub 2}O{sub 3} catalyst was prepared based on the spindle-shaped ?-Fe{sub 2}O{sub 3} with CTAB as the surfactant, which showed excellent photoelectric property and photocatalytic activity. The structural properties of these samples were systematically investigated by X-ray powder diffraction, scanning electronic microscopy, transmission electronic microscopy, energy-dispersive X-ray spectra, and UVVis diffuse reflectance spectroscopy techniques. The photo-induced charge separation in the samples was demonstrated by surface photovoltage measurement. The photocatalytic performances of the Ag/?-Fe{sub 2}O{sub 3} and ?-Fe{sub 2}O{sub 3} samples were comparatively studied in the degradation of toluene under xenon lamp irradiation by in situ FTIR spectroscopy. Benzaldehyde and benzoic acid species could be observed on the ?-Fe{sub 2}O{sub 3} surface rather than Ag/?-Fe{sub 2}O{sub 3} surface. The results indicate that the Ag/?-Fe{sub 2}O{sub 3} sample exhibited higher photocatalytic efficiency.

  11. A pilot-scale field study on the anaerobic biotreatment of soil impacted with highly chlorinated benzenes

    SciTech Connect (OSTI)

    Ramanand, K.; Foulke, B.; Delnicki, W.A.; Ying, A.C.; Baek, N.H.; Coats, M.L.; Duffy, J.J.

    1995-12-31

    An on-site pilot-scale demonstration of anaerobic biodegradation of highly chlorinated benzenes was successfully performed at a chemical manufacturing industrial facility in Niagara Falls, New York. The field investigation was conducted in 6-yd{sup 3} capacity soil boxes. Approximately 4 yd{sup 3} of soil impacted with chlorinated compounds was placed in each soil box. Chlorinated benzenes with 3 or more chlorines accounted for about 85% of the total chemistry in the soil. The soil box amended with water, nutrients, and acclimated soil microbial inoculum exhibited greater than 78% reduction in the levels of highly chlorinated compounds after one year of field study. The total concentrations of hexa-, penta-, tetra-, and trichlorobenzenes decreased from 920 mg/kg to less than 190 mg/kg, while the total concentrations of di-, and monochlorobenzene increased from 8 mg/kg to greater than 400 mg/kg during one year of field operation. The control soil that did not receive any external nutrient or microbial amendments maintained the same percentage of the highly chlorinated benzenes after one year and di-, and monochlorobenzene never exceeded more than 4 mg/kg at any given time period. The anaerobic activity was further confirmed by monitored parameters such as nutrient consumption (butyrate, nitrogen, organic matter), sulfate depletion, and methane production.

  12. Benchmark Theoretical Study of the π–π Binding Energy in the Benzene Dimer

    SciTech Connect (OSTI)

    Miliordos, Evangelos; Apra, Edoardo; Xantheas, Sotiris S.

    2014-09-04

    We establish a new estimate for the interaction energy between two benzene molecules in the parallel displaced (PD) conformation by systematically converging (i) the intra- and intermolecular geometry at the minimum geometry, (ii) the expansion of the orbital basis set and (iii) the level of electron correlation. The calculations were performed at the second order Møller - Plesset perturbation (MP2) and the Coupled Cluster including Singles, Doubles and a perturbative estimate of Triples replacements [CCSD(T)] levels of electronic structure theory. At both levels of theory, by including results corrected for Basis Set Superposition Error (BSSE), we have estimated the Complete Basis Set (CBS) limit by employing the family of Dunning’s correlation consistent polarized valence basis sets. The largest MP2 calculation was performed with the cc-pV6Z basis set (2,772 basis functions), whereas the largest CCSD(T) calculation with the cc-pV5Z basis set (1,752 basis functions). The cluster geometries were optimized with basis sets up to quadruple-ζ quality, observing that both its intra- and inter-molecular parts have practically converged with the triple-ζ quality sets. The use of converged geometries was found to play an important role for obtaining accurate estimates for the CBS limits. Our results demonstrate that the binding energies with the families of the plain (cc-pVnZ) and augmented (aug-cc-pVnZ) sets converge [to within < 0.01 kcal/mol for MP2 and < 0.15 kcal/mol for CCSD(T)] to the same CBS limit. In addition, the average of the uncorrected and BSSEcorrected binding energies was found to converge to the same CBS limit must faster than either of the two constituents (uncorrected or BSSE-corrected binding energies). Due to the fact that the family of augmented basis sets (especially for the larger sets) causes serious linear dependency problems, the plain basis sets (for which no linear dependencies were found) are deemed as a more efficient and

  13. Mobilization and Transport of Organic Compounds from Reservoir Rock and Caprock in Geological Carbon Sequestration Sites

    SciTech Connect (OSTI)

    Zhong, Lirong; Cantrell, Kirk J.; Mitroshkov, Alexandre V.; Shewell, Jesse L.

    2014-05-06

    Supercritical CO2 (scCO2) is an excellent solvent for organic compounds, including benzene, toluene, ethyl-benzene, and xylene (BTEX), phenols, and polycyclic aromatic hydrocarbons (PAHs). Monitoring results from geological carbon sequestration (GCS) field tests has shown that organic compounds are mobilized following CO2 injection. Such results have raised concerns regarding the potential for groundwater contamination by toxic organic compounds mobilized during GCS. Knowledge of the mobilization mechanism of organic compounds and their transport and fate in the subsurface is essential for assessing risks associated with GCS. Extraction tests using scCO2 and methylene chloride (CH2Cl2) were conducted to study the mobilization of volatile organic compounds (VOCs, including BTEX), the PAH naphthalene, and n-alkanes (n-C20 – n-C30) by scCO2 from representative reservoir rock and caprock obtained from depleted oil reservoirs and coal from an enhanced coal-bed methane recovery site. More VOCs and naphthalene were extractable by scCO2 compared to the CH2Cl2 extractions, while scCO2 extractable alkane concentrations were much lower than concentrations extractable by CH2Cl2. In addition, dry scCO2 was found to extract more VOCs than water saturated scCO2, but water saturated scCO2 mobilized more naphthalene than dry scCO2. In sand column experiments, moisture content was found to have an important influence on the transport of the organic compounds. In dry sand columns the majority of the compounds were retained in the column except benzene and toluene. In wet sand columns the mobility of the BTEX was much higher than that of naphthalene. Based upon results determined for the reservoir rock, caprock, and coal samples studied here, the risk to aquifers from contamination by organic compounds appears to be relatively low; however, further work is necessary to fully evaluate risks from depleted oil reservoirs.

  14. Impact of the revised OSHA exposure standard on evaluation and control of benzene and other volatile organic chemicals in the liquid petroleum pipeline industry

    SciTech Connect (OSTI)

    Mercer, D.O.

    1989-01-01

    The primary purpose of this study was to determine the benzene exposure potential of workers in the liquid petroleum pipeline industry and to assess the impact of compliance with the revised standard on this industry. In addition, exposure to ethylene dibromide (EDB), and ethylene dichloride (EDC), which have toxicological profiles similar to that of benzene and are routinely found in this industry, were evaluated and appropriate control protocols were recommended. Exposure potential to benzene in excess of the 0.5 ppm (8-hour TWA) OSHA action level was shown to be limited to three free product handling operations, and that this increased exposure potential was dependent on the length of time necessary to perform the operations. The incidence and magnitude of benzene overexposure was not severe and control could be accomplished with engineering methods, along with work practice controls and personal protective equipment. Through application of a risk assessment model it was shown that 14 excess leukemia deaths per one thousand workers could be expected in the employee population that routinely performs those operation having maximum benzene exposure potential. This compares to less than on excess leukemia death per one thousand workers in the total work population. The evaluation of EDB and EDC indicated that exposure potential to EDB was of greatest concern. Even though exposure could be limited through application of standard industrial hygiene methods, any control protocol short of total elimination of EDB from the product stream may be not sufficient to reduce exposure to accepted levels.

  15. Raman Spectroscopy of the Reaction of Thin Films of Solid-State Benzene with Vapor-Deposited Ag, Mg, and Al

    SciTech Connect (OSTI)

    Schalnat, Matthew C.; Hawkridge, Adam M.; Pemberton, Jeanne E.

    2011-07-21

    Thin films of solid-state benzene at 30 K were reacted with small quantities of vapor-deposited Ag, Mg, and Al under ultrahigh vacuum, and products were monitored using surface Raman spectroscopy. Although Ag and Mg produce small amounts of metalbenzene adduct products, the resulting Raman spectra are dominated by surface enhancement of the normal benzene modes from metallic nanoparticles suggesting rapid Ag or Mg metallization of the film. In contrast, large quantities of Al adduct products are observed. Vibrational modes of the products in all three systems suggest adducts that are formed through a pathway initiated by an electron transfer reaction. The difference in reactivity between these metals is ascribed to differences in ionization potential of the metal atoms; ionization potential values for Ag and Mg are similar but larger than that for Al. These studies demonstrate the importance of atomic parameters, such as ionization potential, in solid-state metalorganic reaction chemistry.

  16. Facile preparation of sphere-like copper ferrite nanostructures and their enhanced visible-light-induced photocatalytic conversion of benzene

    SciTech Connect (OSTI)

    Shen, Yu; Wu, Yanbo; Xu, Hongfeng; Fu, Jie; Li, Xinyong; Zhao, Qidong; Hou, Yang

    2013-10-15

    Graphical abstract: - Highlights: Spinel CuFe{sub 2}O{sub 4} nanospheres were successfully synthesized via a facile method. CuFe{sub 2}O{sub 4} nanospheres showed high photocatalytic activity toward benzene. Ethyl acetate, carboxylic acid and aldehyde were the intermediate products. - Abstract: Spinel copper ferrite nanospheres with diameters of about 116 nm were synthesized in high yield via a facile solvothermal route. The prepared nanospheres had cubic spinel structure and exhibited good size uniformity and regularity. The band-gap energy of CuFe{sub 2}O{sub 4} nanospheres was calculated to be about 1.69 eV, indicating their potential visible-light-induced photocatalytic activity. The dramatically enhanced photocatalytic activity of the CuFe{sub 2}O{sub 4} nanospheres was evaluated via the photocatalytic conversion of benzene under Xe lamp irradiation. By using the in situ FTIR technique, ethyl acetate, carboxylic acid and aldehyde could be regarded as the intermediate products, and CO{sub 2} was produced as the final product during the reaction process. This study provided new insight into the design and preparation of functional nanomaterials with sphere structure in high yield, and the as-grown architectures demonstrated an excellent ability to remove organic pollutants in the atmosphere.

  17. Density functional theory (DFT) and ab initio molecular orbital calculations have been employed to determine the structures and energies of the isomers of the OH-toluene adduct, the methyl hydroxycyclohexadienyl radical, and their corresponding transitio

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Technical Report Laboratory Investigation of Organic Aerosol Formation from Aromatic Hydrocarbons (DOE Award No. DE-FG02-02ER63098) Prepared by Luisa T. Molina, Renyi Zhang and Mario J. Molina Our work for this DOE funded project includes: (1) measurements of the kinetics and mechanism of the gas-phase oxidation reactions of the aromatic hydrocarbons initiated by OH; (2) measurements of aerosol formation from the aromatic hydrocarbons; and (3) theoretical studies to elucidate the OH-toluene

  18. Spectroscopic study on deuterated benzenes. II. High-resolution laser spectroscopy and rotational structure in the S{sub 1} state

    SciTech Connect (OSTI)

    Kunishige, Sachi; Katori, Toshiharu; Baba, Masaaki; Hayashi, Masato; Hasegawa, Hirokazu; Ohshima, Yasuhiro

    2015-12-28

    High-resolution spectra of the S{sub 1}←S{sub 0} transition in jet-cooled deuterated benzenes were observed using pulse dye amplification of single-mode laser light and mass-selective resonance enhanced multiphoton ionization (REMPI) detection. The vibrational and rotational structures were accurately analyzed for the vibronic levels in the S{sub 1} state. The degenerate 6{sup 1} levels of C{sub 6}H{sub 6} or C{sub 6}D{sub 6} are split into 6a{sup 1} and 6b{sup 1} in many of deuterated benzenes. The rigid-rotor rotational constants were assessed and found to be slightly different between 6a and 6b because of different mean molecular structures. Their rotational levels are significantly shifted by Coriolis interactions. It was found that the Coriolis parameter proportionally changed with the number of substituted D atoms.

  19. A density functional theory study of magneto-electric Jones birefringence of noble gases, furan homologues, and mono-substituted benzenes

    SciTech Connect (OSTI)

    Fahleson, Tobias; Norman, Patrick; Coriani, Sonia; Rizzo, Antonio; Rikken, Geert L. J. A.

    2013-11-21

    We report on the results of a systematic ab initio study of the Jones birefringence of noble gases, of furan homologues, and of monosubstituted benzenes, in the gas phase, with the aim of analyzing the behavior and the trends within a list of systems of varying size and complexity, and of identifying candidates for a combined experimental/theoretical study of the effect. We resort here to analytic linear and nonlinear response functions in the framework of time-dependent density functional theory. A correlation is made between the observable (the Jones constant) and the atomic radius for noble gases, or the permanent electric dipole and a structure/chemical reactivity descriptor as the para Hammett constant for substituted benzenes.

  20. Benzene exposure in the petroleum distribution industry associated with leukemia in the United Kingdom: Overview of the methodology of a case-control study

    SciTech Connect (OSTI)

    Rushton, L.

    1996-12-01

    This paper describes basic principles underlying the methodology for obtaining quantitative estimates of benzene exposure in the petroleum marketing and distribution industry. Work histories for 91 cases of leukemia and 364 matched controls (4 per case) identified for a cohort of oil distribution workers up to the end of 1992 were obtained, primarily from personnel records. Information on the distribution sites, more than 90% of which were closed at the time of data collection, was obtained from site visits and archive material. Industrial hygiene measurements measured under known conditions were assembled for different tasks. These were adjusted for conditions where measured data were not available using variables known to influence exposure, such as temperature, technology, percentage of benzene in fuel handled, products handled, number of loads, and job activity. A quantitative estimate of dermal contact and peak exposure was also made. 20 refs., 1 fig., 3 tabs.

  1. Association of genetic polymorphisms in GADD45A, MDM2, and p14{sup ARF} with the risk of chronic benzene poisoning in a Chinese occupational population

    SciTech Connect (OSTI)

    Sun Pin; Zhang Zhongbin; Wan Junxiang; Zhao Naiqing; Jin Xipeng; Xia Zhaolin

    2009-10-01

    Benzene reactive metabolites can lead to DNA damage and trigger the p53-dependent defense responses to maintain genomic stability. We hypothesized that the p53-dependent genes may play a role in the development of chronic benzene poisoning (CBP). In a case-control study of 303 patients with benzene poisoning and 295 workers occupationally exposed to benzene in south China, we investigated associations between the risk of CBP and polymorphisms in three p53-dependent genes. Potential interactions of these polymorphisms with lifestyle factors were also explored. We found p14{sup ARF} rs3731245 polymorphism was associated with risk of CBP (P = 0.014). Compared with those carrying the GG genotype, individuals carrying p14{sup ARF} rs3731245 GA+AA genotypes had a reduced risk of CBP ([adjusted odds ratio (OR{sub adj}) = 0.57, 95%CI = 0.36-0.89]. Further analysis showed p14{sup ARF} TGA/TAG diplotype was associated with an increased risk of CBP (P = 0.0006), whereas p14{sup ARF} TGG/TAA diplotype was associated with a decreased risk of CBP (P = 0.0000001). In addition, we found individuals carrying both MDM2 Del1518 WW genotype and p14{sup ARF} rs3731245 GA+AA genotypes had a lower risk of CBP (OR{sub adj} = 0.25; 95%CI = 0.10-0.62; P = 0.003). Although these results require confirmation and extension, our findings suggest that genetic polymorphisms in p14{sup ARF} may have an impact on the risk of CBP in the study population.

  2. Characterization Of The Hydrogenation Products Of Bix (phenylethynyl) Benzene (DEB) Getter Using Combined GC/FTIR/MS, FT-Raman, and ATR Spectroscopies (U)

    SciTech Connect (OSTI)

    Smyrl, N. R.; Powell, G. L.

    2011-06-09

    Organic hydrogen getters are utilized to minimize hydrogen accumulation in sealed systems where such build up could produce either a safety problem from pressure build up or corrosion problem due the hydriding of metals contained in the sealed vessel. DEB (1,4 bis (phenyl ethynyl) benzene) is a hydrogen getter that is based on the palladium catalyzed hydrogenation of triple bonds to single bonds in aromatic aryl compound. DEB is a getter mixed with 25% carbon and 1% Pd and pressed into pellets with some porosity. The reaction mechanisms are complex involving solid state reactions with a heterogeneous catalyst leading to the many intermediates.

  3. State-selective laser photoionization of neutral benzene molecules ejected from keV ion bombarded C{sub 6}H{sub 6}/Ag{l_brace}111{r_brace}

    SciTech Connect (OSTI)

    Meserole, C. A.; Vandeweert, E.; Chatterjee, R.; Chakraborty, B. R.; Garrison, B. J.; Winograd, N.; Postawa, Z.

    1998-12-16

    One-color two-photon ionization spectroscopy was used to probe state-selectively neutral benzene molecules desorbed from a benzene overlayer physisorbed on a Ag{l_brace}111{r_brace} surface upon 8 keV Ar{sup +} bombardment. Time distributions were measured for benzene molecules ejected in the zero level of the molecular ground state and in the first state of the {nu}{sub 6} ' vibration. These distributions are found to show a strong dependence both on the internal energy of the ejected molecules and the degree of coverage of the Ag surface. Up to monolayer coverages, benzene molecules are ejected by direct collisions with Ag particles sputtered from the underlying substrate. Molecules with higher internal energy leave the surface with a distribution shifted towards lower flight times. At multilayer coverages, a second, thermal-like ejection mechanism gains significance. It is suggested that only molecules excited near the benzene-vacuum interface, survive the ejection process without being deexcited.

  4. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    SciTech Connect (OSTI)

    Al-Hamdani, Yasmine S.; Alf, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

    2014-10-22

    Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B?N?H?) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.

  5. FTIR study of the photocatalytic degradation of gaseous benzene over UV-irradiated TiO{sub 2} nanoballs synthesized by hydrothermal treatment in alkaline solution

    SciTech Connect (OSTI)

    Zhu, Zhengru [Key Laboratory of Industrial Ecology and Environmental Engineering and State Key Laboratory of Fine Chemical, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian 116024 (China)] [Key Laboratory of Industrial Ecology and Environmental Engineering and State Key Laboratory of Fine Chemical, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian 116024 (China); Li, Xinyong, E-mail: xyli@dlut.edu.cn [Key Laboratory of Industrial Ecology and Environmental Engineering and State Key Laboratory of Fine Chemical, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian 116024 (China)] [Key Laboratory of Industrial Ecology and Environmental Engineering and State Key Laboratory of Fine Chemical, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian 116024 (China); Zhao, Qidong; Qu, Zhenping; Hou, Yang; Zhao, Ling [Key Laboratory of Industrial Ecology and Environmental Engineering and State Key Laboratory of Fine Chemical, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian 116024 (China)] [Key Laboratory of Industrial Ecology and Environmental Engineering and State Key Laboratory of Fine Chemical, School of Environmental Sciences and Technology, Dalian University of Technology, Dalian 116024 (China); Liu, Shaomin [Department of Chemical Engineering, Curtin University of Technology, Perth, WA 6845 (Australia)] [Department of Chemical Engineering, Curtin University of Technology, Perth, WA 6845 (Australia); Chen, Guohua [Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong)] [Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong)

    2010-12-15

    In this study, photocatalysts of TiO{sub 2} nanoballs were obtained via a hydrothermal treating of commercial P25 in alkaline solution, and then characterized with SEM, XRD, BET and surface photovoltage spectroscopy techniques. The UV-assisted photodegradation of gaseous benzene over P25 and the prepared TiO{sub 2} nanoballs was monitored by an in situ infrared technique. The results demonstrated that the prepared TiO{sub 2} nanoballs in anatase form were more active than commercial P25 in photocatalytic oxidation of gaseous benzene. The promoted activity of the hydrothermal-treated TiO{sub 2} is attributed to the increasing specific surface area and larger band gap induced by the reduced crystallite size. The spectra of FTIR indicated that weakly adsorbed phenol was formed as the reaction progress. Hydroxyl groups on the surface of TiO{sub 2} nanoballs are able to react with photo-produced phenol, which is then retained on the catalyst surface leading to the progressive deactivation of the catalyst in the gas-solid system.

  6. Assessing electronic structure approaches for gas-ligand interactions in metal-organic frameworks: The CO{sub 2}-benzene complex

    SciTech Connect (OSTI)

    Witte, Jonathon; Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 ; Neaton, Jeffrey B.; Head-Gordon, Martin; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720

    2014-03-14

    Adsorption of gas molecules in metal-organic frameworks is governed by many factors, the most dominant of which are the interaction of the gas with open metal sites, and the interaction of the gas with the ligands. Herein, we examine the latter class of interaction in the context of CO{sub 2} binding to benzene. We begin by clarifying the geometry of the CO{sub 2}benzene complex. We then generate a benchmark binding curve using a coupled-cluster approach with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set (CBS) limit. Against this ?CCSD(T)/CBS standard, we evaluate a plethora of electronic structure approximations: Hartree-Fock, second-order Mller-Plesset perturbation theory (MP2) with the resolution-of-the-identity approximation, attenuated MP2, and a number of density functionals with and without different empirical and nonempirical van der Waals corrections. We find that finite-basis MP2 significantly overbinds the complex. On the other hand, even the simplest empirical correction to standard density functionals is sufficient to bring the binding energies to well within 1 kJ/mol of the benchmark, corresponding to an error of less than 10%; PBE-D in particular performs well. Methods that explicitly include nonlocal correlation kernels, such as VV10, vdW-DF2, and ?B97X-V, perform with similar accuracy for this system, as do ?B97X and M06-L.

  7. Correlating Extent of PtNi Bond Formation with Low-temperature Hydrogenation of Benzene and 1,3-butadiene over Supported Pt/Ni Bimetallic Catalysts

    SciTech Connect (OSTI)

    Lonergan, W.; Vlachos, D; Chen, J

    2010-01-01

    Low-temperature hydrogenation of benzene and 1,3-butadiene on supported Pt/Ni catalysts have been used as probe reactions to correlate hydrogenation activity with the extent of Pt-Ni bimetallic bond formation. Pt/Ni bimetallic and Pt and Ni monometallic catalysts were supported on {gamma}-Al{sub 2}O{sub 3} using incipient wetness impregnation. Two sets of bimetallic catalysts were synthesized: one set to study the effect of metal atomic ratio and the other to study the effect of impregnation sequence. Fourier transform infrared spectroscopy (FTIR) CO adsorption studies were performed to characterize the surface composition of the bimetallic nanoparticles, and transmission electron microscopy (TEM) was utilized to characterize the particle size distribution. Batch reactor studies with FTIR demonstrated that all bimetallic catalysts outperformed monometallic catalysts for both benzene and 1,3-butadiene hydrogenation. Within the two sets of bimetallic catalysts, it was found that catalysts with a smaller Pt:Ni ratio possessed higher hydrogenation activity and that catalysts synthesized using co-impregnation had greater activity than sequentially impregnated catalysts. Extended X-ray absorption fine structure (EXAFS) measurements were performed in order to verify the extent of Pt-Ni bimetallic bond formation, which was found to correlate with the hydrogenation activity.

  8. Trip Report-Produced-Water Field Testing

    SciTech Connect (OSTI)

    Sullivan, Enid J.

    2012-05-25

    Los Alamos National Laboratory (LANL) conducted field testing of a produced-water pretreatment apparatus with assistance from faculty at the Texas A&M University (TAMU) protein separation sciences laboratory located on the TAMU main campus. The following report details all of the logistics surrounding the testing. The purpose of the test was to use a new, commercially-available filter media housing containing modified zeolite (surfactant-modified zeolite or SMZ) porous medium for use in pretreatment of oil and gas produced water (PW) and frac-flowback waters. The SMZ was tested previously in October, 2010 in a lab-constructed configuration ('old multicolumn system'), and performed well for removal of benzene, toluene, ethylbenzene, and xylenes (BTEX) from PW. However, a less-expensive, modular configuration is needed for field use. A modular system will allow the field operator to add or subtract SMZ filters as needed to accommodate site specific conditions, and to swap out used filters easily in a multi-unit system. This test demonstrated the use of a commercial filter housing with a simple flow modification and packed with SMZ for removing BTEX from a PW source in College Station, Texas. The system will be tested in June 2012 at a field site in Pennsylvania for treating frac-flowback waters. The goals of this test are: (1) to determine sorption efficiency of BTEX in the new configuration; and (2) to observe the range of flow rates, backpressures, and total volume treated at a given flow rate.

  9. Surface acoustic wave sensors/gas chromatography; and Low quality natural gas sulfur removal and recovery CNG Claus sulfur recovery process

    SciTech Connect (OSTI)

    Klint, B.W.; Dale, P.R.; Stephenson, C.

    1997-12-01

    This topical report consists of the two titled projects. Surface Acoustic Wave/Gas Chromatography (SAW/GC) provides a cost-effective system for collecting real-time field screening data for characterization of vapor streams contaminated with volatile organic compounds (VOCs). The Model 4100 can be used in a field screening mode to produce chromatograms in 10 seconds. This capability will allow a project manager to make immediate decisions and to avoid the long delays and high costs associated with analysis by off-site analytical laboratories. The Model 4100 is currently under evaluation by the California Environmental Protection Agency Technology Certification Program. Initial certification focuses upon the following organics: cis-dichloroethylene, chloroform, carbon tetrachloride, trichlorethylene, tetrachloroethylene, tetrachloroethane, benzene, ethylbenzene, toluene, and o-xylene. In the second study the CNG Claus process is being evaluated for conversion and recovery of elemental sulfur from hydrogen sulfide, especially found in low quality natural gas. This report describes the design, construction and operation of a pilot scale plant built to demonstrate the technical feasibility of the integrated CNG Claus process.

  10. High-temperature reprocessing of petroleum oily sludges

    SciTech Connect (OSTI)

    Hahn, W.J. )

    1994-08-01

    Crude oil tank bottoms and other petroleum oily sludges and emulsions containing paraffins and volatile hydrocarbons can be economically reprocessed with heavy-oil dehydration facilities to recover residual hydrocarbons and to achieve volume reductions. The main factors affecting the use of this alternative are (1) the characteristics of the sludges requiring treatment, (2) the availability of waste heat or existing high temperature (> 350 F) dehydration facilities, (3) air emissions from the process, and (4) effluent criteria for treated residues. This paper discusses operational variables that affect high-temperature reprocessing (HTR) and illustrates an application of the process. The example pilot project evaluated the feasibility of high-temperature reprocessing for tank-bottom sludges and skim oils from Kern County, CA, light- (>30[degree] API) oil-producing leases. The process performance was quantified in terms of general operating parameters (flash point and paraffin, oil, water, and solids content); specific constituent analyses for benzene, toluene, ethylbenzene, and xylene (BTEX); and analyses for total petroleum hydrocarbons (TPH) content. Information on the percent removal of these parameters, characteristics of the treated residues, and the hydrocarbon recovery efficiency of the process are presented.

  11. Superfund Record of Decision (EPA Region 3): Rhinehart Tire Fire Dump, Operable Unit 2, Winchester, VA. (Second remedial action), September 1992

    SciTech Connect (OSTI)

    Not Available

    1992-09-29

    The Rhinehart Tire Fire Dump site is located in a 22-acre drainage area of a sparsely populated rural area in western Frederick County, Virginia. Surface water runoff flows into a north-south tributary that discharges to Hogue Creek, which is 4,000 feet downstream. Bedrock is noted to be highly fractured, and the ground water flow in the overburden aquifer is toward Massey Run. From 1972 to 1983, the site owner conducted a tire disposal operation, which consisted of transporting discarded tires from various locations and storing them on a 5-acre wooded slope behind his home. An estimated 5 to 7 million tires that had been accumulated caught on fire in October 1983 and burned until July 1984. As a result of the fire, a free-flowing oily-tar, which contained anthracene, benzene, cadmium, chromium, ethylbenzene, napthalene, nickel, pyrene, toluene, and zinc, began to seep out of the tire pile into Massey Run and on to Hogue Creek.

  12. Risk-based approach for bioremediation of fuel hydrocarbons at a major airport

    SciTech Connect (OSTI)

    Wiedemeier, T.H.; Guest, P.R.; Blicker, B.R.

    1994-12-31

    This paper describes a risk-based approach for bioremediation of fuel-hydrocarbon-contaminated soil and ground water at a major airport in Colorado. In situ bioremediation pilot testing, natural attenuation modeling, and full-scale remedial action planning and implementation for soil and ground water contamination has conducted at four airport fuel farms. The sources of fuel contamination were leaking underground storage tanks (USTs) or pipelines transporting Jet A fuel and aviation gasoline. Continuing sources of contamination were present in several small cells of free-phase product and in fuel residuals trapped within the capillary fringe at depths 15 to 20 feet below ground surface. Bioventing pilot tests were conducted to assess the feasibility of using this technology to remediate contaminated soils. The pilot tests included measurement of initial soil gas chemistry at the site, determination of subsurface permeability, and in situ respiration tests to determine fuel biodegradation rates. A product recovery test was also conducted. ES designed and installed four full-scale bioventing systems to remediate the long-term sources of continuing fuel contamination. Benzene, toluene, ethylbenzene, and xylenes (BTEX) and total petroleum hydrocarbons (TPH) were detected in ground water at concentrations slightly above regulatory guidelines.

  13. Operable Unit 1 remedial investigation report, Eielson Air Force Base, Alaska

    SciTech Connect (OSTI)

    Gilmore, T.J.; Fruland, R.M.; Liikala, T.L.

    1994-06-01

    This remedial investigation report for operable Unit 1 (OU-1) at Eielson Air Force Base presents data, calculations, and conclusions as to the nature and extent of surface and subsurface contamination at the eight source areas that make up OU-1. The information is based on the 1993 field investigation result and previous investigations. This report is the first in a set of three for OU-1. The other reports are the baseline risk assessment and feasibility study. The information in these reports will lead to a Record of Decision that will guide and conclude the environmental restoration effort for OU-1 at Eielson Air Force Base. The primary contaminants of concern include fuels and fuel-related contaminants (diesel; benzene, toluene, ethylbenzene, and xylene; total petroleum hydrocarbon; polycyclic aromatic hydrocarbons), maintenance-related solvents and cleaners (volatile chlorinated hydrocarbons such as trichloroothylene), polychlorinated biphenyls, and dichlorodiphenyltrichloroethane (DDT). The origins of contaminants of concern include leaks from storage tanks, drums and piping, and spills. Ongoing operations and past sitewide practices also contribute to contaminants of concern at OU-1 source areas. These include spraying mixed oil and solvent wastes on unpaved roads and aerial spraying of DDT.

  14. Use of Ambersorb{reg_sign} carbonaceous adsorbent for removal of BTEX compounds from oil-field produced water

    SciTech Connect (OSTI)

    Gallup, D.L.; Isacoff, E.G.; Smith, D.N. III

    1996-12-31

    The removal of high concentrations of BTEX compounds (benzene, toluene, ethylbenzene and xylenes) from oil-field produced waters using a carbonaceous adsorbent was successfully demonstrated in the field. The carbonaceous adsorbent was much more effective in removing BTEX compounds from produced water than activated carbon or modified clays. The primary objectives of the field studies were to evaluate the efficiency of oil removal processes to protect the adsorbent from fouling, to determine the BTEX removal efficiency of a carbonaceous adsorbent at a high flow rate loading, and to demonstrate regeneration of the adsorbent. Adsorbent fouling with oil was mitigated by mechanical coalescing for heavier crude and emulsion-breaking for lighter crude. Adsorbent extenders and filters did not control fouling in the presence of exceedingly emulsified crude oil. Carbonaceous adsorbent reduced BTEX compounds levels from the 25-130 mg/l range to less than 1 mg/l treating approximately 500 bed volumes of produced water per cycle. Regeneration of the adsorbent using low pressure steam or solvents was successfully achieved with regeneration efficiencies exceeding 95 percent. 13 refs., 7 figs., 4 tabs.

  15. The oxidation of a gasoline surrogate in the negative temperature coefficient region

    SciTech Connect (OSTI)

    Lenhert, David B.; Miller, David L.; Cernansky, Nicholas P.; Owens, Kevin G.

    2009-03-15

    This experimental study investigated the preignition reactivity behavior of a gasoline surrogate in a pressurized flow reactor over the low and intermediate temperature regime (600-800 K) at elevated pressure (8 atm). The surrogate mixture, a volumetric blend of 4.6% 1-pentene, 31.8% toluene, 14.0% n-heptane, and 49.6% 2,2,4-trimethyl-pentane (iso-octane), was shown to reproduce the low and intermediate temperature reactivity of full boiling range fuels in a previous study. Each of the surrogate components were examined individually to identify the major intermediate species in order to improve existing kinetic models, where appropriate, and to provide a basis for examining constituent interactions in the surrogate mixture. n-Heptane and 1-pentene started reacting at 630 K and 640 K, respectively, and both fuels exhibited a strong negative temperature coefficient (NTC) behavior starting at 700 and 710 K, respectively. Iso-octane showed a small level of reactivity at 630 K and a weak NTC behavior starting at 665 K. Neat toluene was unreactive at these temperatures. The surrogate started reacting at 630 K and exhibited a strong NTC behavior starting at 693 K. The extent of fuel consumption varied for each of the surrogate constituents and was related to their general autoignition behavior. Most of the intermediates identified during the surrogate oxidation were species observed during the oxidation of the neat constituents; however, the surrogate mixture did exhibit a significant increase in intermediates associated with iso-octane oxidation, but not from n-heptane. While neat toluene was unreactive at these temperatures, in the mixture it reacted with the radical pool generated by the other surrogate components, forming benzaldehyde, benzene, phenol, and ethyl-benzene. The observed n-heptane, iso-octane, and surrogate oxidation behavior was compared to predictions using existing kinetic models. The n-heptane model reasonably predicted the disappearance of the fuel

  16. Path integral Monte Carlo simulations of H{sub 2} adsorbed to lithium-doped benzene: A model for hydrogen storage materials

    SciTech Connect (OSTI)

    Lindoy, Lachlan P.; Kolmann, Stephen J.; D’Arcy, Jordan H.; Jordan, Meredith J. T.; Crittenden, Deborah L.

    2015-11-21

    Finite temperature quantum and anharmonic effects are studied in H{sub 2}–Li{sup +}-benzene, a model hydrogen storage material, using path integral Monte Carlo (PIMC) simulations on an interpolated potential energy surface refined over the eight intermolecular degrees of freedom based upon M05-2X/6-311+G(2df,p) density functional theory calculations. Rigid-body PIMC simulations are performed at temperatures ranging from 77 K to 150 K, producing both quantum and classical probability density histograms describing the adsorbed H{sub 2}. Quantum effects broaden the histograms with respect to their classical analogues and increase the expectation values of the radial and angular polar coordinates describing the location of the center-of-mass of the H{sub 2} molecule. The rigid-body PIMC simulations also provide estimates of the change in internal energy, ΔU{sub ads}, and enthalpy, ΔH{sub ads}, for H{sub 2} adsorption onto Li{sup +}-benzene, as a function of temperature. These estimates indicate that quantum effects are important even at room temperature and classical results should be interpreted with caution. Our results also show that anharmonicity is more important in the calculation of U and H than coupling—coupling between the intermolecular degrees of freedom becomes less important as temperature increases whereas anharmonicity becomes more important. The most anharmonic motions in H{sub 2}–Li{sup +}-benzene are the “helicopter” and “ferris wheel” H{sub 2} rotations. Treating these motions as one-dimensional free and hindered rotors, respectively, provides simple corrections to standard harmonic oscillator, rigid rotor thermochemical expressions for internal energy and enthalpy that encapsulate the majority of the anharmonicity. At 150 K, our best rigid-body PIMC estimates for ΔU{sub ads} and ΔH{sub ads} are −13.3 ± 0.1 and −14.5 ± 0.1 kJ mol{sup −1}, respectively.

  17. Synthesis and characterization of d{sup 10} metal complexes with mixed 1,3-di(1H-imidazol-4-yl)benzene and multicarboxylate ligands

    SciTech Connect (OSTI)

    Chen, Zhi-Hao; Zhao, Yue; Chen, Shui-Sheng; Wang, Peng; Sun, Wei-Yin

    2013-06-15

    Seven new coordination polymers [Zn(H{sub 2}L)(mbdc)] (1), [Zn(H{sub 3}L)(btc)] (2), [Zn(H{sub 2}L)(Hbtc)] (3), [Zn(H{sub 2}L)(Hbtc)]H{sub 2}O (4), [Zn{sub 2}(H{sub 2}L)(btc)(?{sub 2}-OH)] (5), [Cd(H{sub 2}L)(mbdc)] (6) and [Cd{sub 3}(H{sub 2}L){sub 2}(btc){sub 2}(H{sub 2}O)]5H{sub 2}O (7) were synthesized by reactions of the corresponding metal salt with rigid ligand 1,3-di(1H-imidazol-4-yl)benzene (H{sub 2}L) and different carboxylic acids of 1,3-benzenedicarboxylic acid (H{sub 2}mbdc) and benzene-1,3,5-tricarboxylic acid (H{sub 3}btc), respectively. The results of X-ray crystallographic analysis indicate that complex 1 is 1D chain while 2 is a (3,3)-connected 2D network with Point (Schlfli) symbol of (4,8{sup 2}). Complexes 3 and 6 are 2D networks, 4 is a 3-fold interpenetrating 3D framework with Point (Schlfli) symbol of (6{sup 5},8) and 5 is a (3,8)-connected 2D network with Point (Schlfli) symbol of (3,4{sup 2}){sub 2}(3{sup 4},4{sup 6},5{sup 6},6{sup 8},7{sup 3},8), while 7 is a (3,10)-connected 3D net with Schlfli symbol of (3,4,5){sub 2}(3{sup 4},4{sup 8},5{sup 18},6{sup 12},7{sup 2},8). The thermal stability and photoluminescence of the complexes were investigated. Furthermore, DFT calculations were performed for 24 to discuss the temperature controlled self-assembly of the complexes. - Graphical abstract: Seven new coordination polymers with multicarboxylate and rigid ditopic 4-imidazole containing ligands have been obtained and found to show different structures and topologies. - Highlights: Metal complexes with diverse structures of 1D chain, 2D network and 3D framework. Mixed ligands of 1,3-di(1H-imidazol-4-yl)benzene and multicarboxylate. Photoluminescence property.

  18. Benzene analogues of (quasi-)planar M@B{sub n}H{sub n} compounds (M = V{sup ?}, Cr, Mn{sup +}): A theoretical investigation

    SciTech Connect (OSTI)

    Li, Lifen; Xu, Chang; Jin, Baokang; Cheng, Longjiu

    2013-11-07

    The stability of M@B{sub n}H{sub n} (M = V{sup ?}, Cr, Mn{sup +}; n = 58) is investigated by density functional theory. For n = 68, the isomers possess (quasi-)planar local minima showed by geometry optimization at TPSSh/6-311+G{sup **} level. All the optimized structures are thermodynamics stable according to the large HOMO-LUMO gap, binding energy, vertical ionization potential, and vertical electron affinity analysis. The peripheral and central atomic radius fit each other best at n = 7 confirmed by the variation of the binding energy values. The availability of d atom orbitals in M for participation in the ?-delocalized bonding with the peripheral ring leads to the aromaticity of the (quasi-)planar structures and makes them the benzene analogues. This work establishes firmly the metal-doped borane rings as a new type of aromatic molecule.

  19. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    SciTech Connect (OSTI)

    Al-Hamdani, Yasmine S.; Michaelides, Angelos; Alf, Dario; Lilienfeld, O. Anatole von

    2014-11-14

    Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B{sub 3}N{sub 3}H{sub 6}) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.

  20. Quantum effects and anharmonicity in the H{sub 2}-Li{sup +}-benzene complex: A model for hydrogen storage materials

    SciTech Connect (OSTI)

    Kolmann, Stephen J.; D'Arcy, Jordan H.; Jordan, Meredith J. T.

    2013-12-21

    Quantum and anharmonic effects are investigated in H{sub 2}-Li{sup +}-benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials. Three- and 8-dimensional quantum diffusion Monte Carlo (QDMC) and rigid-body diffusion Monte Carlo (RBDMC) simulations are performed on potential energy surfaces interpolated from electronic structure calculations at the M05-2X/6-31+G(d,p) and M05-2X/6-311+G(2df,p) levels of theory using a three-dimensional spline or a modified Shepard interpolation. These calculations investigate the intermolecular interactions in this system, with three- and 8-dimensional 0 K H{sub 2} binding enthalpy estimates, ?H{sub bind} (0 K), being 16.5 kJmol{sup ?1} and 12.4 kJmol{sup ?1}, respectively: 0.1 and 0.6 kJmol{sup ?1} higher than harmonic values. Zero-point energy effects are 35%of the value of ?H{sub bind} (0 K) at M05-2X/6-311+G(2df,p) and cannot be neglected; uncorrected electronic binding energies overestimate ?H{sub bind} (0 K) by at least 6 kJmol{sup ?1}. Harmonic intermolecular binding enthalpies can be corrected by treating the H{sub 2} helicopter and ferris wheel rotations as free and hindered rotations, respectively. These simple corrections yield results within 2% of the 8-dimensional anharmonic calculations. Nuclear ground state probability density histograms obtained from the QDMC and RBDMC simulations indicate the H{sub 2} molecule is delocalized above the Li{sup +}-benzene system at 0 K.

  1. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

    2014-10-22

    Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we showmore » that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B₃N₃H₆) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.« less

  2. A case report of motor neuron disease in a patient showing significant level of DDTs, HCHs and organophosphate metabolites in hair as well as levels of hexane and toluene in blood

    SciTech Connect (OSTI)

    Kanavouras, Konstantinos; Tzatzarakis, Manolis N.; Mastorodemos, Vasileios; Plaitakis, Andreas; Tsatsakis, Aristidis M.

    2011-11-15

    Motor neuron disease is a devastating neurodegenerative condition, with the majority of sporadic, non-familial cases being of unknown etiology. Several epidemiological studies have suggested that occupational exposure to chemicals may be associated with disease pathogenesis. We report the case of a patient developing progressive motor neuron disease, who was chronically exposed to pesticides and organic solvents. The patient presented with leg spasticity and developed gradually clinical signs suggestive of amyotrophic lateral sclerosis, which was supported by the neurophysiologic and radiological findings. Our report is an evidence based case of combined exposure to organochlorine (DDTs), organophosphate pesticides (OPs) and organic solvents as confirmed by laboratory analysis in samples of blood and hair confirming systematic exposure. The concentration of non-specific dialkylphosphates metabolites (DAPs) of OPs in hair (dimethyphopshate (DMP) 1289.4 pg/mg and diethylphosphate (DEP) 709.4 pg/mg) and of DDTs (opDDE 484.0 pg/mg, ppDDE 526.6 pg/mg, opDDD 448.4 pg/mg, ppDDD + opDDT 259.9 pg/mg and ppDDT 573.7 pg/mg) were considerably significant. Toluene and n-hexane were also detected in blood on admission at hospital and quantified (1.23 and 0.87 {mu}g/l, respectively), while 3 months after hospitalization blood testing was found negative for toluene and n-hexane and hair analysis was provided decrease levels of HCHs, DDTs and DAPs. -- Highlights: Black-Right-Pointing-Pointer Exposure to pesticides and organic solvents might be a risk factor for sporadic MND. Black-Right-Pointing-Pointer We report a patient who developed progressive upper and lower motor neuron disease. Black-Right-Pointing-Pointer The patient had a history of occupational exposure to pesticides and solvents. Black-Right-Pointing-Pointer High DDTs' levels and increased levels of DMP and DEP were measured in his hair. Black-Right-Pointing-Pointer The patients' exposure to chemicals might have played

  3. Absorption of ethanol, acetone, benzene and 1,2-dichloroethane through human skin in vitro: a test of diffusion model predictions

    SciTech Connect (OSTI)

    Gajjar, Rachna M.; Kasting, Gerald B.

    2014-11-15

    The overall goal of this research was to further develop and improve an existing skin diffusion model by experimentally confirming the predicted absorption rates of topically-applied volatile organic compounds (VOCs) based on their physicochemical properties, the skin surface temperature, and the wind velocity. In vitro human skin permeation of two hydrophilic solvents (acetone and ethanol) and two lipophilic solvents (benzene and 1,2-dichloroethane) was studied in Franz cells placed in a fume hood. Four doses of each {sup 14}C-radiolabed compound were tested — 5, 10, 20, and 40 μL cm{sup −2}, corresponding to specific doses ranging in mass from 5.0 to 63 mg cm{sup −2}. The maximum percentage of radiolabel absorbed into the receptor solutions for all test conditions was 0.3%. Although the absolute absorption of each solvent increased with dose, percentage absorption decreased. This decrease was consistent with the concept of a stratum corneum deposition region, which traps small amounts of solvent in the upper skin layers, decreasing the evaporation rate. The diffusion model satisfactorily described the cumulative absorption of ethanol; however, values for the other VOCs were underpredicted in a manner related to their ability to disrupt or solubilize skin lipids. In order to more closely describe the permeation data, significant increases in the stratum corneum/water partition coefficients, K{sub sc}, and modest changes to the diffusion coefficients, D{sub sc}, were required. The analysis provided strong evidence for both skin swelling and barrier disruption by VOCs, even by the minute amounts absorbed under these in vitro test conditions. - Highlights: • Human skin absorption of small doses of VOCs was measured in vitro in a fume hood. • The VOCs tested were ethanol, acetone, benzene and 1,2-dichloroethane. • Fraction of dose absorbed for all compounds at all doses tested was less than 0.3%. • The more aggressive VOCs absorbed at higher levels than

  4. Ultra-low-temperature reactions of C({sup 3}P{sub 0}) atoms with benzene molecules in helium droplets

    SciTech Connect (OSTI)

    Krasnokutski, Serge A. Huisken, Friedrich

    2014-12-07

    The reaction of carbon atoms with benzene has been investigated in liquid helium droplets at T = 0.37 K. We found an addition of the carbon atom to form an initial intermediate complex followed by a ring opening and the formation of a seven-membered ring. In contrast to a previous gas phase study, the reaction is frozen after these steps and the loss of hydrogen does not occur. A calorimetric technique was applied to monitor the energy balance of the reaction. It was found that more than 267 kJ mol{sup ?1} were released in this reaction. This estimation is in line with quantum chemical calculations of the formation energy of a seven-membered carbon ring. It is suggested that reactions of this kind could be responsible for the low abundance of small polycyclic aromatic hydrocarbon molecules in the interstellar medium. We also found the formation of weakly bonded water-carbon adducts, in which the carbon atom is linked to the oxygen atom of the water molecule with a binding energy of about 33.4 kJ mol{sup ?1}.

  5. Treatment of Produced Water Using a Surfactant Modified Zeolite/Vapor Phase Bioreactor System

    SciTech Connect (OSTI)

    Lynn E. Katz; Kerry A. Kinney; Robert S. Bowman; Enid J. Sullivan; Soondong Kwon; Elaine B. Darby; Li-Jung Chen; Craig R. Altare

    2006-01-31

    Co-produced water from the oil and gas industry accounts for a significant waste stream in the United States. Produced waters typically contain a high total dissolved solids content, dissolved organic constituents such as benzene and toluene, an oil and grease component as well as chemicals added during the oil-production process. It has been estimated that a total of 14 billion barrels of produced water were generated in 2002 from onshore operations (Veil, 2004). Although much of this produced water is disposed via reinjection, environmental and cost considerations can make surface discharge of this water a more practical means of disposal. In addition, reinjection is not always a feasible option because of geographic, economic, or regulatory considerations. In these situations, it may be desirable, and often necessary from a regulatory viewpoint, to treat produced water before discharge. It may also be feasible to treat waters that slightly exceed regulatory limits for re-use in arid or drought-prone areas, rather than losing them to reinjection. A previous project conducted under DOE Contract DE-AC26-99BC15221 demonstrated that surfactant modified zeolite (SMZ) represents a potential treatment technology for produced water containing BTEX. Laboratory and field experiments suggest that: (1) sorption of benzene, toluene, ethylbenzene and xylenes (BTEX) to SMZ follows linear isotherms in which sorption increases with increasing solute hydrophobicity; (2) the presence of high salt concentrations substantially increases the capacity of the SMZ for BTEX; (3) competitive sorption among the BTEX compounds is negligible; and, (4) complete recovery of the SMZ sorption capacity for BTEX can be achieved by air sparging the SMZ. This report summarizes research for a follow on project to optimize the regeneration process for multiple sorption/regeneration cycles, and to develop and incorporate a vapor phase bioreactor (VPB) system for treatment of the off-gas generated during

  6. Tank Closure and Waste Management Environmental Impact Statement...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... as shown in Table 5-192; toluene (339); formaldehyde (80); and benzene (17) (SAIC 2011a). ... and 3, which are included, respectively, in Alternative Combinations 2 and 3 (SAIC 2011a). ...

  7. Modeling of 1,3-hexadiene, 2,4-hexadiene and 1,4-hexadiene-doped methane flames: Flame modeling, benzene and styrene formation

    SciTech Connect (OSTI)

    Sharma, Sandeep; Harper, Michael R.; Green, William H.

    2010-07-15

    In this work, we have developed a detailed chemical kinetic model and reacting flow simulation for the hexadiene-doped 2-d methane diffusion flames studied experimentally by McEnally and Pfefferle. The GRI-Mech 2.11 methane oxidation and Lawrence Livermore butane oxidation mechanisms were used as the base mechanism to which hexadiene chemistry generated by Reaction Mechanism Generator (RMG) was added. Some important chemically activated pathways leading to aromatic species formation, including the reactions on C{sub 5}H{sub 7}, C{sub 6}H{sub 10}, C{sub 6}H{sub 9}, C{sub 6}H{sub 7}, C{sub 8}H{sub 8} and C{sub 8}H{sub 9} potential energy surfaces, are examined in great detail using quantum chemistry (CBS-QB3) and master equation analysis as implemented in Variflex. An efficient program to solve the doped methane diffusion flame was developed. The solver uses the method of lines to solve the species mass balance equation arising in the diffusion flame. It assumes that the temperature and velocity profiles of the doped flame are the same as those of the undoped flame. The mole fractions of various species as predicted by our model are compared to the experimentally measured mole fractions. The agreement between theory and experiments is quite good for most molecules. The added hexadiene dopants to the flame decompose to produce significant amount of cyclopentadienyl radical, which combines with methyl radical to produce benzene. We also show that styrene is formed primarily by recombination of cyclopentadienyl and propargyl radicals, a pathway which to our knowledge, has not been included in prior flame simulations. (author)

  8. Assessment and remediation at former manufactured gas plants

    SciTech Connect (OSTI)

    Mehan, D.G.

    1995-12-01

    Over 1,000 former Manufactured Gas Plants (MGP) have been identified in the United States. Gal Plants were used to produce gas for lighting and heating from coal and oil from the mid-1800s until the 1950s. Former MGP sites are typically impacted by a variety of compounds that do not collectively lend themselves to {open_quotes}standard{close_quotes} assessment and remedial solutions. These compounds include the volatile organic compounds (VOCs) benzene, toluene, ethylbenzene, and xylene, a variety of semi-volatile organic compound, and inorganic compounds (iron and cyanide). The assessment of former MGP sites is complicated because many former sites are now located in developed and industrialized areas. MGP wastes and by-products were typically disposed on-site. Many modern buildings are now located over former MGP sites. Standard assessment tools such as augering and drilling tend to encounter former structures, making their use difficult and ineffective. Assessment by excavation and geophysical methods allows the acquisition of only shallow data. The remediation of impacted soils and ground water at former MGP sites poses significant challenges due to the differing characteristics of the typical MGP compounds. For example, soil vapor extraction and ground water treatment may decrease VOC concentrations, yet be ineffective on the inorganic and PAH compounds. Because of the variety of typical MGP associated wastes, risk assessment is a vital tool in assessing and selecting the appropriate remedial strategies. Several states have aggressively adopted clean-up programs that rely on risk assessment to determine the appropriate remedial strategy at former MGP sites. At numerous sites, no further action is employed because of the VOCs have attenuated over time, the PAH and inorganic compounds are relatively immobile, ground water contamination plumes are limited, and risk assessment indicates acceptable risks.

  9. A lean methane premixed laminar flame doped with components of diesel fuel part III: Indane and comparison between n-butylbenzene, n-propylcyclohexane and indane

    SciTech Connect (OSTI)

    Pousse, E.; Tian, Z.Y.; Glaude, P.A.; Fournet, R.; Battin-Leclerc, F. [Laboratoire des Reactions et de Genie des Procedes, CNRS, Nancy Universite, 1 rue Grandville, BP 20451, 54001 NANCY Cedex (France)

    2010-07-15

    To better understand the chemistry of the combustion of components of diesel fuel, the structure of a laminar lean premixed methane flame doped with indane has been investigated. The inlet gases contained 7.1% (molar) of methane, 36.8% of oxygen and 0.9% of indane corresponding to an equivalence ratio of 0.67 and a ratio C{sub 10}H{sub 14}/CH{sub 4} of 12.8%. The flame has been stabilized on a burner at a pressure of 6.7 kPa (50 Torr) using argon as diluent, with a gas velocity at the burner of 49.1 cm s{sup -1} at 333 K. Quantified species included the usual methane C{sub 0}-C{sub 2} combustion products, but also 16 C{sub 3}-C{sub 5} non-aromatic hydrocarbons, 6 C{sub 1}-C{sub 3} non-aromatic oxygenated compounds, as well as 22 aromatic products, namely benzene, toluene, xylenes, phenylacetylene, ethylbenzene, styrene, propenylbenzene, allylbenzene, n-propylbenzene, methylstyrenes, ethyltoluenes, trimethylbenzenes, n-butylbenzene, dimethylethylbenzene, indene, methylindenes, methylindane, benzocyclobutene, naphthalene, phenol, benzaldehyde, and benzofuran. A new mechanism for the oxidation of indane was proposed whose predictions were in satisfactory agreement with measured species profiles in both flames and jet-stirred reactor experiments. The main reaction pathways of consumption of indane have been derived from flow rate analyses in the two types of reactors. A comparison of the effect of the addition of three components of diesel fuel, namely indane, n-butylbenzene and n-propylcyclohexane (parts I and II of this series of paper), on the structure of a laminar lean premixed methane flame is also presented. (author)

  10. Metagenomics, metatranscriptomics and single cell genomics reveal functional response of active Oceanospirillales to Gulf oil spill

    SciTech Connect (OSTI)

    Mason, Olivia U.; Hazen, Terry C.; Borglin, Sharon; Chain, Patrick S. G.; Dubinsky, Eric A.; Fortney, Julian L.; Han, James; Holman, Hoi-Ying N.; Hultman, Jenni; Lamendella, Regina; Mackelprang, Rachel; Malfatti, Stephanie; Tom, Lauren M.; Tringe, Susannah G.; Woyke, Tanja; Zhou, Jizhong; Rubin, Edward M.; Jansson, Janet K.

    2012-06-12

    The Deepwater Horizon oil spill in the Gulf of Mexico resulted in a deep-sea hydrocarbon plume that caused a shift in the indigenous microbial community composition with unknown ecological consequences. Early in the spill history, a bloom of uncultured, thus uncharacterized, members of the Oceanospirillales was previously detected, but their role in oil disposition was unknown. Here our aim was to determine the functional role of the Oceanospirillales and other active members of the indigenous microbial community using deep sequencing of community DNA and RNA, as well as single-cell genomics. Shotgun metagenomic and metatranscriptomic sequencing revealed that genes for motility, chemotaxis and aliphatic hydrocarbon degradation were significantly enriched and expressed in the hydrocarbon plume samples compared with uncontaminated seawater collected from plume depth. In contrast, although genes coding for degradation of more recalcitrant compounds, such as benzene, toluene, ethylbenzene, total xylenes and polycyclic aromatic hydrocarbons, were identified in the metagenomes, they were expressed at low levels, or not at all based on analysis of the metatranscriptomes. Isolation and sequencing of two Oceanospirillales single cells revealed that both cells possessed genes coding for n-alkane and cycloalkane degradation. Specifically, the near-complete pathway for cyclohexane oxidation in the Oceanospirillales single cells was elucidated and supported by both metagenome and metatranscriptome data. The draft genome also included genes for chemotaxis, motility and nutrient acquisition strategies that were also identified in the metagenomes and metatranscriptomes. These data point towards a rapid response of members of the Oceanospirillales to aliphatic hydrocarbons in the deep sea.

  11. Is It Homogeneous or Heterogeneous Catalysis Derived from [RhCp*Cl2]2? In Operando-XAFS, Kinetic and Crucial Kinetic Poisoning Evidence for Subnanometer Rh4 Cluster-Based Benzene Hydrogenation Catalysis

    SciTech Connect (OSTI)

    Bayram, Ercan; Linehan, John C.; Fulton, John L.; Roberts, John A.; Szymczak, Nathaniel; Smurthwaite, Tricia D.; Ozkar, Saim; Balasubramanian, Mahalingam; Finke, Richard G.

    2011-11-23

    Determining the true, kinetically dominant catalytically active species, in the classic benzene hydrogenation system pioneered by Maitlis and co-workers 34 years ago starting with [RhCp*Cl2]2 (Cp* = [{eta}5-C5(CH3)5]), has proven to be one of the most challenging case studies in the quest to distinguish single-metal-based 'homogeneous' from polymetallic, 'heterogeneous' catalysis. The reason, this study will show, is the previous failure to use the proper combination of (i) operando spectroscopy to determine the dominant form(s) of the precatalyst's mass under catalysis (i.e., operating) conditions, plus then and crucially also (ii) the previous lack of the necessary kinetic studies, catalysis being a 'wholly kinetic phenomenon' as J. Halpern long ago noted. An important contribution from this study will be to reveal the power of quantitiative kinetic poisoning experiments for distinguishing single-metal, or in this case subnanometer Rh4 cluster-based catalysis from larger, polymetallic Rh(0)n nanoparticle catalysis, at least under favorable conditions. The combined operando-XAFS (X-ray absorption fine structure) spectroscopy and kinetic evidences provide a compelling case for Rh4-based, with average stoichiometry 'Rh4Cp*2.4Cl4Hc', benzene hydrogenation catalysis in 2-propanol with added Et3N and at 100 C and 50 atm initial H2 pressure. The results also reveal, however, that if even ca. 1.4% of the total soluble Rh(0)n had formed nanoparticles, then those Rh(0)n nanoparticles would have been able to account for all the observed benzene hydrogenation catalytic rate (using commercial, ca. 2 nm, polyethyleneglycol-dodecylether hydrosol stabilized Rh(0)n nanoparticles as a model system). The results 'especially the poisoning methodology developed and employed' are of significant, broader interest since determining the nature of the true catalyst continues to be a central, often vexing issue in any and all catalytic reactions. The results are also of fundamental

  12. Method of uranium reclamation from aqueous systems by reactive ion exchange. [US DOE patent application; anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands

    DOE Patents [OSTI]

    Maya, L.

    1981-11-05

    A reactive ion exchange method for separation and recovery of values of uranium, neptunium, plutonium, or americium from substantially neutral aqueous systems of said metals comprises contacting said system with an effective amount of a basic anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands to achieve nearly 100% sorption of said actinyl ion onto said resin and an aqueous system practically free of said actinyl ions. The method is operational over an extensive range of concentrations from about 10/sup -6/ M to 1.0 M actinyl ion and a pH range of about 4 to 7. The method has particulr application to treatment of waste streams from Purex-type nuclear fuel reprocessing facilities and hydrometallurgical processes involving U, Np, P, or Am.

  13. Rapid microwave hydrothermal synthesis of ZnGa{sub 2}O{sub 4} with high photocatalytic activity toward aromatic compounds in air and dyes in liquid water

    SciTech Connect (OSTI)

    Sun Meng; Li Danzhen; Zhang Wenjuan; Chen Zhixin; Huang Hanjie; Li Wenjuan; He Yunhui; Fu Xianzhi

    2012-06-15

    ZnGa{sub 2}O{sub 4} was synthesized from Ga(NO{sub 3}){sub 3} and ZnCl{sub 2} via a rapid and facile microwave-assisted hydrothermal method. The photocatalytic properties of the as-prepared ZnGa{sub 2}O{sub 4} were evaluated by the degradation of pollutants in air and aqueous solution under ultraviolet (UV) light illumination. The results demonstrated that ZnGa{sub 2}O{sub 4} had exhibited efficient photocatalytic activities higher than that of commercial P25 (Degussa Co.) in the degradation of benzene, toluene, and ethylbenzene, respectively. In the liquid phase degradation of dyes (methyl orange, Rhodamine B, and methylene blue), ZnGa{sub 2}O{sub 4} has also exhibited remarkable activities higher than that of P25. After 32 min of UV light irradiation, the decomposition ratio of methyl orange (10 ppm, 150 mL) over ZnGa{sub 2}O{sub 4} (0.06 g) was up to 99%. The TOC tests revealed that the mineralization ratio of MO (10 ppm, 150 mL) was 88.1% after 90 min of reaction. A possible mechanism of the photocatalysis over ZnGa{sub 2}O{sub 4} was also proposed. - Graphical abstract: In the degradation of RhB under UV light irradiation, ZnGa{sub 2}O{sub 4} had exhibited efficient photo-activity, and after only 24 min of irradiation the decomposition ratio was up to 99.8%. Highlights: Black-Right-Pointing-Pointer A rapid and facile M-H method to synthesize ZnGa{sub 2}O{sub 4} photocatalyst. Black-Right-Pointing-Pointer The photocatalyst exhibits high activity toward benzene and dyes. Black-Right-Pointing-Pointer The catalyst possesses more surface hydroxyl sites than TiO{sub 2} (P25). Black-Right-Pointing-Pointer Deep oxidation of different aromatic compounds and dyes over catalyst.

  14. Variations in the structure of aromatic solvents under the influence of microadditives of the C{sub 60} fullerene

    SciTech Connect (OSTI)

    Ginzburg, B. M. Tuichiev, Sh.

    2007-02-15

    The structural ordering of aromatic solvents is investigated using wide-angle X-ray diffraction. It is shown that the degree of structural ordering of aromatic solvents at room temperature decreases in the following sequence: benzene, toluene, and n-xylene. The introduction of the C{sub 60} fullerene ({approx}0.001%) into these solvents leads to an increase in the degree of their ordering. Upon introduction of the fullerene, the degree of structural ordering increases significantly in n-xylene and only slightly in toluene and remains virtually unchanged in benzene. An analysis of the small-angle X-ray diffraction patterns of C{sub 60} fullerene solutions in benzene likewise demonstrates that the introduction of the fullerene into benzene leads to an insignificant change in the degree of structural ordering of this solvent. The specific features of the structure and behavior of benzene upon interaction with C{sub 60} fullerene additives are discussed.

  15. Infrared identification of the {sigma}-complex of Cl-C{sub 6}H{sub 6} in the reaction of chlorine atom and benzene in solid para-hydrogen

    SciTech Connect (OSTI)

    Bahou, Mohammed; Witek, Henryk; Lee, Yuan-Pern

    2013-02-21

    The reaction of a chlorine atom with benzene (C{sub 6}H{sub 6}) is important in organic chemistry, especially in site-selective chlorination reactions, but its product has been a subject of debate for five decades. Previous experimental and theoretical studies provide no concrete conclusion on whether the product is a {pi}- or {sigma}-form of the Cl-C{sub 6}H{sub 6} complex. We took advantage of the diminished cage effect of para-hydrogen (p-H{sub 2}) to produce Cl in situ to react with C{sub 6}H{sub 6} (or C{sub 6}D{sub 6}) upon photolysis of a Cl{sub 2}/C{sub 6}H{sub 6} (or C{sub 6}D{sub 6})/p-H{sub 2} matrix at 3.2 K. The infrared spectrum, showing intense lines at 1430.5, 833.6, 719.8, 617.0, and 577.4 cm{sup -1}, and several weaker ones for Cl-C{sub 6}H{sub 6}, and the deuterium shifts of observed new lines unambiguously indicate that the product is a 6-chlorocyclohexadienyl radical, i.e., the {sigma}-complex of Cl-C{sub 6}H{sub 6}. Observation of the {sigma}-complex rather than the {pi}-complex indicates that the {sigma}-complex is more stable in solid p-H{sub 2} at 3.2 K. The spectral information is crucial for further investigations of the Cl + C{sub 6}H{sub 6} reaction either in the gaseous or solution phase.

  16. Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes

    SciTech Connect (OSTI)

    Maranzana, Andrea E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it Giordana, Anna E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it Indarto, Antonius Tonachini, Glauco; Barone, Vincenzo E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it; Causà, Mauro E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it; Pavone, Michele E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it

    2013-12-28

    Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔE{sub AB}. Counterpoise-corrected interaction energies ΔE{sub AB} are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A−B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [E{sub MP2/CBS}] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔE{sub CC-MP}, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔE{sub AB} with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting

  17. Evaluation of a Polyvinyl Toluene Neutron Counter Array (Conference...

    Office of Scientific and Technical Information (OSTI)

    Results demonstrate that analysis with Monte Carlo N-Particle (MCNP) can be used to obtain a better understanding of field measurement results and aid in algorithm development for ...

  18. Density and viscosity for mixtures of propanoic acid with aromatic hydrocarbons at 298.15 K

    SciTech Connect (OSTI)

    Singh, M.; Gupta, P.C.; Kesharwani, R.N.

    1995-03-01

    The density and viscosity of binary mixtures of propanic acid + benzene, + toluene, and + o-, + m-, and + p-xylenes have been measured at 298.15 K. Excess volumes have been calculated. The interactions existing between the components have been discussed. The results are used to theoretically justify the validity of the viscosity models.

  19. Investigation of Phase and Emulsion Behavior, Surfactant Retention and Condensate Recovery for Condensate/Water/Ethanol Mixtures

    SciTech Connect (OSTI)

    Ramanathan Sampath

    2004-09-30

    This semi-annual technical progress report describes work performed at Morehouse College under DOE Grant No. DE-FG26-02NT15447 during the period April 01, 2004 to September 30, 2004 which covers the fourth six months of the project. Presently work is in progress to characterize phase and emulsion behavior for ethylbenzene/water/ethanol system. Ethylbenzene that has the equivalent carbon number is used as the model condensate. During this reporting period, work was under way and the electrical conductivity experimental system was set up at the Atlanta University Center. Following the set-up of the emulsion measurement system, the electronic instruments and data acquisition modules involved were tested for proper operation of the system. Then, the conductivity output was normalized with that obtained for 10mM NaCl water. Radial coreflooding experiments with ethanol injection prior to and after water injection were completed to assess the effectiveness of the surfactant flooding in the recovery of condensate by our industrial partner, Surtek, CO, in this reporting period. In Run 1, 10 mM NaCl without ethanol injection recovered 31.5% of the initial ethyl benzene saturation. Injection of ethanol following 10 mM NaCl produced a tertiary ethyl benzene bank with maximum ethyl benzene cuts of 32%. In Run 2, 50 vol% of pure (100%) ethanol was injected and flowed through the Berea sandstone after Ethyl Benzene Saturation. 69% of the initial ethyl benzene was recovered. Results of the radial corefloods are very encouraging. Emulsion conductivity measurements for conjugate pair phases are in progress at Morehouse.

  20. Direct Push Groundwater Circulation Wells for Remediation of BTEX and Volatile Organics

    SciTech Connect (OSTI)

    Borden, R. E.; Cherry, Robert Stephen

    2000-09-01

    Direct push groundwater circulation wells (DP-GCW) are a promising technology for remediation of groundwater contaminated with dissolved hydrocarbons and chlorinated solvents. In these wells, groundwater is withdrawn from the formation at the bottom of the well, aerated and vapor stripped and injected back into the formation at or above the water table. Previous field studies have shown that: (a) GCWs can circulate significant volumes of groundwater; and (b) GCWs can effectively remove volatile compounds and add oxygen. In this work, we describe the development and field-testing of a system of DP-GCWs for remediation of volatile organics such as benzene, toluene, ethylbenzene, and toluene (BTEX). The GCWs were constructed with No. 20 slotted well screen (2.4 cm ID) and natural sand pack extending from 1.5 to 8.2 m below grade. Air is introduced ~7.5 m below grade via 0.6 cm tubing. Approximately 15% of the vertical length of the air supply tubing is wrapped in tangled mesh polypropylene geonet drainage fabric to provide surface area for biological growth and precipitation of oxidized iron. These materials were selected to allow rapid installation of the GCWs using 3.8 cm direct push Geoprobe® rods, greatly reducing well installation costs. Laboratory testing of these sparged wells and computational fluid dynamics (CFD) modeling showed that these wells, although they used only about 1 L/min of air, could circulate about 1 L/min of water through the surrounding aquifer. This flow was sufficient to capture all of a flowing contaminant if the wells are sufficiently closely together, about 1 meter on center depending on the air flow rate supplied, in a line across the plume. The CFD work showed the details of this ability to capture, and also showed that unforeseen heterogeneities in the aquifer such as a gradient of permeability or a thin impermeable layer (such as a clay layer) did not prevent the system from working largely as intended. The system was tested in a

  1. Direct Push Groundwater Circulation Wells for Remediation of BTEX and Volatile Organics

    SciTech Connect (OSTI)

    Borden, R.C.; Cherry, R.S.

    2000-09-30

    Direct push groundwater circulation wells (DP-GCW) are a promising technology for remediation of groundwater contaminated with dissolved hydrocarbons and chlorinated solvents. In these wells, groundwater is withdrawn from the formation at the bottom of the well, aerated and vapor stripped and injected back into the formation at or above the water table. Previous field studies have shown that: (a) GCWs can circulate significant volumes of groundwater; and (b) GCWs can effectively remove volatile compounds and add oxygen. In this work, we describe the development and field-testing of a system of DP-GCWs for remediation of volatile organics such as benzene, toluene, ethylbenzene, and toluene (BTEX). The GCWs were constructed with No. 20 slotted well screen (2.4 cm ID) and natural sand pack extending from 1.5 to 8.2 m below grade. Air is introduced {approximately}7.5 m below grade via 0.6 cm tubing. Approximately 15% of the vertical length of the air supply tubing is wrapped in tangled mesh polypropylene geonet drainage fabric to provide surface area for biological growth and precipitation of oxidized iron. These materials were selected to allow rapid installation of the GCWs using 3.8 cm direct push Geoprobe{reg_sign} rods, greatly reducing well installation costs. Laboratory testing of these sparged wells and computational fluid dynamics (CFD) modeling showed that these wells, although they used only about 1 L/min of air, could circulate about 1 L/min of water through the surrounding aquifer. This flow was sufficient to capture all of a flowing contaminant if the wells are sufficiently closely together, about 1 meter on center depending on the air flow rate supplied, in a line across the plume. The CFD work showed the details of this ability to capture, and also showed that unforeseen heterogeneities in the aquifer such as a gradient of permeability or a thin impermeable layer (such as a clay layer) did not prevent the system from working largely as intended. The

  2. A novel plug-flow digester for biogasification of conventional and hazardous organics

    SciTech Connect (OSTI)

    Ghosh, S.; Kato, Y.; Liu, T.; Fukushi, K.

    1996-12-31

    A novel plug-flow digestion system of simple construction was designed, fabricated and operated for several years with a synthetic mixture of solid and liquid wastes simulating conditions south of the US-Mexican border and other developing countries. Benzene, toluene, and o-xylene (BTX) were mixed with the synthetic feed in several phases of this research to simulate field conditions where these solvents are discharged to public sewers and mixed with non-hazardous pollutants. The mesophilic plug-flow digester exhibited a high gas yield of 0.46 SCM /kg VS added, a methane content of 77 mol%, and a VS reduction of 75% at an HRT of 13 days with a 96% biodegradation of the feed toluene. At a feed concentration of 50 mg/l, toluene did not inhibit anaerobic fermentation. Gas and methane yields, and VS and COD conversion efficiencies were about the same with or without toluene present in the feed. At a reduced HRT of 8 days, a high feed COD concentration of 50,000 mg/l, and a loading rate of 0.48 kg VS/m{sup 3}-day, the digester afforded a gas yield of 3.1 SCM /kg VS added, and a methane content of 67 mol%. Benzene, toluene, and o-xylene were biodegraded at efficiencies of 94%, 90%, and 88%, respectively. The degradation kinetics of the xenobiotic compound could be described by a model based on cometabolic degradation of these secondary substrates.

  3. PREPARATION OF HIGH PURITY UF$sub 4$

    DOE Patents [OSTI]

    Magner, J.E.; Long, R.S.; Ellis, D.A.; Grinstead, R.R.

    1962-04-17

    S>A process for preparing very highly pure uranous tetrafluoride from impure uranium laden solvent extraction strip solutions, ion exchange process and resin-inpulp process eluate solutions which are at least 8M in hydrochloric acid is described. The process first comprises treating any of the above-mentioned solutions with a reducing agent to reduce the uranium to the + 4 oxidation state, and then contacting the reduced solution with an extractant phase comprising about 10 to 70% of tri-butyl phosphate in an organic solvent-diluent selected from benzene, ethyl-benzene, chlorobenzene, xylene, kerosene, or the like. The uranium is extracted into the extractant phase and is subsequently precipitated by treating the extractant with an aqueous fluoride solution. The highly pure uranous tetrafluoride precipitate is separated from the phases and recovered for subsequent utilization. (AEC)

  4. Chemistry of Furan Conversion into Aromatics and Olefins over HZSM-5: A Model Biomass Conversion Reaction

    SciTech Connect (OSTI)

    Cheng, Yu-Ting; Huber, George W.

    2011-06-03

    The conversion of furan (a model of cellulosic biomass) over HZSM-5 was investigated in a thermogravimetric analysismass spectrometry system, in situ Fourier transform infrared analysis, and in a continuous-flow fixed-bed reactor. Furan adsorbed as oligomers at room temperature with a 1.73 of adsorbed furan/Al ratio. These oligomers were polycyclic aromatic compounds that were converted to CO, CO?, aromatics, and olefins at temperatures from 400 to 600 C. Aromatics (e.g., benzene, toluene, and naphthalene), oligomer isomers (e.g., benzofuran, 2,2-methylenebisfuran, and benzodioxane), and heavy oxygenates (C??{sub +} oligomers) were identified as intermediates formed inside HZSM-5 at different reaction temperatures. During furan conversion, graphite-type coke formed on the catalyst surface, which caused the aromatics and olefins formation to deactivate within the first 30 min of time on-stream. We have measured the effects of space velocity and temperature for furan conversion to help us understand the chemistry of biomass conversion inside zeolite catalysts. The major products for furan conversion included CO, CO?, allene, C?C? olefins, benzene, toluene, styrene, benzofuran, indene, and naphthalene. The aromatics (benzene and toluene) and olefins (ethylene and propylene) selectivity decreased with increasing space velocity. Unsaturated hydrocarbons such as allene, cyclopentadiene, and aromatics selectivity increased with increasing space velocity. The product distribution was selective to olefins and CO at high temperatures (650 C) but was selective to aromatics (benzene and toluene) at intermediate temperatures (450600 C). At low temperatures (450 C), benzofuran and coke contributed 60% of the carbon selectivity. Several different reactions were occurring for furan conversion over zeolites. Some important reactions that we have identified in this study include DielsAlder condensation (e.g., two furans form benzofuran and water), decarbonylation (e

  5. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Processing Area Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Conventional Blendstock for Oxygenate Blending (CBOB)

  6. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Imports & Exports Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether),

  7. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Production Capacity of Operable Petroleum Refineries Definitions Key Terms Definition Alkylate The product of an alkylation reaction. It usually refers to the high octane product from alkylation units. This alkylate is used in blending high octane gasoline. Aromatics Hydrocarbons characterized by unsaturated ring structures of carbon atoms. Commercial petroleum aromatics are benzene, toluene, and xylene (BTX). Asphalt A dark-brown-to-black cement-like material containing bitumens as the

  8. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Input Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Conventional Blendstock for Oxygenate Blending (CBOB) Motor

  9. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    and Blender Net Inputs Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Blending Plant A facility which has no

  10. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Inputs & Utilization Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether),

  11. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Total Stocks Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether), butane, and

  12. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Weekly Supply Estimates Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether),

  13. Electron localization in a mixed-valence diniobium benzene complex...

    Office of Scientific and Technical Information (OSTI)

    Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral ...

  14. Electron localization in a mixed-valence diniobium benzene complex

    Office of Scientific and Technical Information (OSTI)

    Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral ...

  15. The use of white-rot fungi as active biofilters

    SciTech Connect (OSTI)

    Braun-Luellemann, A.; Johannes, C.; Majcherczyk, A.; Huettermann, A.

    1995-12-31

    White-rot fungi, growing on lignocellulosic substrates, have been successfully used as active organisms in biofilters. Filters using these fungi have a very high biological active surface area, allowing for high degrees of retention, a comparatively low pressure drop, and a high physical stability. The unspecific action of the extracellular enzymes of the white-rot fungi allows for the degradation of a wide variety of substances by the same organism. Degradation of several compounds in the gas phase by the white-rot fungi Trametes versicolor, Pleurotus ostreatus, Bjerkandera adusta, and Phanerochaete chrysosporium was tested. Among the aromatic solvents, styrene was the compound that was most readily degraded, followed by ethylbenzene, xylenes, and toluene. Tetrahydrofuran and dichloromethane were also degraded, whereas dioxane could not be attacked by fungi under the conditions used. Acrylonitrile and aniline were degraded very well, whereas pyridine was resistant to degradation. The process for removing styrene is now in the scaling-up stage.

  16. Analysis of low molecular weight hydrocarbons including 1,3-butadiene in engine exhaust gases using an aluminum oxide porous-layer open-tubular fused-silica column

    SciTech Connect (OSTI)

    Pelz, N.; Dempster, N.M.; Shore, P.R. )

    1990-05-01

    A method for the quantitative analysis of individual hydrocarbons in the C1-C8 range emitted in engine exhaust gases is described. The procedure provides base-line or near base-line resolution of C4 components including 1,3-butadiene. With a run time of less than 50 min, the light aromatics (benzene, toluene, ethyl benzene, p- and m-xylene, and o-xylene) are resolved during the same analysis as aliphatic hydrocarbons in the C1-C8 range. It is shown that typical 1,3-butadiene levels in engine exhaust are about 5 ppm at each of two engine conditions. Aromatic hydrocarbon levels show a dependence on engine operating conditions, benzene being about 20 ppm at high speed and about 40 ppm at idle.

  17. INVESTIGATION OF PHASE AND EMULSION BEHAVIOR, SURFACTANT RETENTION, AND CONDENSATE RECOVERY FOR CONDENSATE/WATER/ETHANOL MIXTURES

    SciTech Connect (OSTI)

    Ramanathan Sampath

    2005-12-01

    This final technical report describes work performed at Morehouse College under DOE Grant No. DE-FG26-02NT15447 during the period October 01, 2002 to September 30, 2005, which covers the total performance period of the project. During this period, work was conducted to characterize phase and emulsion behavior for ethylbenzene/water/ethanol system. Ethylbenzene that has the equivalent carbon number was used as the model condensate. Salinity scans were performed for 0, 5, 10, 20, 50, 100, 250, 500, and 1000 mM salt concentrations at room temperature to identify the optimal salinity and salinity intervals in which all phases coexisted. It was found that only two phases formed, and salinity has no significant effect in the volumes of the phases formed. Experiments were repeated at 30 C and observed salinity has no effect at higher temperatures as well. Following the salinity experiments, measurements were made with 10mM NaCl water for surfactant concentrations from 2 to 70 volume percent at room temperature. It was found that only two phases were formed upto 60 vol% concentration of the surfactant. Above 60 vol% surfactant, the mixture produced only a single phase. Experiments were repeated from 2 to 70 C and observed that temperature has no significant effect on the number of phases formed. At the temperatures and surfactant concentration tested, volume fraction of the aqueous bottom phase was found to be larger than that of the top phase. Electrical conductivity measurements were then conducted for bottom/top, and top/bottom conjugate pair phases of the ethylbenzene/water/ethanol system formed by mixing ethanol at various volume percentages including 2,10,33,and 56% while keeping the volumes of ethylbenzene and water the same in the mixture. Electrical conductivity of the bottom phase decreased as ethanol volume fraction in the mixture increased. Conductivity of the top phase was found small and remained almost the same for variations in ethanol volume fraction in

  18. Public health assessment for Petro-Chemical, Inc. (Turtle Bayou) Liberty, Liberty County, Texas, Region 6. CERCLIS No. TXD980873350. Final report

    SciTech Connect (OSTI)

    Not Available

    1993-03-30

    The Petro-Chemical Systems, Inc. site, located near Liberty, Texas, is a site where unauthorized disposal of petroleum-based oils has taken place. Although there is evidence of past exposure to site contaminants, the best available evidence does not indicate that humans are currently being exposed to site contaminants at levels that could cause adverse health effects. Contaminated ground water, surface water, soils, and surface water sediments have been found on the site. Although sampling was done for 144 priority pollutants, the primary contaminants of concern are benzene, ethylbenzene, xylene, naphthalene, polycyclic aromatic hydrocarbons, and lead. Because the greatest threat to public health would be contamination of drinking water, the Agency for Toxic Substances and Disease Registry (ATSDR) has recommended that necessary actions are taken to insure that private wells do not become contaminated with site contaminants.

  19. Chemical structures of low-pressure premixed methylcyclohexane flames as benchmarks for the development of a predictive combustion chemistry model

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Skeen, Scott A.; Yang, Bin; Jasper, Ahren W.; Pitz, William J.; Hansen, Nils

    2011-11-14

    The chemical compositions of three low-pressure premixed flames of methylcyclohexane (MCH) are investigated with the emphasis on the chemistry of MCH decomposition and the formation of aromatic species, including benzene and toluene. The flames are stabilized on a flat-flame (McKenna type) burner at equivalence ratios of φ = 1.0, 1.75, and 1.9 and at low pressures between 15 Torr (= 20 mbar) and 30 Torr (= 40 mbar). The complex chemistry of MCH consumption is illustrated in the experimental identification of several C7H12, C7H10, C6H12, and C6H10 isomers sampled from the flames as a function of distance from the burner.more » Three initiation steps for MCH consumption are discussed: ring-opening to heptenes and methyl-hexenes (isomerization), methyl radical loss yielding the cyclohexyl radical (dissociation), and H abstraction from MCH. Mole fraction profiles as a function of distance from the burner for the C7 species supplemented by theoretical calculations are presented, indicating that flame structures resulting in steeper temperature gradients and/or greater peak temperatures can lead to a relative increase in MCH consumption through the dissociation and isomerization channels. Trends observed among the stable C6 species as well as 1,3-pentadiene and isoprene also support this conclusion. Relatively large amounts of toluene and benzene are observed in the experiments, illustrating the importance of sequential H-abstraction steps from MCH to toluene and from cyclohexyl to benzene. Furthermore, modeled results using the detailed chemical model of Pitz et al. (Proc. Combust. Inst.2007, 31, 267–275) are also provided to illustrate the use of these data as a benchmark for the improvement or future development of a MCH mechanism.« less

  20. Make aromatics from LPG

    SciTech Connect (OSTI)

    Doolan, P.C. ); Pujado, P.R. )

    1989-09-01

    Liquefied petroleum gas (LPG) consists mainly of the propane and butane fraction recovered from gas fields, associated petroleum gas and refinery operations. Apart from its use in steam cracking and stream reforming, LPG has few petrochemical applications. The relative abundance of LPG and the strong demand for aromatics - benzene, toluene and xylenes (BTX) - make it economically attractive to produce aromatics via the aromatization of propane and butanes. This paper describes the Cyclar process, which is based on a catalyst formulation developed by BP and which uses UOP's CCR catalyst regeneration technology, converts propane, butanes or mixtures thereof to petrochemical-quality aromatics in a single step.

  1. Secondary battery containing zinc electrode with modified separator and method

    DOE Patents [OSTI]

    Poa, D.S.

    1984-02-16

    A battery containing a zinc electrode with a porous separator between the anode and cathode. The separator is a microporous substrate carrying therewith an organic solvent of benzene, toluene or xylene with a tertiary organic amine therein, wherein the tertiary amine has three carbon chains each containing from six to eight carbon atoms. The separator reduces the rate of zinc dentrite growth in the separator during battery operation prolonging battery life by preventing short circuits. A method of making the separator is also disclosed.

  2. Secondary battery containing zinc electrode with modified separator and method

    DOE Patents [OSTI]

    Poa, David S.; Yao, Neng-Ping

    1985-01-01

    A battery containing a zinc electrode with a porous separator between the anode and cathode. The separator is a microporous substrate carrying therewith an organic solvent of benzene, toluene or xylene with a tertiary organic amine therein, wherein the tertiary amine has three carbon chains each containing from six to eight carbon atoms. The separator reduces the rate of zinc dentrite growth in the separator during battery operation prolonging battery life by preventing short circuits. A method of making the separator is also disclosed.

  3. Storm-water characterization and lagoon sediment analysis, Grand Forks Air Force Base, North Dakota. Final report

    SciTech Connect (OSTI)

    Garland, J.G.; Vaughn, R.W.; Scott, P.T.

    1990-08-01

    Sampling was conducted in the wastewater treatment lagoons and stormwater runoff at Grand Forks AFB. The base was concerned about whether the unlined lagoons were creating a potential groundwater contamination problem and whether their stormwater runoff met North Dakota state stream standards. Lagoon sediment did not contain Extraction Procedure hazardous chemicals. Stormwater runoff exceeded state standards for boron, phosphates, and phenols and contained trace levels of methylene chloride. Characterization of lagoon influent showed it to be generally representative of domestic sewage, but also contained trace levels of boron, phenols, toluene, cyanide, chloroform, methylene chloride and ethyl benzene.

  4. Health assessment for Chemsol Inc. , Piscataway, Middlesex County, New Jersey, Region 2. CERCLIS No. NJD980528889. Preliminary report

    SciTech Connect (OSTI)

    Not Available

    1989-04-10

    The Chemsol Inc. Site is on the National Priorities List. The inactive 12-acre site is located in Piscataway (Middlesex County), New Jersey. EPA suspects that 40 drums of chemical waste are buried on-site. Access to the site is restricted. Removal actions have not occurred. Preliminary on-site sampling results have identified various volatile organic compounds. They include chloroform, tetrachloroethylene, trichloroethylene, carbon tetrachloride, toluene, and benzene. Neither the sampling results nor the environmental media where the contaminants were found were reported. The site is considered to be of potential public health concern because of the risk to human health caused by the possibility of human exposure to hazardous substances.

  5. Superfund Record of Decision (EPA region 5): Seymour Recycling Corporation, Seymour, Indiana, September 1986. Final report

    SciTech Connect (OSTI)

    Not Available

    1986-09-30

    The Seymour Recycling Corporation (SRC) operated a processing center for waste chemicals. Toxic and hazardous wastes, including solvents, metal finishing wastes, and other materials, accumulated on the site in 55-gallon drums, bulk tanks, and other containers. Wastes leaked and spilled from the drums creating fire and odor problems. A Consent Decree resulted in the removal of the upper one foot of contaminated soil from about 75% of the site's surface. Contaminated soil remains, however, and extends throughout the shallow and deep aquifer. The primary contaminants of concern include: VOCs, organics, TCE, DCE, benzene, toluene, and heavy metals. Selected remedies have been proposed and are included.

  6. Asymmetric energy flow in liquid alkylbenzenes: A computational study

    SciTech Connect (OSTI)

    Leitner, David M.; Pandey, Hari Datt

    2015-10-14

    Ultrafast IR-Raman experiments on substituted benzenes [B. C. Pein et al., J. Phys. Chem. B 117, 10898–10904 (2013)] reveal that energy can flow more efficiently in one direction along a molecule than in others. We carry out a computational study of energy flow in the three alkyl benzenes, toluene, isopropylbenzene, and t-butylbenzene, studied in these experiments, and find an asymmetry in the flow of vibrational energy between the two chemical groups of the molecule due to quantum mechanical vibrational relaxation bottlenecks, which give rise to a preferred direction of energy flow. We compare energy flow computed for all modes of the three alkylbenzenes over the relaxation time into the liquid with energy flow through the subset of modes monitored in the time-resolved Raman experiments and find qualitatively similar results when using the subset compared to all the modes.

  7. Superfund Record of Decision (EPA Region 2): Sayreville Landfill site, Borough of Sayreville, Middlesex County, New Jersey (first remedial action), September 28, 1990

    SciTech Connect (OSTI)

    Not Available

    1990-09-28

    The 35-acre Sayreville Landfill site is an inactive municipal and industrial landfill in the Borough of Sayreville, Middlesex County, New Jersey. Beginning in 1971, the landfill was used to dispose of municipal and hazardous wastes, including an estimated 50 to 150 drums containing hazardous wastes. The drums were buried in a 20-acre area of the site. In 1977, landfill operations ceased, but subsequent unauthorized dumping of hazardous waste may have occurred. In 1980, a landfill closure plan was implemented by the borough, but was not properly completed. In 1981, the State excavated 30 drums containing benzene, pesticide-, and acid-contaminated liquids. The Record of Decision (ROD) addresses remediation of onsite drummed wastes. A subsequent ROD will address further source remediation (leachate) and remediation of ground and surface waters. The primary contaminants of concern affecting the soil and debris are VOCs including benzene, toluene, and xylenes; other organics including pesticides and phenols; acids; and metals including arsenic, chromium, and lead.

  8. Investigation of optical limiting properties of Aluminium nanoparticles prepared by pulsed laser ablation in different carrier media

    SciTech Connect (OSTI)

    Kuladeep, Rajamudili; Jyothi, L.; Narayana Rao, D.; Prakash, P.; Mayank Shekhar, S.; Durga Prasad, M.

    2013-12-28

    In this communication, we carried out the systematic investigation of nonlinear absorption and scattering properties of Aluminium nanoparticles (Al NPs) in various polar and non-polar solvents. Al NPs were synthesized with pulsed Nd:YAG laser operated at 1064 nm by ablating Al target in polar and non-polar liquid environment like chloroform, chlorobenzene, toluene, benzene, and carbon tetrachloride. Synthesized Al NPs colloids of various solvents differ in appearance and UV-Vis extinction spectra exhibit absorption in the UV region. The characterization of Al NPs performed by Transmission electron microscopy (TEM) studies reveal that NPs are made up of a well crystallized Al inner part (bright zone) embedded with an amorphous metal Al shell (dark region). Growth, aggregation, and precipitation mechanisms which influence the optical properties and stability of NPs are found to be related to the dipole moment of the surrounding liquid environment. The nonlinear absorption and scattering studies are performed by open aperture Z-scan technique with 532 nm under nanosecond pulse excitation. The Z-scan measurements are fitted theoretically to estimate both two-photon absorption (TPA) and nonlinear scattering (NLS) coefficients. In polar solvents like chlorobenzene, chloroform synthesized Al NPs exhibited higher TPA, NLS coefficient values, and lower optical limiting threshold values in comparison with partially polar solvent like toluene and non-polar solvents like benzene and carbontetrachloride. These results indicate the potential use of Al NPs as a versatile optical limiting material.

  9. Carbon-Supported bimetallic Pd-Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol

    SciTech Connect (OSTI)

    Sun, Junming; Karim, Ayman M.; Zhang, He; Kovarik, Libor; Li, Xiaohong S.; Hensley, Alyssa; McEwen, Jean-Sabin; Wang, Yong

    2013-10-01

    Abstract Carbon supported metal catalysts (Cu/C, Fe/C, Pd/C, Pt/C, PdFe/C and Ru/C) have been prepared, characterized and tested for vapor-phase hydrodeoxygenation (HDO) of guaiacol (GUA) at atmospheric pressure. Phenol was the major intermediate on all catalysts. Over the noble metal catalysts saturation of the aromatic ring was the major pathway observed at low temperature (250 C), forming predominantly cyclohexanone and cyclohexanol. Substantial ring opening reaction was observed on Pt/C and Ru/C at higher reaction temperatures (e.g., 350 C). Base metal catalysts, especially Fe/C, were found to exhibit high HDO activity without ring-saturation or ring-opening with the main products being benzene, phenol along with small amounts of cresol, toluene and trimethylbenzene (TMB). A substantial enhancement in HDO activity was observed on the PdFe/C catalysts. Compared with Fe/C, the yield to oxygen-free aromatic products (i.e., benzene/toluene/TMB) on PdFe/C increased by a factor of four at 350 C, and by approximately a factor of two (83.2% versus 43.3%) at 450 C. The enhanced activity of PdFe/C is attributed to the formation of PdFe alloy as evidenced by STEM, EDS and TPR.

  10. Effect of hydrotropic salts on phase relationships involving hydrocarbons, water, and alcohols

    SciTech Connect (OSTI)

    Ho, P.C.; Kraus, K.A.

    1980-01-01

    Hydrotropic salts, which can increase the solubility of organic materials in aqueous solutions, are useful to tertiary oil recovery. We have examined effects on solubility of hydrocarbons in water (with and without alcohols) through addition of inorganic hydrotropic salts, such as perchlorates, thiocyanates, and iodides - high in the usual Hofmeister series - and of organic salts such as short chain alkyl benzene sulfonates and other salts based on substituted benzene derivatives. Although the inorganic salts are relatively ineffective in increasing solubility of hydrocarbons in water, many of the organic salts are excellent hydrotropic agents for hydrocarbons. We have examined the phase relationships for several series of aromatic salts such as sulfonates, carboxylates and hydroxycarboxylates, as a function of alkyl-carbon substitution in three-component (hydrocarbon, salt, water) and in four-component (hydrocarbon, salt, alcohol, water) systems. We have also examined miscibility relationships for a given hydrotropic salt as the chain length of alkanes and alkyl benzenes is systematically varied. While miscibilities decrease with increase in chain length of the hydrocarbon, the hydrotropic properties in these systems increase rapidly with the number of alkyl carbons on the benzene ring of the salts and they are relatively insensitive to the type of charged group (sulfonate vs carboxylate) attached to the benzene ring. However, there were significant increases in hydrotropy as one goes from equally substituted sulfonates or carboxylates to salicylates. A number of salts have been identified which have much greater hydrotropic properties for hydrocarbons than such well-known hydrotropic materials as toluene and xylene sulfonates.

  11. Benzene TCLP results from saltstone prepared with 2X ITP flowsheet concentrations of phenylborates

    SciTech Connect (OSTI)

    Poirier, M.R.

    2000-07-25

    The Savannah River Site (SRS) teamed with the Pacific Northwest National Laboratory (PNNL), Oak Ridge National Laboratory (ORNL), and ITT Flygt Corporation to conduct a test program evaluating shrouded axial propeller mixers (Flygt mixers) for heel removal in SRS Tank 19. SRS is identifying and investigating techniques to remove sludge heels from waste tanks such as Tank 19.

  12. Non-Incineration Treatment to Reduce Benzene and VOC Emissions from Green Sand Molding Systems

    SciTech Connect (OSTI)

    Fred S. Cannon; Robert C. Voigt

    2002-06-28

    Final report describing laboratory, pilot scale and production scale evaluation of advanced oxidation systems for emissions and cost reduction in metal casting green sand systems.

  13. Mass transfer of volatile organic compounds from drinking water to indoor air: The role of residential dishwashers

    SciTech Connect (OSTI)

    Howard-Reed, C.; Corsi, R.L.; Moya, J.

    1999-07-01

    Contaminated tap water may be a source of volatile organic compounds (VOCs) in residential indoor air. To better understand the extent and impact of chemical emissions from this source, a two-phase mass balance model was developed based on mass transfer kinetics between each phase. Twenty-nine experiments were completed using a residential dishwasher to determine model parameters. During each experiment, inflow water was spiked with a cocktail of chemical tracers with a wide range of physicochemical properties. In each case, the effects of water temperature, detergent, and dish-loading pattern on chemical stripping efficiencies and mass transfer coefficients were determined. Dishwasher headspace ventilation rates were also measured using an isobutylene tracer gas. Chemical stripping efficiencies for a single cycle ranged from 18% to 55% for acetone, from 96% to 98% for toluene, and from 97% to 98% for ethylbenzene and were consistently 100% for cyclohexane. Experimental results indicate that dishwashers have a relatively low but continuous ventilation rate that results in significant chemical storage within the headspace of the dishwasher. In conjunction with relatively high mass transfer coefficients, low ventilation rates generally lead to emissions that are limited by equilibrium conditions after approximately 1--2 min of dishwasher operation.

  14. Methods for chemical recovery of non-carrier-added radioactive tin from irradiated intermetallic Ti-Sb targets

    DOE Patents [OSTI]

    Lapshina, Elena V.; Zhuikov, Boris L.; Srivastava, Suresh C.; Ermolaev, Stanislav V.; Togaeva, Natalia R.

    2012-01-17

    The invention provides a method of chemical recovery of no-carrier-added radioactive tin (NCA radiotin) from intermetallide TiSb irradiated with accelerated charged particles. An irradiated sample of TiSb can be dissolved in acidic solutions. Antimony can be removed from the solution by extraction with dibutyl ether. Titanium in the form of peroxide can be separated from tin using chromatography on strong anion-exchange resin. In another embodiment NCA radiotin can be separated from iodide solution containing titanium by extraction with benzene, toluene or chloroform. NCA radiotin can be finally purified from the remaining antimony and other impurities using chromatography on silica gel. NCA tin-117m can be obtained from this process. NCA tin-117m can be used for labeling organic compounds and biological objects to be applied in medicine for imaging and therapy of various diseases.

  15. Surfactant-modified zeolites as permeable barriers to organic and inorganic groundwater contaminants

    SciTech Connect (OSTI)

    Bowman, R.S.; Sullivan, E.J.

    1995-10-01

    We have shown in laboratory experiments that natural zeolites treated with hexadecyltrimethylammonium (HDTMA) are effective sorbents for nonpolar organics, inorganic cations, and inorganic anions. Due to their low cost ({approximately}$0.75/kg) and granular nature, HDTMA-zeolites appear ideal candidates for reactive, permeable subsurface barriers. The HDTMA-zeolites are stable over a wide range of pH (3-13), ionic strength (1 M Cs{sup +} or Ca{sup 2+}), and in organic solvents. Surfactant-modified zeolites sorb nonpolar organics (benzene, toluene, xylene, chlorinated aliphatics) via a partitioning mechanism, inorganic cations (Pb{sup 2+}) via ion exchange and surface complexation, and inorganic anions (CrO{sub 4}{sup 2-}, SeO{sub 4}{sup 2-}, SO{sub 4}{sup 2-}) via surface precipitation.The goal of this work is to demonstrate the use of surfactant-modified zeolite as a permeable barrier to ground water contaminants.

  16. Superfund Record of Decision (EPA Region 2): Hooker-102nd Street Landfill, Niagara Falls, NY. (First remedial action), September 1990. Final report

    SciTech Connect (OSTI)

    Not Available

    1990-09-26

    The 22-acre Hooker-102nd Street site is a former industrial landfill in the city of Niagara Falls, Niagara County, New York. The site is adjacent to, and partially within the Niagara River's 100-year floodplain. These studies and the Remedial Investigation (RI) initiated in 1984, identified contamination in ground water, onsite and offsite soil, rivershore sediment, and within a storm sewer. Additionally, the presence of a leachate plume of non-aqueous phase liquids (NAPLs) was discovered emanating from the landfill area. The Record of Decision (ROD) is the final remedy which addresses all of the contaminated media. The primary contaminants of concern affecting the soil, sediment, and ground water are VOCs including benzene, TCE, and toluene; other organics including PCBs and phenols; and metals including arsenic.

  17. Catalytic Fast Pyrolysis for the Production of the Hydrocarbon Biofuels

    SciTech Connect (OSTI)

    Nimlos, M. R.; Robichaud, D. J.; Mukaratate, C.; Donohoe, B. S.; Iisa, K.

    2013-01-01

    Catalytic fast pyrolysis is a promising technique for conversion of biomass into hydrocarbons for use as transportation fuels. For over 30 years this process has been studied and it has been demonstrated that oils can be produced with high concentrations of hydrocarbons and low levels of oxygen. However, the yields from this type of conversion are typically low and the catalysts, which are often zeolites, are quickly deactivated through coking. In addition, the hydrocarbons produced are primarily aromatic molecules (benzene, toluene, xylene) that not desirable for petroleum refineries and are not well suited for diesel or jet engines. The goals of our research are to develop new multifunction catalysts for the production of gasoline, diesel and jet fuel range molecules and to improve process conditions for higher yields and low coking rates. We are investigating filtration and the use of hydrogen donor molecules to improve catalyst performance.

  18. Product analysis from direct liquefaction of several high-moisture biomass feedstocks

    SciTech Connect (OSTI)

    Elliott, D.C.; Sealock, L.J. Jr.; Butner, R.S.

    1987-04-01

    Product analysis in support of the process development research in biomass direct liquefaction began at rudimentary level of determining solvent-soluble portions of the product. Analysis was soon extended to elemental analyses and proximate analyses, such as ash and moisture. Later, spectrometric analyses were performed followed by detailed chemical analyses used in conjunction with chromatographic separation techniques. At all stages of development, the significant differences in composition between the products of flash pyrolysis and high-pressure processing have been evident. While polar solvents are most effective for both products, less polar solvents such as methylene chloride and even benzene and toluene have been used as extractants for high-pressure product oils.

  19. Selective aromatization of C[sub 3] and C[sub 4] paraffins over modified encilite catalysts. 1. Qualitative study

    SciTech Connect (OSTI)

    Jana, A.K.; Rao, M.S. . Department of Chemical Engineering)

    1993-06-01

    The catalytic activity of Zn-encilite in the aromatization of propane and n-butane has been studied by a comparative study of the yields of benzene, toluene, and xylenes (BTX) using propane and n-butane as feeds. The results showed that n-butane had better activity and selectivity to BTX than propane. The effects of reaction temperature, contact time, inlet concentration, poisoning with ammonia on H-encilite, and different degrees of ion exchange with Zn[sup 2+] ion were studied in detail in order to obtain information on the reaction mechanism. The results indicated that the activity and the selectivity were dictated by the acidity and Zn loading on the catalyst.

  20. Superfund record of decision (EPA Region 2): Evor Phillips Leasing Company, Old Bidge Township, Middlesex County, NJ. (First remedial action), September 1992

    SciTech Connect (OSTI)

    Not Available

    1992-09-30

    The 6.5-acre Evor Phillips Leasing Company site is a former disposal facility in Old Bridge Township, Middlesex County, New Jersey. Beginning in 1969, Evor Phillips used the site for hauling activities until leasing the property to North American Metal and Chemical Company (NAMCC) in 1971. Silver recovery operations were conducted at the site by NAMCC. Additionally, the Naval Ammunition Depot Earle sent 2,000 gallons of drummed spent potassium hydroxide to the NAMCC. The ROD addresses an interim remedy for contaminated ground water at the site and a final remedy for the drum disposal areas as OU1. The primary contaminants of concern affecting the debris, and ground water are VOCs, including benzene, TCE, PCE, and toluene; other organics; and inorganics.

  1. Permeable sorptive walls for treatment of hydrophobic organic contaminant plumes in groundwater

    SciTech Connect (OSTI)

    Grathwohl, P.; Peschik, G.

    1997-12-31

    Highly hydrophobic contaminants are easily adsorbed from aqueous solutions. Since for many of these compounds sorption increases with increasing organic carbon content natural materials such as bituminous shales and coals may be used in permeable sorptive walls. This, however, only applies if sorption is at equilibrium, which may not always be the case in groundwater treatment using a funnel-and-gate system. In contrast to the natural solids, granular activated carbons (GACs) have very high sorption capacities and reasonably fast sorption kinetics. The laboratory results show that application of GACs (e.g. F100) is economically feasible for in situ removal of polycyclic aromatic hydrocarbons (PAH) from groundwater at a former manufactured gas plant site (MGP). For less sorbing compounds (such as benzene, toluene, xylenes) a combination of adsorption and biodegradation is necessary (i.e. sorptive + reactive treatment).

  2. Devices and methods to detect and quantify trace gases

    DOE Patents [OSTI]

    Allendorf, Mark D.; Robinson, Alex

    2016-05-03

    Sensing devices based on a surface acoustic wave ("SAW") device coated with an absorbent crystalline or amorphous layer for detecting at least one chemical analyte in a gaseous carrier. Methods for detecting the presence of a chemical analyte in a gaseous carrier using such devices are also disclosed. The sensing devices and methods for their use may be configured for sensing chemical analytes selected from the group consisting of water vapor, carbon dioxide, methanol, ethanol, carbon monoxide, nitric oxide, nitrous oxide, organic amines, organic compounds containing NO.sub.2 groups, halogenated hydrocarbons, acetone, hexane, toluene, isopropanol, alcohols, alkanes, alkenes, benzene, functionalized aromatics, ammonia (NH.sub.3), phosgene (COCl.sub.2), sulfur mustard, nerve agents, sulfur dioxide, tetrahydrofuran (THF) and methyltertbutyl ether (MTBE) and combinations thereof.

  3. Testing decisions of the TSCA Interagency Testing Committee for chemicals on the Canadian Environmental Protection Act Domestic Substances List and Priority Substances List: Di-tert-butylphenol, ethyl benzene, brominated flame retardants, phthalate esters, chloroparaffins, chlorinated benzenes, and anilines

    SciTech Connect (OSTI)

    Walker, J.D.

    1996-12-31

    In 1976, under section 4(e) of the Toxic Substances Control Act (TSCA), the US Congress created the TSCA Interagency Testing Committee (ITC) to decide which chemicals should be recommended to the Administrator of the US Environmental Protection Agency for testing. In 1988, under the Canadian Environmental Protection Act (CEPA), the Government of Canada created the Domestic Substances List and Priority Substances List. This paper briefly describes the ITC, the different ITC testing decisions and a few of the ITC`s 11,150 testing decisions for the 21,413 chemicals on the CEPA Domestic Substances List and some of the 24 testing decisions for the 44 chemicals and chemical groups on the CEPA.

  4. The benzene⋯naphthalene complex: A more challenging system than the benzene dimer for newly developed computational methods

    SciTech Connect (OSTI)

    Wang, Weizhou E-mail: ybw@gzu.edu.cn; Zhang, Yu; Sun, Tao; Wang, Yi-Bo E-mail: ybw@gzu.edu.cn

    2015-09-21

    High-level coupled cluster singles, doubles, and perturbative triples [CCSD(T)] computations with up to the aug-cc-pVQZ basis set (1924 basis functions) and various extrapolations toward the complete basis set (CBS) limit are presented for the sandwich, T-shaped, and parallel-displaced benzene⋯naphthalene complex. Using the CCSD(T)/CBS interaction energies as a benchmark, the performance of some newly developed wave function and density functional theory methods has been evaluated. The best performing methods were found to be the dispersion-corrected PBE0 functional (PBE0-D3) and spin-component scaled zeroth-order symmetry-adapted perturbation theory (SCS-SAPT0). The success of SCS-SAPT0 is very encouraging because it provides one method for energy component analysis of π-stacked complexes with 200 atoms or more. Most newly developed methods do, however, overestimate the interaction energies. The results of energy component analysis show that interaction energies are overestimated mainly due to the overestimation of dispersion energy.

  5. Genome analysis and physiological comparison of Alicycliphilus denitrificans strains BC and K601T

    SciTech Connect (OSTI)

    Oosterkamp, Margreet J.; Veuskens, Teun; Saia, Flavia Talarico; Weelink, Sander A.B.; Goodwin, Lynne A.; Daligault, Hajnalka E.; Bruce, David; Detter, J. Chris; Tapia, Roxanne; Han, Cliff; Land, Miriam L; Hauser, Loren John; Langenhoff, A. M.; Gerritse, Jan; Van Berkel, Willem J. H.; Pieper, Dietmar; Junca, Howard; Smidt, Hauke; Schraa, Gosse; Davids, Mark; Schaap, Peter J; Plugge, Caroline M.; Stams, Alfons J. M.

    2013-01-01

    The genomes of the Betaproteobacteria Alicycliphilus denitrificans strains BC and K601T have been sequenced to get insight into the physiology of the two strains. Strain BC degrades benzene with chlorate as electron acceptor. The cyclohexanol-degrading denitrifying strain K601T is not able to use chlorate as electron acceptor, while strain BC cannot degrade cyclohexanol. The 16S rRNA sequences of strains BC and K601T are identical and the fatty acid methyl ester patterns of the strains are similar. Basic Local Alignment Search Tool (BLAST) analysis of predicted open reading frames of both strains showed most hits with Acidovorax sp. JS42, a bacterium that degrades nitro-aromatics. The genomes include strain-specific plasmids (pAlide201 in strain K601T and pAlide01 and pAlide02 in strain BC). Key genes of chlorate reduction in strain BC were located on a 120 kb megaplasmid (pAlide01), which was absent in strain K601T. Genes involved in cyclohexanol degradation were only found in strain K601T. Benzene and toluene are degraded via oxygenase-mediated pathways in both strains. Genes involved in the meta-cleavage pathway of catechol are present in the genomes of both strains. Strain BC also contains all genes of the ortho-cleavage pathway. The large number of mono- and dioxygenase genes in the genomes suggests that the two strains have a broader substrate range than known thus far.

  6. Fossil fuel and hydrocarbon conversion using hydrogen-rich plasmas. Topical report February 1994--February 1995

    SciTech Connect (OSTI)

    1995-02-01

    Experiments were made on use of H and CH plasmas for converting waste materials and heavy oils to H-rich transportation fuels. Batch and continuous experiments were conducted with an industrial microwave generator and a commercial microwave oven. A continuously circulating reactor was constructed for conducting experiments on flowing oils. Experiments on decomposition of scrap tires showed that microwave plasmas can be used to decompose scrap tires into potentially useful liquid products. In a batch experiment using a commercial microwave oven, about 20% of the tire was converted to liquid products in about 9 minutes. Methane was decomposed in a microwave plasma to yield a liquid products composed of various compound types; GC/MS analyses identified unsaturated compounds including benzene, toluene, ethyl benzene, methyl and ethyl naphthalene, small amounts of larger aromatic rings, and olefinic compounds. Experiments on a crude oil in a continuously flowing reactor showed that distillate materials are produced using H and CH plasmas. Also, the recycle oils had an overall carbon aromaticity lower than that of starting feed material, indicating that some hydrogenation and methanation had taken place in the recycle oils.

  7. Introducing constricted variational density functional theory in its relaxed self-consistent formulation (RSCF-CV-DFT) as an alternative to adiabatic time dependent density functional theory for studies of charge transfer transitions

    SciTech Connect (OSTI)

    Krykunov, Mykhaylo; Seth, Mike; Ziegler, Tom

    2014-05-14

    We have applied the relaxed and self-consistent extension of constricted variational density functional theory (RSCF-CV-DFT) for the calculation of the lowest charge transfer transitions in the molecular complex X-TCNE between X = benzene and TCNE = tetracyanoethylene. Use was made of functionals with a fixed fraction (α) of Hartree-Fock exchange ranging from α = 0 to α = 0.5 as well as functionals with a long range correction (LC) that introduces Hartree-Fock exchange for longer inter-electronic distances. A detailed comparison and analysis is given for each functional between the performance of RSCF-CV-DFT and adiabatic time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation. It is shown that in this particular case, all functionals afford the same reasonable agreement with experiment for RSCF-CV-DFT whereas only the LC-functionals afford a fair agreement with experiment using TDDFT. We have in addition calculated the CT transition energy for X-TCNE with X = toluene, o-xylene, and naphthalene employing the same functionals as for X = benzene. It is shown that the calculated charge transfer excitation energies are in as good agreement with experiment as those obtained from highly optimized LC-functionals using adiabatic TDDFT. We finally discuss the relation between the optimization of length separation parameters and orbital relaxation in the RSCF-CV-DFT scheme.

  8. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    SciTech Connect (OSTI)

    Keith James Stanger

    2003-05-31

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-{alpha}-acetamidocinnamate (MAC), has the illustrated structure as established by {sup 31}P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]{sub 4}, [Rh(COD){sub 2}]{sup +}BF{sub 4}{sup -}, [Rh(COD)Cl]{sub 2}, and RhCl{sub 3} {center_dot} 3H{sub 2}O, adsorbed on SiO{sub 2} are optimally activated for toluene hydrogenation by pretreatment with H{sub 2} at 200 C. The same complexes on Pd-SiO{sub 2} are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH{sub 2}){sub 3}s-]Re(O)(Me)(PPh{sub 3}) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  9. Functionalization/passivation of porous graphitic carbon with di-tert-amylperoxide

    SciTech Connect (OSTI)

    Jensen, David S.; Gupta, Vipul; Olsen, Rebecca E.; Miller, Alex T.; Davis, Robert C.; Ess, Daniel; Zhu, Zihua; Vail, Michael A.; Dadson, Andrew; Linford, Matthew R.

    2011-11-18

    Porous graphitic carbon (PGC) particles were functionalized/passivated in situ in packed beds at elevated temperature with neat di-tert-amylperoxide (DTAP) in a column oven. The performance of these particles for high performance liquid chromatography (HPLC) was assayed before and after this chemistry with the following analytes: benzene, toluene, ethyl benzene, n-propyl benzene, n-butyl benzene, p-xylene, phenol, 4-methylphenol, phenetole, 3,5-xylenol, and anisole. After the first functionalization/passivation, the retention factors, k, of these compounds decreased by about 5% and the number of theoretical plates (N) increased by ca. 15%. These values of k then remained roughly constant after a second functionalization/ passivation but a further increase in N was noticed. In addition, after each of the reactions, the peak asymmetries decreased by ca. 15%, for a total of ca. 30%. The columns were then subjected twice to methanol at 100 C for 5 h at 1 mL/min. After these stability tests, the values of k remained roughly constant, the number of plates increased, which is favorable, and the asymmetries rose and then declined, where they remained below the initial values for the unfunctionalized columns. Functionalized and unfunctionalized particles were characterized by scanning electron microscopy and BET measurements, which showed no difference between the functionalized and unfunctionalized materials, and X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), where ToF-SIMS suggested some chemical differences between the functionalized and unfunctionalized materials. In particular ToF-SIMS suggested that the expected five-carbon fragments from DTAP exist at higher concentrations on DTAP-functionalized PGC. First principle calculations on model graphitic surfaces suggest that the first addition of a DTAP radical to the surface proceeds in an approximately isothermal or slightly favorable fashion, but that subsequent DTAP

  10. Source Term Modeling for Evaluating the Potential Impacts to Groundwater of Fluids Escaping from a Depleted Oil Reservoir Used for Carbon Sequestration

    SciTech Connect (OSTI)

    Cantrell, Kirk J.; Brown, Christopher F.

    2014-06-13

    In recent years depleted oil reservoirs have received special interest as carbon storage reservoirs because of their potential to offset costs through collaboration with enhanced oil recovery projects. Modeling is currently being conducted to evaluate potential risks to groundwater associated with leakage of fluids from depleted oil reservoirs used for storage of CO2. Modeling results reported here focused on understanding how toxic organic compounds found in oil will distribute between the various phases within a storage reservoir after introduction of CO2, understanding the migration potential of these compounds, and assessing potential groundwater impacts should leakage occur. Two model scenarios were conducted to evaluate how organic components in oil will distribute among the phases of interest (oil, CO2, and brine). The first case consisted of 50 wt.% oil and 50 wt.% water; the second case was 90 wt.% CO2 and 10 wt.% oil. Several key organic compounds were selected for special attention in this study based upon their occurrence in oil at significant concentrations, relative toxicity, or because they can serve as surrogate compounds for other more highly toxic compounds for which required input data are not available. The organic contaminants of interest (COI) selected for this study were benzene, toluene, naphthalene, phenanthrene, and anthracene. Partitioning of organic compounds between crude oil and supercritical CO2 was modeled using the Peng-Robinson equation of state over temperature and pressure conditions that represent the entire subsurface system (from those relevant to deep geologic carbon storage environments to near surface conditions). Results indicate that for a typical set of oil reservoir conditions (75°C, and 21,520 kPa) negligible amounts of the COI dissolve into the aqueous phase. When CO2 is introduced into the reservoir such that the final composition of the reservoir is 90 wt.% CO2 and 10 wt.% oil, a significant fraction of the oil

  11. Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10(trans-dpmn) and 1,2-Os3(CO)10(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os3(CO)10(dpmn) and Isomer-Dependent Diphosphine Ligand Activation

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Yang, Li; Nesterov, Vladimir N.; Wang, Xiaoping; Richmond, Michael G.

    2014-07-23

    The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os3(CO)10(MeCN)2 (1) to furnish the corresponding ligand-bridged clusters Os3(CO)10(trans-dpmn) (2) and Os3(CO)10(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os3(CO)8(μ-OH)2(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373 K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C-H bonds and one P-C(phenyl) bond, tomore » furnish the dihydride cluster H2Os3(CO)8[μ3-2-PhPC-3-endo-Ph2PCH2(C7H7)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph2PCH2(C7H7) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3→ 5 + 2CO + benzene is computed to be exergonic by 12.7 kcal/mol and is entropically favored due to the release of the CO and benzene by-products.« less

  12. Flash methanolysis of wood for the production of fuels and chemicals

    SciTech Connect (OSTI)

    Steinberg, M.; Fallon, P.T.; Sundaram, M.S.

    1983-01-01

    Biomass in the form of less than 1000 micron oven dried fir wood particles was flash pyrolyzed in the presence of methane (methanolysis) in a downflow 1 in. I.D. tubular reactor at pressures of 20 to 200 psi and temperatures between 800/sup 0/ and 1050/sup 0/C. The major products were benzene, toluene and xylene (BTX), a heavy oily liquid (greater than or equal to C/sub 9/), ethylene and carbon monoxide. As much as 12% of the available carbon in the wood was converted to BTX, 21% to ethylene and 48% to carbon monoxide at 50 psi and 1000/sup 0/C. The maximum heavier oil yield of 11% was observed at 50 psi and 800/sup 0/C. Wood particle residence times for all experiments were calculated to be less than 1 second at 20 and 50 psi and up to 2.8 sec at 200 psi. The yelds were found to be greatly influenced by the methane to wood feed ratio. Experiments were conducted to insure the results to be that produced from the wood and methane and not a catalytic effect of the reactor wall of foreign matter. Material balance, including char analyses, indicate approximately 75 to 80% of the available carbon in the feed wood reacted. Methane balances were within the margin of error of the measuring equipment showing that there is no significant net production or consumption of methane. A preliminary economic evaluation of a 2000 ton/day wood processing plant producing ethylene, benzene and methanol showed a reasonably cmpetitive plant investment of $29,000/barrel fuel oil equivalent/day assuming 15% return on investment and present market values for the products.

  13. Process for the production of ethylene and other hydrocarbons from coal

    DOE Patents [OSTI]

    Steinberg, M.; Fallon, P.

    1984-02-15

    The subject invention comprises the steps of first reacting particulate coal with methane at a temperature in the approximate range of 500/sup 0/C to 1100/sup 0/C and at a partial pressure of methane of less than about 200 psig for a period of less than 10 seconds. More preferably, the method of the subject invention is carried out at a temperature of approximately 850/sup 0/C to 1000/sup 0/C and a pressure of 50 psig for a period of approximately 1.5 seconds. Surprisingly, it has been found that in the practice of the subject invention not only are commercially significant quantities of ethylene produced, namely yields in excess of 10% (percent carbon converted to product), along with economically significant quantities of-benzene and light oils, namely toluene and xylene, but also that there is little, if any, net consumption of methane in the reaction and possibly even a small net production. Since it is apparent that the carbonaceous solids or char remaining after the reaction is carried out may be burned to provide the necessary energy to carry out the process of the subject invention, it is apparent that the subject invention advantageously provides a method for the conversion of coal to economically significant quantities of ethylene, benzene and light oils while requiring only coal and, possibly, small amounts of make-up methane. Other objects and advantages of the subject invention will be apparent to those skilled in the art from a consideration of the attached drawings, the detailed description of the invention, and the experimental examples set forth below.

  14. SYNTHESIS OF THE FULLY PROTECTED PHOSPHORAMIDITE OF THE BENZENE-DNA ADDUCT, N2- (4-HYDROXYPHENYL)-2'-DEOXYGUANOSINE AND INCORPORATION OF THE LATER INTO DNA OLIGOMERS

    SciTech Connect (OSTI)

    Chenna, Ahmed; Gupta, Ramesh C.; Bonala, Radha R.; Johnson, Francis; Huang, Bo

    2008-06-09

    N2-(4-Hydroxyphenyl)-2'-deoxyguanosine-5'-O-DMT-3'-phosphoramidite has been synthesized and used to incorporate the N2-(4-hydroxyphenyl)-2'-dG (N2-4-HOPh-dG) into DNA, using solid-state synthesis technology. The key step to obtaining the xenonucleoside is a palladium (Xantphos-chelated) catalyzed N2-arylation (Buchwald-Hartwig reaction) of a fully protected 2'-deoxyguanosine derivative by 4-isobutyryloxybromobenzene. The reaction proceeded in good yield and the adduct was converted to the required 5'-O-DMT-3'-O-phosphoramidite by standard methods. The latter was used to synthesize oligodeoxynucleotides in which the N2-4-HOPh-dG adduct was incorporated site-specifically. The oligomers were purified by reverse-phase HPLC. Enzymatic hydrolysis and HPLC analysis confirmed the presence of this adduct in the oligomers.

  15. Application and results of whole-body autoradiography in distribution studies of organic solvents

    SciTech Connect (OSTI)

    Bergman, K.

    1983-01-01

    With the growing concern for the health hazards of occupational exposure to toxic substances attention has been focused on the organic solvents, which are associated with both deleterious nervous system effects and specific tissue injuries. Relatively little is known about the distribution of organic solvents and their metabolites in the living organism. Knowledge of the specific tissue localizations and retention of solvents and solvent metabolites is of great value in revealing and understanding the sites and mechanisms of organic solvent toxicity. Whole-body autoradiography has been modified and applied to distribution studies of benzene, toluene, m-xylene, styrene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene and carbon disulfide. The high volatility of these substances has led to the development of cryo-techniques. Whole-body autoradiographic techniques applicable to the study of volatile substances are reviewed. The localizations of nonvolatile solvent metabolites and firmly bound metabolites have also been examined. The obtained results are discussed in relation to toxic effects and evaluated by comparison with other techniques used in distribution studies of organic solvents and their metabolites.

  16. Fullerene (C60) films for solid lubrication

    SciTech Connect (OSTI)

    Bhushan, B.; Gupta, B.K.; Van Cleef, G.W.; Capp, C.E.; Coe, J.V. )

    1993-10-01

    The advent of techniques for producing gram quantities of a new form of stable, pure, solid carbon, designated as fullerene, opens a profusion of possibilities to be explored in many disciplines including tribology. Fullerenes take the form of hollow geodesic domes, which are formed from a network of pentagons and hexagons with covalently bonded carbon atoms. The C60 molecule has the highest possible symmetry (icosahedral) and assumes the shape of a soccer ball. At room temperature, fullerene molecules pack in an fcc lattice bonded with weak van der Waals attractions. Fullerenes can be dissolved in solvents such as toluene and benzene and are easily sublimed. The low surface energy, high chemical stability, spherical shape, weak intermolecular bonding, and high load bearing capacity of C60 molecules offer potential for various mechanical and tribological applications. This paper describes the crystal structure and properties of fullerenes and proposes a mechanism for self-lubricating action. Sublimed films of C60 have been produced and friction and wear performance of these films in various operating environments are the subject of this paper. The results of this study indicate that C60, owing to its unique crystal structure and bonding, may be a promising solid lubricant. 31 refs.

  17. Furan production from glycoaldehyde over HZSM-5

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kim, Seonah; Evans, Tabitha J.; Mukarakate, Calvin; Bu, Lintao; Beckham, Gregg T.; Nimlos, Mark R.; Paton, Robert S.; Robichaud, David J.

    2016-04-03

    Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300 degrees C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalyticmore » fast pyrolysis conditions (>400 degrees C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts.« less

  18. PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

    DOE Patents [OSTI]

    Levine, C.A.; Skiens, W.E.; Moore, G.R.

    1960-08-01

    A process for providing superior solvent extractants for metal recovery processes is given wherein the extractant comprises an alkyl pyrophosphoric acid ester dissolved in an organic solvent diluent. Finely divided solid P/sub 2/O/ sub 5/ is slurried in an organic solvent-diluent selected from organic solvents such as kerosene, benzene, chlorobenzene, toluene, etc. An alcohol selected from the higher alcohols having 4 to 17 carbon atoms. e.g.. hexanol-1. heptanol-3, octanol-1. 2.6-dimethyl-heptanol-4, and decanol-1, is rapidly added to the P/sub 2/O/sub 5/ slurry in the amount of about 2 moles of alcohol to 1 mole of P/sub 2/ O/sub 5/. The temperature is maintained below about 110 deg C during the course of the P/sub 2/O/sub 5/-alcohol reaction. An alkyl pyrophosphate extractant compound is formed as a consequence of the reaction process. The alkyl pyrophosphate solvent-diluent extractant phase is useful in solvent extraction metal recovery processes.

  19. Field-usable portable analyzer for chlorinated organic compounds

    SciTech Connect (OSTI)

    Buttner, W.J.; Penrose, W.R.; Stetter, J.R.

    1995-10-01

    Transducer Research, Inc. (TRI) has been working with the DOE Morgantown Energy Technology Center to develop a new chemical monitor based on a unique sensor which responds selectively to vapors of chlorinated solvents. We are also developing field applications for the monitor in actual DOE cleanup operations. During the initial phase, prototype instruments were built and field tested. Because of the high degree of selectivity that is obtained, no response was observed with common hydrocarbon organic compounds such as BTX (benzene, toluene, xylene) or POLs (petroleum, oil, lubricants), and in fact, no non-halogen-containing chemical has been identified which induces a measurable response. By the end of the Phase I effort, a finished instrument system was developed and test marketed. This instrument, called the RCL MONITOR, was designed to analyze individual samples or monitor an area with automated repetitive analyses. Vapor levels between 0 and 500 ppm can be determined in 90 s with a lower detection limit of 0.2 ppm using the handportable instrument. In addition to the development of the RCL MONITOR, advanced sampler systems are being developed to: (1) extend the dynamic range of the instrument through autodilution of the vapor and (2) allow chemical analyses to be performed on aqueous samples. When interfaced to the samplers, the RCL MONITOR is capable of measuring chlorinated solvent contamination in the vapor phase up to 5000 ppm and in water and other condensed media from 10 to over 10,000 ppb(wt)--without hydrocarbon and other organic interferences.

  20. Photophysics and Luminescence Spectroelectrochemistry of [Tc(dmpe)3]+/2+ (dmpe = 1,2-bis(dimethylphosphino)ethane)

    SciTech Connect (OSTI)

    Chatterjee, Sayandev; Del Negro, Andrew S.; Smith, Frances N.; Wang, Zheming; Hightower, Sean E.; Sullivan, Brian P.; Heineman, William R.; Seliskar, Carl J.; Bryan, Samuel A.

    2013-12-05

    The ligand-to-metal charge transfer (LMCT) excited state luminescence of [Tc(dmpe)3]2+ (dmpe is 1,2-bis-(dimethylphosphino)ethane) has been measured in solution at room temperature, and is compared to its Re analogue. Surprisingly, both [M(dmpe)3]2+* (M = Re, Tc) species have extremely large excited-state potentials (ESPs) as oxidants - the highest for any simple coordination complex of a transition metal. Furthermore, this potential is available using a photon of visible light (calculated for M = Re(Tc); E1/2* = +2.61(2.48) V versus SCE; ?max = 526(585) nm). Open shell TDDFT calculations support the assignment of the lowest energy transition in both the technetium and rhenium complexes to be a doublet-doublet process that involve predominantly LMCT (dmpe-to-metal) character and is in agreement with past assignments for the Re system. As expected for highly oxidizing excited state potentials, quenching is observed for the excited states by both the rhenium and technetium complexes. Stern-Volmer analysis resulted in quenching parameters for both the rhenium and technetium complexes under identical conditions, and are compared using Rehm-Weller analysis. Of particular interest is the fact that both benzene and toluene are oxidized by both the Re and Tc systems.

  1. Superfund Record of Decision (EPA Region 7): Vogel Paint and Wax, Maurice, IA. (First remedial action), September 1989. Final report

    SciTech Connect (OSTI)

    Not Available

    1989-09-20

    The Vogel Paint and Wax (VPW) site is an approximately two-acre disposal area two miles southwest of the town of Maurice, in Sioux County, Iowa. Adjacent land uses are primarily agricultural; however, several private residences are within one-quarter mile of the site. A surficial sand and gravel aquifer underlies the site and supplies nearby private wells and the Southern Sioux County Rural Water System, located a mile and one half southeast of the site. Paint sludge, resins, solvents, and other paint-manufacturing wastes were disposed of at the site between 1971 and 1979. VPW records indicate that approximately 43,000 gallons of aliphatic and aromatic hydrocarbons and 6,000 pounds of metals waste were buried at the site. The primary contaminants of concern affecting the soil and ground water are VOCs including benzene, toluene, and xylenes; and metals including chromium and lead. The selected remedial action for this site includes excavation of contaminated soil and separation of solid and liquid wastes; onsite bioremediation of 3,000 cubic yards of the contaminated soil in a fully contained surface impoundment unit, or onsite thermal treatment if soil contains high metal content; and stabilization of treated soil, if necessary to prevent leaching of metals, followed by disposal in the excavated area.

  2. Superfund record of decision (EPA Region 4): Whitehouse Waste Oil Pits Site, Duval County, Jacksonville, FL. (First remedial action), (Amendment), June 1992. Final report

    SciTech Connect (OSTI)

    Not Available

    1992-06-16

    The 7-acre Whitehouse Waste Oil Pits site was used by Allied Petroleum Products (Allied) to dispose of acidic waste oil sludges from its oil reclamation process in Whitehouse, Duval County, Florida. A cypress swamp system and residential area are immediately adjacent to the site. The acid sludge produced in the first step and clay used to decolorize the oil were dumped into the unlined pits at the site. A 1985 ROD addressed source control as a containment remedy consisting of a slurry wall construction, soil cap, and a ground water recovery and treatment system; however, EPA has re-evaluated the 1985 ROD selection and determined that the containment remedy failed to meet the requirements of SARA. As a result, the ROD Amendment focuses on an alternative for treating Whitehouse wastes by eliminating direct contact risk associated with pit soil/sludge wastes and preventing contaminated ground water in the surficial aquifer from migrating laterally. The primary contaminants of concern that affect the soil, sediment, surface water, and ground water are VOCs, including benzene, toluene, and xylenes; organics, including PCBs and phenols; and metals, including arsenic, chromium, and lead. The amended remedial action for the site are included.

  3. Source profiles for nonmethane organic compounds in the atmosphere of Cairo, Egypt.

    SciTech Connect (OSTI)

    Doskey, P. V.; Fukui, Y.; Sultan, M.; Maghraby, A. A.; Taher, A.; Environmental Research; Cairo Univ.

    1999-07-01

    Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas (LPG), and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C{sub 5} and C{sub 6} saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in the vehicle emission profile. High levels of the C{sub 2}-C{sub 4} saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.

  4. Vapor Sensing Using Conjugated Molecule-Linked Au Nanoparticles in a Silica Matrix

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Dirk, Shawn M.; Howell, Stephen W.; Price, B. Katherine; Fan, Hongyou; Washburn, Cody; Wheeler, David R.; Tour, James M.; Whiting, Joshua; Simonson, R. Joseph

    2009-01-01

    Cross-linkedmore » assemblies of nanoparticles are of great value as chemiresistor-type sensors. Herein, we report a simple method to fabricate a chemiresistor-type sensor that minimizes the swelling transduction mechanism while optimizing the change in dielectric response. Sensors prepared with this methodology showed enhanced chemoselectivity for phosphonates which are useful surrogates for chemical weapons. Chemoselective sensors were fabricated using an aqueous solution of gold nanoparticles that were then cross-linked in the presence of the silica precursor, tetraethyl orthosilicate with the α -, ω -dithiolate (which is derived from the in situ deprotection of 1,4-di(Phenylethynyl- 4 ′ , 4 ″ -diacetylthio)-benzene ( 1 ) with wet triethylamine). The cross-linked nanoparticles and silica matrix were drop coated onto interdigitated electrodes having 8  μ m spacing. Samples were exposed to a series of analytes including dimethyl methylphosphonate (DMMP), octane, and toluene. A limit of detection was obtained for each analyte. Sensors assembled in this fashion were more sensitive to dimethyl methylphosphonate than to octane by a factor of 1000.« less

  5. Health-hazard evaluation report HETA 91-254-2186, Ropes and Gray Photocopy Center, Boston, Massachusetts

    SciTech Connect (OSTI)

    Cook, C.K.; Crandall, M.S.

    1992-03-01

    In response to a request from a group of employees at the Pitney Bowes Management Services, Ropes and Gray Photocopy Center (SIC-7334), Boston, Massachusetts, an evaluation was undertaken of worker exposures to photocopy emissions. The photocopy center has been in operation for 2 years. Six full time employees worked the day shift operating six photocopiers of various models. Approximately 1 million copies were generated monthly at the site. Qualitative and quantitative analyses of air samples taken for volatile organic carbons revealed trace amounts of 1,1,1-trichloroethane (71556), isooctane (540841), toluene (108883), xylene (1330207), and benzene (71432). Ozone (10028156) concentrations as high as 0.41 parts per million (ppm) were detected at approximately 3 feet from the exhaust of each photocopier. Carbon-dioxide (124389) concentrations ranged from 300 to 825ppm. Respirable dust concentrations ranged from less than 10 to 50 micrograms per cubic meter. Carbon-monoxide (630080) was not detected. The authors conclude that the evaluation did not reveal a hazard to explain the respiratory symptoms experienced by the workers. The finding that the ventilation system moved too small an amount of air in a measured period of time may account for the accumulation of airborne contaminants within the building. Recommendations were made to improve the ventilation.

  6. Pyrolysis of scrap tires: Can it be profitable?

    SciTech Connect (OSTI)

    Wojtowicz, M.A.; Serio, M.A.

    1996-10-01

    Pyrolysis--the thermal degradation in the absence of oxygen--is one way to reprocess scrap tires. The products are fuel gas, oils, and a solid residue (char), which contains appreciable quantities of mineral matter and low-grade carbon black. The three products have comparable yields by weight. The two most important factors affecting process economics are the tipping fees charged for tire disposal and the selling prices of the products. Selling prices of the products yield low returns because of the low market value of the fuels and the low quality of the recovered char or carbon black. Therefore, to obtain a positive cash flow, it would be desirable to develop a process based on the recovery of value-added products such as high-grade carbon black, activated carbon, or valuable chemicals (e.g., benzene, toluene, and xylene). The authors believe that significant improvement in the economics can be accomplished by upgrading the primary pyrolysis products to secondary products of higher value.

  7. Semi volatile organic compounds in ambient PM2.5. Seasonal trends and daily resolved source contributions

    SciTech Connect (OSTI)

    Juergen Schnelle-Kreis; Martin Sklorz; Juergen Orasche; Matthias Stoelzel; Annette Peters; Ralf Zimmermann

    2007-06-01

    Concentrations of ambient semivolatile organic compounds (SVOC) in the PM2.5 fraction of Augsburg, Germany, have been monitored on a daily basis from January 2003 through December 2004. Samples were taken in a large garden in the city center. Quantitative analysis of n-alkanes, alkanones, alkanoic acid methylesters, long chain linear alkyl benzenes and toluenes, hopanes, polycyclic aromatic hydrocarbons (PAH) and oxidized PAH, and some abietan type diterpenes was done. All compounds showed distinct seasonal variations in concentration. Most compounds showed highest concentrations during the cold seasons, but some n-alkanones and 6,10,14-trimethylpentadecanone showed maximum concentration during summer. Changes in patterns between and within compound classes were obvious, e.g., the hopane pattern exhibited a strong seasonal variation. The main source related contributions to changes observed were discussed. Using positive matrix factorization (PMF) for the statistical investigation of the data set, five factors have been separated. These factors are dominated by the pattern of single sources or groups of similar sources: factor 1, lubricating oil; factor 2, emissions of unburned diesel and heating oil consumption; factor 3, wood combustion; factor 4, brown coal combustion; and factor 5, biogenic emissions and transport components. Like the SVOC, the factors showed strong seasonality with highest values in winter for factors 1-4 and in summer for factor 5. 56 refs., 3 figs., 1 tab.

  8. Superfund Record of Decision (EPA Region 7): John Deere DDubuque Works, Dubuque, Iowa (first remedial action), September 1988. Final report

    SciTech Connect (OSTI)

    Not Available

    1988-09-29

    The John Deere Dubuque Works site is located approximately 2.5 miles north of the City of Dubuque, Iowa. The site is owned by Deere and Company, which has operated a manufacturing plant at the site since 1946. The plant property includes an area of 1,447 acres located in the flood plain at the confluence of the Little Maquoketa River and the Mississippi River. The waste-management history of the plant is complex, but the primary area of concern is an unlined landfill originally placed in a natural depression caused by the Little Maquoketa River. Prior to 1968, wastes were placed in the low areas of the landfill and combustible materials were burned. Another area of concern at the facility is the site of a 1980, 200,000-gallon diesel fuel spill. Investigations conducted by John Deere indicated that human health hazards at the landfill could be considered minimal with the primary hazard being the possibility of dissolved organic chemicals impacting offsite domestic wells located east of the plant along the Mississippi River. The primary contaminants of concern affecting the ground water are volatile organic compounds including benzene, PCE, TCE, and toluene. The selected remedial action for the site is included.

  9. A Feasibility Study for Recycling Used Automotive Oil Filters In A Blast Furnace

    SciTech Connect (OSTI)

    Ralph M. Smailer; Gregory L. Dressel; Jennifer Hsu Hill

    2002-01-21

    This feasibility study has indicated that of the approximately 120,000 tons of steel available to be recycled from used oil filters (UOF's), a maximum blast furnace charge of 2% of the burden may be anticipated for short term use of a few months. The oil contained in the most readily processed UOF's being properly hot drained and crushed is approximately 12% to 14% by weight. This oil will be pyrolized at a rate of 98% resulting in additional fuel gas of 68% and a condensable hydrocarbon fraction of 30%, with the remaining 2% resulting as carbon being added into the burden. Based upon the writer's collected information and assessment, there appears to be no operational problems relating to the recycling of UOF's to the blast furnace. One steel plant in the US has been routinely charging UOF's at about 100 tons to 200 tons per month for many years. Extensive analysis and calculations appear to indicate no toxic consideration as a result of the pyrolysis of the small contained oil ( in the 'prepared' UOFs) within the blast furnace. However, a hydrocarbon condensate in the ''gasoline'' fraction will condense in the blast furnace scrubber water and may require additional processing the water treatment system to remove benzene and toluene from the condensate. Used oil filters represent an additional source of high quality iron units that may be effectively added to the charge of a blast furnace for beneficial value to the operator and to the removal of this resource from landfills.

  10. Initial site characterization, environmental assessment, and corrective actions for underground storage tank 2315-U, Pine Ridge East Repeater Station, Oak Ridge Y-12 Plant, Oak Ridge, Tennessee

    SciTech Connect (OSTI)

    Eaton, J.M.; Ingram, E.M. )

    1991-02-01

    This document presents the Initial Site Characterization Report and information to date regarding environmental assessment and corrective actions for Underground Storage Tank (UST) 2315-U at the Pine Ridge East Repeater Station, Oak Ridge Y-12 Plant, Oak Ridge, Tennessee. This document was prepared following guidance in US Environmental Protection Agency (EPA) regulations promulgated under 40 CFR 280. The Pine Ridge East Repeater Station is located on Pine Ridge, which borders the Y-12 Plant to the north. One 64-gallon, asphalt-coated steel tank was located adjacent to the Repeater Station. This tank was used to store gasoline for the station's emergency power generator. Tank 2315-U was exempted from regulation under 40 CFR 280 and Tennessee Department of Health and Environment (TDHE) Rules 1200-1-15.-01 through 1200-1-15-.07 due to size and emergency generator exemptions. Because of an identified release discovered during initial corrective actions, TDHE requirements in revised Rule 1200-1-15-.06, promulgated April 15, 1990, regarding release response and corrective actions, apply to the site (TDHE, 1990). This report documents all activities, including initial abatement, initial site characterization, environmental assessment sampling, and corrective actions conducted to comply with TDHE regulations. Initial site characterization sampling data revealed that benzene, toluene, and xylene (BTX) concentrations exceeded applicable regulatory guidelines and lead values were elevated above levels expected for clean soils. 17 refs., 10 figs., 8 tabs.

  11. Superfund Record of Decision (EPA Region 2): Chemsol, Inc. , Piscataway, Middlesex County, NJ. (First remedial action), September 1991

    SciTech Connect (OSTI)

    Not Available

    1991-09-20

    The 40-acre Chemsol site is a former solvent recovery and waste reprocessing facility in Piscataway Township, Middlesex County, New Jersey. Land use in the area is predominantly commercial and residential, with an onsite marshy area that may be considered a wetlands. The site overlies a bedrock aquifer that is used as a regional drinking water source. Between 1980 and 1990, sampling of residential wells indicated the presence of organic contaminants and PCBs. The Record of Decision (ROD) provides an interim remedy to restrict the offsite migration of highly contaminated ground water. The primary contaminants of concern affecting the ground water are VOCs including benzene, toluene, and xylenes; other organics including pesticides and phenols; and metals including arsenic, chromium, and lead. The selected remedial action for this interim remedy includes installing a ground water collection trench; installing three ground water extraction wells to a depth of 130 feet; constructing an onsite treatment plant and treating contaminated ground water using air stripping, biological filtration, and activated carbon adsorption.

  12. Superfund Record of Decision (EPA Region 8): Rocky Mountain Arsenal (Operable Unit 21), CO. (Ninth remedial action), June 1991

    SciTech Connect (OSTI)

    Not Available

    1991-06-06

    The Rocky Mountain Arsenal (RMA) (Operable Unit 21) site comprises part of the 17,000-acre RMA site, which is a former U.S. Army chemical warfare and incendiary munitions manufacturing and assembly plant in Adams County, Colorado. From the 1950s until late 1969, the U.S. Army used the RMA facility to produce the nerve agent GB (isopropylmethyl-phosphonofluoridate). In addition, between 1947 and 1982, private industries leased major portions of the plant's facilities to manufacture various insecticides and herbicides. Operable Unit 21 (OU21), the South Tank Farm Plume (STFP), is one of several areas being addressed as part of the Other Contaminated Sources IRA. From 1947 to 1978, STF tanks 464A, 464B, and others were used intermittently to store bicycloheptadiene (BCHPD) and dicyclopentadiene (DCPD) bottoms generated from pesticide manufacturing. A number of U.S. Army investigations have revealed ground water contamination originating from the areas of light nonaqueous phase liquid (LNAPL) located near tank 464A. Recent investigations have shown that the STFP does not pose significant risk to public health or the environment. The ROD addresses interim management of migration of the STFP and is consistent with the Final Response Action. The primary contaminants of concern affecting the ground water are VOCs including benzene, toluene, and xylenes. The selected interim remedial action for the site is included.

  13. Investigation of Phase and Emulsion Behavior, Surfactant Retention and Condensate Recovery for Condensate/Water/Ethanol Mixtures

    SciTech Connect (OSTI)

    Ramanathan Sampath

    2004-03-31

    This semi-annual technical progress report describes work performed at Morehouse College under DOE Grant No. DE-FG26-02NT15447 during the period October 01, 2003 to March 31, 2004 which covers the third six months of the project. Presently work is in progress to characterize phase and emulsion behavior for ethylbenzene/water/ethanol system. Ethylbenzene that has the equivalent carbon number is used as the model condensate. During this reporting period, temperature scans were performed mixing equal volumes of ethylbenzene and 10mM NaCl water with various concentrations of ethanol ranging from 2 to 70 vol%. For the range of temperatures tested (2 to 70 C), results indicate that temperature is invariant and produced a single phase for ethanol concentrations greater than 60 vol%. For ethanol concentrations less than 60 vol%, only two phases were obtained with aqueous rich bottom phase more in volume than that of the ethylbenzene rich top phase. Linear coreflooding experiments were completed by our industrial partner in this project, Surtek, CO, to measure the condensate recovery in flooding processes. It was found about 30% ethylbenzene recovery was obtained by the waterflooding, however, 2wt% ethanol flooding did not produce incremental recovery of the ethylbenzene. Radial coreflooding with ethanol injection prior to water injection is in progress to assess the effectiveness of the surfactant flooding in the recovery of condensate.

  14. Electrolytes for power sources

    DOE Patents [OSTI]

    Doddapaneni, Narayan; Ingersoll, David

    1995-01-01

    Electrolytes for power sources, particularly alkaline and acidic power sources, comprising benzene polysulfonic acids and benzene polyphosphonic acids or salts of such acids.

  15. Electrolytes for power sources

    DOE Patents [OSTI]

    Doddapaneni, N.; Ingersoll, D.

    1995-01-03

    Electrolytes are disclosed for power sources, particularly alkaline and acidic power sources, comprising benzene polysulfonic acids and benzene polyphosphonic acids or salts of such acids. 7 figures.

  16. Metabolic analysis of the soil microbe Dechloromonas aromatica str. RCB: indications of a surprisingly complex life-style and cryptic anaerobic pathways for aromatic degradation

    SciTech Connect (OSTI)

    Salinero, Kennan Kellaris; Keller, Keith; Feil, William S.; Feil, Helene; Trong, Stephan; Di Bartolo, Genevieve; Lapidus, Alla

    2008-11-17

    Initial interest in Dechloromonas aromatica strain RCB arose from its ability to anaerobically degrade benzene. It is also able to reduce perchlorate and oxidize chlorobenzoate, toluene, and xylene, creating interest in using this organism for bioremediation. Little physiological data has been published for this microbe. It is considered to be a free-living organism. The a priori prediction that the D. aromatica genome would contain previously characterized 'central' enzymes involved in anaerobic aromatic degradation proved to be false, suggesting the presence of novel anaerobic aromatic degradation pathways in this species. These missing pathways include the benzyl succinyl synthase (bssABC) genes (responsible for formate addition to toluene) and the central benzoylCoA pathway for monoaromatics. In depth analyses using existing TIGRfam, COG, and InterPro models, and the creation of de novo HMM models, indicate a highly complex lifestyle with a large number of environmental sensors and signaling pathways, including a relatively large number of GGDEF domain signal receptors and multiple quorum sensors. A number of proteins indicate interactions with an as yet unknown host, as indicated by the presence of predicted cell host remodeling enzymes, effector enzymes, hemolysin-like proteins, adhesins, NO reductase, and both type III and type VI secretory complexes. Evidence of biofilm formation including a proposed exopolysaccharide complex with the somewhat rare exosortase (epsH), is also present. Annotation described in this paper also reveals evidence for several metabolic pathways that have yet to be observed experimentally, including a sulphur oxidation (soxFCDYZAXB) gene cluster, Calvin cycle enzymes, and nitrogen fixation (including RubisCo, ribulose-phosphate 3-epimerase, and nif gene families, respectively). Analysis of the D. aromatica genome indicates there is much to be learned regarding the metabolic capabilities, and life-style, for this microbial species

  17. Synthesis of the Stereoisomeric Clusters 1,2-Os3(CO)10(trans-dpmn) and 1,2-Os3(CO)10(cis-dpmn) [where dpmn = 2,3-bis(diphenylphosphinomethyl)-5-norbornene]: DFT Evaluation of the Isomeric Clusters 1,2-Os3(CO)10(dpmn) and Isomer-Dependent Diphosphine Ligand Activation

    SciTech Connect (OSTI)

    Yang, Li; Nesterov, Vladimir N.; Wang, Xiaoping; Richmond, Michael G.

    2014-07-23

    The bicyclic diphosphines trans- and cis-2,3-bis(diphenylphosphinomethyl)-5-norbornene (dpmn) react with 1,2-Os3(CO)10(MeCN)2 (1) to furnish the corresponding ligand-bridged clusters Os3(CO)10(trans-dpmn) (2) and Os3(CO)10(cis-dpmn) (3). Both new products have been isolated and the molecular structures established by X-ray diffraction analyses. The dihydroxyl-bridged cluster 1,2-Os3(CO)8(μ-OH)2(cis-dpmn) (4), which accompanied the formation of 3 in one reaction, has been isolated and characterized by mass spectrometry and X-ray crystallography. Whereas cluster 2 is stable in toluene at 373 K, 3 is thermally sensitive under identical conditions and undergoes loss of CO (2 equiv), coupled with the activation of three norbornene C-H bonds and one P-C(phenyl) bond, to furnish the dihydride cluster H2Os3(CO)83-2-PhPC-3-endo-Ph2PCH2(C7H7)] (5). The solid-state structure of 5 confirms the multiple activation of the cis-dpmn ligand and accompanying formation of the face-capping 2-PhPC-3-endo-Ph2PCH2(C7H7) moiety in the product. DFT calculations on 2 and 3 indicate that the former cluster is the thermodynamically more stable isomer, and the conversion of 3→ 5 + 2CO + benzene is computed to be exergonic by 12.7 kcal/mol and is entropically favored due to the release of the CO and benzene by-products.

  18. Effect of uncertain hydraulic conductivity on the fate and transport of BTEX compounds at a field site

    SciTech Connect (OSTI)

    Lu, Guoping; Zheng, Chunmiao; Wolfsberg, Andrew

    2002-01-05

    A Monte Carlo analysis was conducted to investigate the effect of uncertain hydraulic conductivity on the fate and transport of BTEX compounds (benzene, toluene, ethyl benzene, and xylene) at a field site on Hill Air Force Base, Utah. Microbially mediated BTEX degradation has occurred at the site through multiple terminal electron-accepting processes, including aerobic respiration, denitrification, Fe(III) reduction, sulfate reduction, and methanogenesis degradation. Multiple realizations of the hydraulic conductivity field were generated and substituted into a multispecies reactive transport model developed and calibrated for the Hill AFB site in a previous study. Simulation results show that the calculated total BTEX masses (released from a constant-concentration source) that remain in the aquifer at the end of the simulation period statistically follow a lognormal distribution. In the first analysis (base case), the calculated total BTEX mass varies from a minimum of 12% less and a maximum of 60% more than that of the previously calibrated model. This suggests that the uncertainty in hydraulic conductivity can lead to significant uncertainties in modeling the fate and transport of BTEX. Geometric analyses of calculated plume configurations show that a higher BTEX mass is associated with wider lateral spreading, while a lower mass is associated with longer longitudinal extension. More BTEX mass in the aquifer causes either a large depletion of dissolved oxygen (DO) and NO{sub 3}{sup -}, or a large depletion of DO and a large production of Fe{sup 2+}, with moderately depleted NO{sub 3}{sup -}. In an additional analysis, the effect of varying degrees of aquifer heterogeneity and associated uncertainty is examined by considering hydraulic conductivity with different variances and correlation lengths. An increase in variance leads to a higher average BTEX mass in the aquifer, while an increase in correlation length results in a lower average. This observation is

  19. SALTSTONE VAULT CLASSIFICATION SAMPLES MODULAR CAUSTIC SIDE SOLVENT EXTRACTION UNIT/ACTINIDE REMOVAL PROCESS WASTE STREAM APRIL 2011

    SciTech Connect (OSTI)

    Eibling, R.

    2011-09-28

    Savannah River National Laboratory (SRNL) was asked to prepare saltstone from samples of Tank 50H obtained by SRNL on April 5, 2011 (Tank 50H sampling occurred on April 4, 2011) during 2QCY11 to determine the non-hazardous nature of the grout and for additional vault classification analyses. The samples were cured and shipped to Babcock & Wilcox Technical Services Group-Radioisotope and Analytical Chemistry Laboratory (B&W TSG-RACL) to perform the Toxic Characteristic Leaching Procedure (TCLP) and subsequent extract analysis on saltstone samples for the analytes required for the quarterly analysis saltstone sample. In addition to the eight toxic metals - arsenic, barium, cadmium, chromium, mercury, lead, selenium and silver - analytes included the underlying hazardous constituents (UHC) antimony, beryllium, nickel, and thallium which could not be eliminated from analysis by process knowledge. Additional inorganic species determined by B&W TSG-RACL include aluminum, boron, chloride, cobalt, copper, fluoride, iron, lithium, manganese, molybdenum, nitrate/nitrite as Nitrogen, strontium, sulfate, uranium, and zinc and the following radionuclides: gross alpha, gross beta/gamma, 3H, 60Co, 90Sr, 99Tc, 106Ru, 106Rh, 125Sb, 137Cs, 137mBa, 154Eu, 238Pu, 239/240Pu, 241Pu, 241Am, 242Cm, and 243/244Cm. B&W TSG-RACL provided subsamples to GEL Laboratories, LLC for analysis for the VOCs benzene, toluene, and 1-butanol. GEL also determines phenol (total) and the following radionuclides: 147Pm, 226Ra and 228Ra. Preparation of the 2QCY11 saltstone samples for the quarterly analysis and for vault classification purposes and the subsequent TCLP analyses of these samples showed that: (1) The saltstone waste form disposed of in the Saltstone Disposal Facility in 2QCY11 was not characteristically hazardous for toxicity. (2) The concentrations of the eight RCRA metals and UHCs identified as possible in the saltstone waste form were present at levels below the UTS. (3) Most of the

  20. TREATMENT OF PRODUCED OIL AND GAS WATERS WITH SURFACTANT-MODIFIED ZEOLITE

    SciTech Connect (OSTI)

    Lynn E. Katz; R.S. Bowman; E.J. Sullivan

    2003-11-01

    Co-produced water from the oil and gas industry accounts for a significant waste stream in the United States. It is by some estimates the largest single waste stream in the country, aside from nonhazardous industrial wastes. Characteristics of produced water include high total dissolved solids content, dissolved organic constituents such as benzene and toluene, an oil and grease component, and chemicals added during the oil-production process. While most of the produced water is disposed via reinjection, some must be treated to remove organic constituents before the water is discharged. Current treatment options are successful in reducing the organic content; however, they cannot always meet the levels of current or proposed regulations for discharged water. Therefore, an efficient, cost-effective treatment technology is needed. Surfactant-modified zeolite (SMZ) has been used successfully to treat contaminated ground water for organic and inorganic constituents. In addition, the low cost of natural zeolites makes their use attractive in water-treatment applications. This report summarizes the work and results of this four-year project. We tested the effectiveness of surfactant-modified zeolite (SMZ) for removal of BTEX with batch and column experiments using waters with BTEX concentrations that are comparable to those of produced waters. The data from our experimental investigations showed that BTEX sorption to SMZ can be described by a linear isotherm model, and competitive effects between compounds were not significant. The SMZ can be readily regenerated using air stripping. We field-tested a prototype SMZ-based water treatment system at produced water treatment facilities and found that the SMZ successfully removes BTEX from produced waters as predicted by laboratory studies. When compared to other existing treatment technologies, the cost of the SMZ system is very competitive. Furthermore, the SMZ system is relatively compact, does not require the storage of

  1. Synthesis metal nanoparticle

    DOE Patents [OSTI]

    Bunge, Scott D.; Boyle, Timothy J.

    2005-08-16

    A method for providing an anhydrous route for the synthesis of amine capped coinage-metal (copper, silver, and gold) nanoparticles (NPs) using the coinage-metal mesityl (mesityl=C.sub.6 H.sub.2 (CH.sub.3).sub.3 -2,4,6) derivatives. In this method, a solution of (Cu(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5, (Ag(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.4, or (Au(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5 is dissolved in a coordinating solvent, such as a primary, secondary, or tertiary amine; primary, secondary, or tertiary phosphine, or alkyl thiol, to produce a mesityl precursor solution. This solution is subsequently injected into an organic solvent that is heated to a temperature greater than approximately 100.degree. C. After washing with an organic solvent, such as an alcohol (including methanol, ethanol, propanol, and higher molecular-weight alcohols), oxide free coinage NP are prepared that could be extracted with a solvent, such as an aromatic solvent (including, for example, toluene, benzene, and pyridine) or an alkane (including, for example, pentane, hexane, and heptane). Characterization by UV-Vis spectroscopy and transmission electron microscopy showed that the NPs were approximately 9.2.+-.2.3 nm in size for Cu.degree., (no surface oxide present), approximately 8.5.+-.1.1 nm Ag.degree. spheres, and approximately 8-80 nm for Au.degree..

  2. Remediation of a Classified Waste Landfill at Sandia National Laboratories, NM

    SciTech Connect (OSTI)

    Ward, D.C.

    1998-10-20

    The Sandia National Laboratory es/New Mexico (SNLiNM) Environmental Restoration Project is currently excavating the Classified Waste Landfill in Technical Area II (TA-H), which consists of disposal pits and trenches with discrete disposal cells. TA-11 is a secure, controlled assess, research facility managed by SNIJNM for the US Department of Energy (DOE). The 45-acre facility was established in 1948 for the assembly and maintenance of nuclear weapons. The assembly of weapons was discontinued in 1954. Since that time, TA-11 has been used primarily for explosive research and testing. Beginning is 1984, the DOE Er,vironmental Restoration Program conducted several environmental investigations across TA-11 and SNMNM. These investigations identified sites requiring firther study and possible corrective action. The majority of these sites were grouped into operable units (OUS). The TA-11 OU included 13 sites, one of which is identified as the Classified Waste Landfill (CWLF). The CWLF covers about 2.5 acres and was operated from approximately 1947 through 1987. It was the site for disposal of classified weapon components, s ome of which are potentially explosive, hazardous, ardor radioactively contarninatod. Until about 1958, no records were maintained for material disposed of in the CWLF. Information on the CWLF has been assembled horn interview notes, delivery to reckmation records and other sources. Items disposed of included security containers, hoppers, skids, missiles, wooden boxes, deactivated heat sources, tntium boosters, scintillation cocktails, weapons cases, shells, lasers, radar equipment and accountable mata-ials. Potential contaminants include tritium, thorium, cesium-137, strontium-90, uraniun, plutonium, beryllium, cadmium, lithium, chloroform, toluene, benzene ad other solvents.

  3. Non-Aqueous Phase Liquid Calculator

    Energy Science and Technology Software Center (OSTI)

    2004-02-19

    Non-Aqueous Phase Liquid or "NPAL" is a term that most environmental professionals are familiar with because NAPL has been recognized in the literature as a significant source of groundwater contamination. There are two types of NAPL: DNAPL and LNAPL. DNAPL is a ‘dense’ non-aqueous phase liquid. In this context, dense means having a density greater than water (1.0 kg/L). Trichloroethylene (TCE) and tetrachioroethylene (PCE) are examples of DNAPL compounds. A compound that is heaver thanmore » water means this type of NAPL will sink in an aquifer. Conversely, LNAPL is a ‘light’ non-aqueous phase liquid with a density less than water, and will float on top of the aquifer. Examples of LNAPL’s are benzene and toluene. LNAPL or DNAPL often manifest as a complex, multi-component mixture of organic compounds that can occur in environmental media. Complex multi-component mixtures distributed in soil pore-air, pore-water, soil particles and in free phase complicate residual saturation of single and multi component NAPL compounds in soil samples. The model output also includes estimates of the NAPL mass and volume and other physical and chemical properties that may be useful for characterization, modeling, and remedial system design and operation. The discovery of NAPL in the aquifer usually leads to a focused characterization for possible sources of NAPL in the vadose zone using a variety of innovative technologies and characterization methods. Often, the analytical data will indicated the presence of NAPL, yet, the NAPL will go unrecognized. Failure to recognize the NAPL can be attributed to the complicated processes of inter-media transfer or a general lack of knowledge about the physical characteristics of complex organic mixtures in environmental samples.« less

  4. Compounds for neutron radiation detectors and systems thereof

    DOE Patents [OSTI]

    Payne, Stephen A; Stoeffl, Wolfgang; Zaitseva, Natalia P; Cherepy, Nerine J; Carman, M. Leslie

    2014-05-27

    A material according to one embodiment exhibits an optical response signature for neutrons that is different than an optical response signature for gamma rays, said material exhibiting performance comparable to or superior to stilbene in terms of distinguishing neutrons from gamma rays, wherein the material is not stilbene, the material comprising a molecule selected from a group consisting of: two or more benzene rings, one or more benzene rings with a carboxylic acid group, one or more benzene rings with at least one double bound adjacent to said benzene ring, and one or more benzene rings for which at least one atom in the benzene ring is not carbon.

  5. "Title","Creator/Author","Publication Date","OSTI Identifier...

    Office of Scientific and Technical Information (OSTI)

    BENZENE; LEUKEMOGENESIS; GEOTHERMAL INDUSTRY; ENVIRONMENTAL IMPACTS; HEALTH HAZARDS; HYDROGEN SULFIDES; BIOLOGICAL EFFECTS; MERCURY; RADON; SULFATES; ACCIDENTS; AIR POLLUTION;...

  6. TITLE AUTHORS SUBJECT SUBJECT RELATED DESCRIPTION PUBLISHER AVAILABILI...

    Office of Scientific and Technical Information (OSTI)

    BENZENE LEUKEMOGENESIS GEOTHERMAL INDUSTRY ENVIRONMENTAL IMPACTS HEALTH HAZARDS HYDROGEN SULFIDES BIOLOGICAL EFFECTS MERCURY RADON SULFATES ACCIDENTS AIR POLLUTION...

  7. Layton, D.W.; Anspaugh, L.R.; O'Banion, K.D. 15 GEOTHERMAL ENERGY...

    Office of Scientific and Technical Information (OSTI)

    BENZENE; LEUKEMOGENESIS; GEOTHERMAL INDUSTRY; ENVIRONMENTAL IMPACTS; HEALTH HAZARDS; HYDROGEN SULFIDES; BIOLOGICAL EFFECTS; MERCURY; RADON; SULFATES; ACCIDENTS; AIR POLLUTION;...

  8. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... less Full Text Available April 2008 , Health Physics http:www.ncbi.nlm.nih.govpubmed18332729 Evaluation of a Polyvinyl Toluene Neutron Counter Array Robert Hayes The ...

  9. DE-FE0000833

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Toluene 56. Diesel Range Organic C10-C28 57. Ethane 58. Formaldehyde 59. Methane 60. Methanol 61. Alkalinity, Carbonate 62. Alkalinity, Hydroxide 63. Alkalinity, Phenolphthalein...

  10. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    States) Fernald Environmental Management Project, OH (United States) FluxNet General ... backbone was varied from 8 to 85. The global conformation of the polymers in toluene ...